CN113213968B - Micron-sized metastable phase epsilon-Fe 2 O 3 Preparation method of (1) - Google Patents

Micron-sized metastable phase epsilon-Fe 2 O 3 Preparation method of (1) Download PDF

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CN113213968B
CN113213968B CN202110444244.9A CN202110444244A CN113213968B CN 113213968 B CN113213968 B CN 113213968B CN 202110444244 A CN202110444244 A CN 202110444244A CN 113213968 B CN113213968 B CN 113213968B
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glaze
sized
micron
raw materials
metastable phase
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CN113213968A (en
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王甜
梁家祥
王芬
朱建锋
张佩
施佩
任肇
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention discloses a micron-sized metastable phase epsilon-Fe 2 O 3 Belonging to the technical field of inorganic nonmetallic materials. Crushing the raw materials to prepare glaze slip; applying the glaze slip on the biscuit for glazing treatment and then drying to prepare a blank containing a glaze layer; sintering the blank containing the glaze layer at high temperature and then cooling to obtain a product mixture; etching the product mixture, and collecting a solid product; washing and drying the solid product to obtain a target product; wherein, the raw materials comprise the following components: feldspar, quartz, calcite, talc, kaolin and an iron source, wherein the iron source comprises at least one of purple sandy soil, ferroferric oxide and ferric oxide. The invention can stably synthesize and obtain the particles with uniform size and distribution, and has the advantages of simple process, low cost, nontoxic raw materials and mild preparation conditions.

Description

Micron-sized metastable phase epsilon-Fe 2 O 3 Preparation method of (1)
Technical Field
The invention belongs to the technical field of inorganic non-metallic materials, and relates to micron-sized metastable phase epsilon-Fe 2 O 3 The preparation method of (1).
Background
High-purity epsilon-Fe in ancient porcelain temmoku glaze 2 O 3 Has attracted high attention of ancient ceramic and modern material researchers. Relating to epsilon-Fe in glaze 2 O 3 The study on the chemical composition and microstructure of the devitrified layer shows that ferrous iron is more than ferric iron in the glaze, the sintering atmosphere is presumed to be partial reduction, and unmelted crystals (anorthite and mullite) exist to promote epsilon-Fe 2 O 3 And proposes a polycrystalline branch of epsilon-Fe 2 O 3 The growth process of (2) is as follows: nucleation → with four main branchesTwo-dimensional dendritic structure → epitaxial growth of multiple auxiliary branches → polycrystalline branch dendritic structure. epsilon-Fe 2 O 3 The crystal is a rare iron oxide crystal, has larger coercive force (room temperature of 45k Oe) and excellent magnetoelectric coupling performance, and is considered to have great application potential in the field of ultrahigh density storage. To date, ε -Fe 2 O 3 The material is mainly made of Fe 3 O 4 →ε-Fe 2 O 3 Or gamma-Fe 2 O 3 →ε-Fe 2 O 3 →α-Fe 2 O 3 Phase transition, wet process, but the product is only nano-sized and contains other types of iron oxide impurities. Meanwhile, the prior studies have been on ε -Fe 2 O 3 The preparation process of (2) often has the production defects of poor structural stability, difficult pure phase preparation, complex preparation process and high energy consumption, so that the preparation process cannot be applied to expanded production. Thus how to prepare stable and uniformly sized epsilon-Fe 2 O 3 Materials remain a problem to be solved in this field.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a micron-sized metastable phase epsilon-Fe 2 O 3 The preparation method solves the existing preparation of epsilon-Fe 2 O 3 The product has the problems of more impurities and uneven size distribution.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a micron-sized metastable phase epsilon-Fe 2 O 3 The preparation method comprises the steps of crushing the raw materials to prepare glaze slurry; applying the obtained glaze slip on a biscuit for glazing treatment and then drying to obtain a blank containing a glaze layer; sintering the obtained blank containing the glaze layer at high temperature and then cooling to obtain a product mixture; etching the obtained product mixture, and collecting a solid product; washing and drying the obtained solid product to obtain micron-sized metastable phase epsilon-Fe 2 O 3 (ii) a Wherein, the raw materials comprise the following components: feldspar, quartz, calcite, talcum and iron source, wherein the iron source comprises purple sand, kaolin, ferroferric oxide and ferric oxideAt least one of (1).
Preferably, the feedstock also comprises alumina.
Further preferably, the raw materials comprise the following components in percentage by mass: 7 to 24 percent of feldspar, 14.6 to 50 percent of quartz, 3.8 to 5 percent of calcite, 1.6 to 5 percent of talcum, 0 to 15 percent of aluminum oxide, 0 to 73 percent of purple sandy soil, 0 to 2 percent of kaolin, 0 to 5 percent of ferric oxide and 0 to 5 percent of ferroferric oxide; wherein the mass of the purple sandy soil, the kaolin, the ferroferric oxide and the ferric oxide is not 0 at the same time.
Preferably, the operation of preparing the glaze slurry by crushing the raw materials comprises the following steps: uniformly mixing all components in the raw materials, adding the mixture into water, and carrying out ball milling to prepare glaze slurry; wherein the volume ratio of the raw materials to the water is 1:0.8 to 1.
Further preferably, al is used 2 O 3 Ball milling with ball mill, raw material and Al 2 O 3 The volume ratio of the ball grinding stone is 1:2.
further preferably, the ball milling rotating speed is 300-350 r/min, and the ball milling time is 30-45 min.
Preferably, glazing treatment is carried out by adopting a glaze dipping method or a glaze dropping method; in the obtained blank containing the glaze layer, the thickness of the glaze layer is 1.5-2 mm.
Preferably, the high-temperature sintering adopts multi-stage heating, and the specific operating parameters thereof comprise: raising the temperature to 400-450 ℃ at a heating rate of 3-5 ℃/min, raising the temperature to 1100-1150 ℃ at a heating rate of 3 ℃/min, raising the temperature to 1280-1300 ℃ at a heating rate of 1 ℃/min, and finally preserving the heat for 2-3 h at the temperature of 1280-1300 ℃.
Preferably, the resulting product mixture is etched with sodium hydroxide solution to remove impurities.
Further preferably, the concentration of the sodium hydroxide solution is 4mol · L -1 The etching time is 2-3 h.
Preferably, the operation of washing and drying includes: washing with water for 3-5 times, and drying at 60-65 deg.C.
Preferably, the resulting micro-scale metastable phase ε -Fe 2 O 3 Has a particle diameter of 10 to 20 μm。
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a micron-sized metastable phase epsilon-Fe 2 O 3 The preparation method of (1) can effectively reduce the impurity content in the product by adding different iron sources into the raw materials for sintering and etching treatment; feldspar, quartz, calcite and talc are used as glaze making base materials, an iron source is added for high-temperature sintering, impurities in products are removed through etching, and a complex separation and impurity removal process can be avoided. In addition, the iron source in the raw materials selected by the invention can be purple sandy soil, ferroferric oxide or ferric oxide, and the cost investment of the preparation method can be effectively reduced. Therefore, the preparation method of the invention is adopted to stably synthesize the epsilon-Fe 2 O 3 Metastable phase, micron-sized metastable phase epsilon-Fe with uniform size distribution 2 O 3 The preparation method has the advantages of simple process, low cost, nontoxic raw materials, mild preparation conditions and the like, and is suitable for industrial large-scale production and application.
Further, the Al/Si ratio in the reaction can be adjusted by adding aluminum oxide into the raw material, so that the generation of SiO impurity is reduced 2 The amount of (c).
Furthermore, by adjusting the amount of water, the ball milling time and the thickness of the glaze layer, the components in the mixed glaze slip can be uniformly distributed, so that the sintering reaction is thorough, and the impurity types of the obtained product are reduced.
Furthermore, stable single metastable phase epsilon-Fe can be ensured to be obtained by multi-section temperature rise heating 2 O 3 。
Further, the main impurity phase SiO in the product is removed by etching reaction with sodium hydroxide alkali solution 2 In a specific embodiment of the invention, a single stable, metastable, micron-sized phase of ε -Fe is obtained 2 O 3 As shown in fig. 3. The impurity phase can be reacted away by adjusting the etching time. The invention prepares single uniform metastable phase epsilon-Fe by a fused silicate-alkali etching method through reducing the generation of impurity phases and processing the unreacted impurity phases 2 O 3 。
Drawings
FIG. 1 is a graph of the micron-sized metastable phase ε -Fe prepared by the present invention 2 O 3 The super depth of field map of (1);
FIG. 2 is a graph of the micron-sized metastable phase ε -Fe prepared by the present invention 2 O 3 A Raman graph of (a);
FIG. 3 is a graph of the micron-sized metastable phase ε -Fe prepared by the present invention 2 O 3 SEM image of (d).
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is further illustrated by the following specific examples.
Example one
1. Preparing glaze: the preparation method comprises the following steps of (1) mixing the required raw materials (the raw materials comprise the following components in percentage by mass:7% of feldspar, 14.6% of quartz, 3.8% of calcite, 1.6% of talcum and 73% of purple clay) according to the proportion, adding Al 2 O 3 Ball millstone and water in a ratio of 1:2:1 putting the mixture into a planetary ball mill to ball mill for 30min at the speed of 350r/min to prepare glaze slip.
2. Glazing: and (3) applying the glaze on the biscuit by a glaze dipping method or a glaze dropping method, repeatedly applying the glaze to enable the thickness of the glaze to reach about 2mm, and naturally drying.
3. And (3) sintering: and (3) putting the dried sample into a muffle furnace for high-temperature sintering, heating to 450 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1150 ℃ at a heating rate of 3 ℃/min, then heating to 1300 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and naturally cooling along with the furnace to obtain the sample.
4. Etching: the cooled sample was added to a sodium hydroxide solution (4 mol. L) -1 ) Etching for 3h, washing the etched sample for 5 times by deionized water, and finally drying in a vacuum drying oven at 60 ℃ to obtain the final sample. Namely obtaining the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 20 μm.
Example two
1. Preparing glaze: weighing and mixing required raw materials (the raw materials comprise 24% of feldspar, 50% of quartz, 4% of calcite, 4% of talcum, 2% of kaolin, 11% of aluminum oxide and 5% of ferric oxide) according to a certain proportion, adding Al 2 O 3 Ball millstone and water in a ratio of 1:2:0.8 putting the mixture into a planetary ball mill to ball mill for 30min at the speed of 300r/min to prepare glaze slip.
2. Glazing: applying the glaze on the biscuit by a glaze dipping method or a glaze dropping method, repeatedly applying the glaze to enable the thickness of the glaze to reach about 1.5mm, and naturally drying.
3. And (3) sintering: and (3) putting the dried sample into a muffle furnace for high-temperature sintering, heating to 450 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1150 ℃ at a heating rate of 3 ℃/min, then heating to 1300 ℃ at a heating rate of 1 ℃/min, preserving heat for 3h, cooling and naturally cooling to obtain the sample.
4. Etching: adding the cooled sample into sodium hydroxide lye (4 mol. L) -1 ) Etching for 3h, washing the etched sample for 5 times by deionized water, and finally drying in a vacuum drying oven at 60 ℃ to obtain the final sample. Namely obtaining the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 15 μm.
EXAMPLE III
1. Preparing glaze: weighing and mixing the required raw materials (the raw materials comprise 20% of feldspar, 50% of quartz, 5% of calcite, 5% of talcum, 15% of aluminum oxide, 2% of kaolin and 3% of ferric oxide according to mass percentage), adding Al 2 O 3 Ball grindstone, water, raw material, al 2 O 3 The volume ratio of the ball grindstone to the water is 1:2:0.9 putting the mixture into a planetary ball mill to ball mill for 45min at the speed of 320r/min to prepare glaze slip.
2. Glazing: and (3) applying the obtained glaze slip on the biscuit by using a glaze dipping method or a glaze dropping method, repeatedly applying the glaze slip to enable the thickness of the glaze layer to reach 2mm, and naturally drying to obtain the blank containing the glaze layer.
3. And (3) sintering: and (3) putting the dried blank containing the glaze layer into a muffle furnace for high-temperature sintering, heating to 400 ℃ from room temperature at a heating rate of 3 ℃/min, then heating to 1100 ℃ at a heating rate of 3 ℃/min, then heating to 1290 ℃ at a heating rate of 1 ℃/min, preserving heat for 2.5h, cooling and naturally cooling to obtain a product mixture.
4. Etching: the cooled product mixture was added to sodium hydroxide solution (4 mol. L) -1 ) Etching for 2.5h, washing the etched solid product for 3 times by deionized water, and finally drying in a vacuum drying oven at 65 ℃ to obtain a final sample, namely the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 10 μm.
Example four
1. Preparing glaze: mixing the required raw materials (each group of raw materials)Comprises the following components by mass percent: 9% feldspar, 15% quartz, 4% calcite, 2% talc, 70% purple sandy soil) in proportion, adding Al 2 O 3 Ball grindstone, water, raw material, al 2 O 3 The volume ratio of the ball grindstone to the water is 1:2:0.9 putting the mixture into a planetary ball mill to ball mill for 40min at the speed of 320r/min to prepare glaze slip.
2. Glazing: and (3) applying the obtained glaze slip on the biscuit by using a glaze dipping method or a glaze dropping method, repeatedly applying the glaze slip to enable the thickness of the glaze layer to reach 1.7mm, and naturally drying to obtain the blank containing the glaze layer.
3. And (3) sintering: and (3) putting the dried blank containing the glaze layer into a muffle furnace for high-temperature sintering, heating to 430 ℃ from room temperature at a heating rate of 4 ℃/min, then heating to 1120 ℃ at a heating rate of 3 ℃/min, then heating to 1280 ℃ at a heating rate of 1 ℃/min, preserving heat for 2.5h, cooling and naturally cooling to obtain a product mixture.
4. Etching: the cooled product mixture was added to sodium hydroxide solution (4 mol. L) -1 ) Etching for 2.5h, washing the etched solid product for 4 times by deionized water, and finally drying in a vacuum drying oven at 62 ℃ to obtain a final sample, namely the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 18 μm.
EXAMPLE five
1. Preparing glaze: weighing and mixing the required raw materials (the raw materials comprise 21% of feldspar, 50% of quartz, 5% of calcite, 5% of talcum, 13% of aluminum oxide, 1% of kaolin and 5% of ferric oxide according to mass percentage), adding Al 2 O 3 Ball grindstone, water, raw material, al 2 O 3 The volume ratio of the ball grindstone to the water is 1:2:0.85 is put into a planetary ball mill to be ball-milled for 35min at the speed of 330r/min, and glaze slip is prepared.
2. Glazing: and (3) applying the obtained glaze slip on the biscuit by using a glaze dipping method or a glaze dropping method, repeatedly applying the glaze slip to enable the thickness of the glaze layer to reach 1.9mm, and naturally drying to obtain the blank containing the glaze layer.
3. And (3) sintering: and (3) putting the dried blank containing the glaze layer into a muffle furnace for high-temperature sintering, heating to 440 ℃ from room temperature at a heating rate of 4 ℃/min, then heating to 1130 ℃ at a heating rate of 3 ℃/min, then heating to 1285 ℃ at a heating rate of 1 ℃/min, preserving heat for 2.5h, cooling and naturally cooling to obtain a product mixture.
4. Etching: the cooled product mixture was added to sodium hydroxide solution (4 mol. L) -1 ) Etching for 2h, washing the etched solid product for 4 times by deionized water, and finally drying in a vacuum drying oven at 64 ℃ to obtain a final sample, namely the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 20 μm.
EXAMPLE six
1. Preparing glaze: weighing and mixing the required raw materials (the raw materials comprise 24% of feldspar, 50% of quartz, 4% of calcite, 4% of talcum, 11% of aluminum oxide, 2% of kaolin and 5% of ferroferric oxide in percentage by mass), adding Al 2 O 3 Ball grindstone, water, raw material, al 2 O 3 The volume ratio of the ball grindstone to the water is 1:2:1, putting the mixture into a planetary ball mill, and ball-milling the mixture for 38min at the speed of 340r/min to prepare glaze slip.
2. Glazing: and (3) applying the obtained glaze slip on the biscuit by using a glaze dipping method or a glaze dropping method, repeatedly applying the glaze slip to enable the thickness of the glaze layer to reach 1.5mm, and naturally drying to obtain the blank containing the glaze layer.
3. And (3) sintering: and (3) putting the dried blank containing the glaze layer into a muffle furnace for high-temperature sintering, heating to 400 ℃ from room temperature at a heating rate of 4 ℃/min, then heating to 1140 ℃ at a heating rate of 3 ℃/min, then heating to 1280 ℃ at a heating rate of 1 ℃/min, preserving heat for 2.5h, cooling and naturally cooling to obtain a product mixture.
4. Etching: the cooled product mixture was added to sodium hydroxide solution (4 mol. L) -1 ) Etching for 2h, washing the etched solid product for 3 times by deionized water, finally drying in a vacuum drying oven at 65 ℃ to obtain a final sample,namely obtaining the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 10 μm.
EXAMPLE seven
1. Preparing glaze: weighing and mixing the required raw materials (the raw materials comprise 20% of feldspar, 50% of quartz, 5% of calcite, 5% of talcum, 15% of aluminum oxide, 2% of kaolin and 3% of ferroferric oxide in percentage by mass), adding Al 2 O 3 Ball grindstone, water, raw material, al 2 O 3 The volume ratio of the ball grindstone to the water is 1:2:0.8, putting the mixture into a planetary ball mill, and ball-milling the mixture for 43min at the speed of 300r/min to prepare glaze slip.
2. Glazing: and (3) applying the obtained glaze slip on the biscuit by using a glaze dipping method or a glaze dropping method, repeatedly applying the glaze slip to enable the thickness of the glaze layer to reach 1.7mm, and naturally drying to obtain the blank containing the glaze layer.
3. And (3) sintering: and (3) putting the dried blank containing the glaze layer into a muffle furnace for high-temperature sintering, heating to 400 ℃ from room temperature at a heating rate of 3 ℃/min, then heating to 1100 ℃ at a heating rate of 3 ℃/min, then heating to 1300 ℃ at a heating rate of 1 ℃/min, preserving heat for 3h, cooling and naturally cooling to obtain a product mixture.
4. Etching: the cooled product mixture was added to sodium hydroxide solution (4 mol. L) -1 ) Etching for 2.5h, washing the etched solid product with deionized water for 5 times, and finally drying in a vacuum drying oven at 60 ℃ to obtain a final sample, namely the micron-sized metastable phase epsilon-Fe 2 O 3 。
5. The micron-sized metastable phase epsilon-Fe prepared in the example 2 O 3 The particle size was 12 μm.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, it can be seen that a large number of dendrite precipitations appear on the surface of the sintered sample.
Referring to FIG. 2, it can be seen that by measuring the Raman activity of the devitrification, the peak shown in the figure is exactly the metastable phase ε -Fe 2 O 3 。
Referring to fig. 3, it can be seen that the SEM image of the post-etch sample measured exhibits a single and uniformly distributed dendrite, which corresponds to the super-depth-of-field image of fig. 1.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims (5)

1. Micron-sized metastable phase epsilon-Fe 2 O 3 The preparation method is characterized in that the raw materials are crushed to prepare glaze slip; applying the obtained glaze slurry on a biscuit, glazing, and drying to obtain a blank containing a glaze layer; sintering the obtained blank containing the glaze layer at high temperature and then cooling to obtain a product mixture; etching the obtained product mixture, and collecting a solid product; washing and drying the obtained solid product to obtain micron-sized metastable phase epsilon-Fe 2 O 3 ；
Wherein, the raw materials comprise the following components: feldspar, quartz, calcite, talcum and an iron source, wherein the iron source comprises at least one of purple sandy soil, ferroferric oxide and ferric oxide;
the raw material also comprises aluminum oxide;
the raw materials comprise the following components in percentage by mass: 7% -24% of feldspar, 14.6% -50% of quartz, 3.8% -5% of calcite, 1.6% -5% of talcum, 0% -15% of aluminum oxide, 0% -73% of purple sand, 0% -5% of ferric oxide and 0~5% of ferroferric oxide; wherein the mass of the purple sandy soil, the ferroferric oxide and the ferric oxide is not 0 at the same time;
the high-temperature sintering adopts multi-section heating, and the specific operating parameters comprise:
raising the temperature to 400-450 ℃ at a temperature raising rate of 3~5 ℃/min, raising the temperature to 1100-1150 ℃ at a temperature raising rate of 3 ℃/min, raising the temperature to 1280-1300 ℃ at a temperature raising rate of 1 ℃/min, and finally preserving the heat for 2-3h at a temperature of 1280-1300 ℃;
etching the obtained product mixture by using a sodium hydroxide solution to remove impurities;
the concentration of the sodium hydroxide solution was 4 mol. L -1 The etching time is 2 to 3h.
2. A micron-sized metastable phase e-Fe according to claim 1 2 O 3 The preparation method is characterized in that the operation of preparing the glaze slip by crushing the raw materials comprises the following steps:
uniformly mixing all components in the raw materials, and adding the mixture into water for ball milling to prepare glaze slurry;
wherein the volume ratio of the raw materials to the water is 1:0.8 to 1.
3. A micron-sized metastable phase e-Fe according to claim 2 2 O 3 The preparation method is characterized in that the ball milling rotating speed is 300 to 350r/min, and the ball milling time is 30 to 45min.
4. A micron-sized metastable phase e-Fe according to claim 1 2 O 3 The preparation method is characterized in that a glaze dipping method or a glaze dropping method is adopted for glazing; in the obtained blank containing the glaze layer, the thickness of the glaze layer is 1.5 to 2mm.
5. A micron-sized metastable phase e-Fe according to claim 1 2 O 3 Characterized in that the obtained micron-sized metastable phase epsilon-Fe 2 O 3 The particle diameter of (B) is 10 to 20 μm.
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