Preparation method of low-temperature ball-milling orthorhombic nano-sb2o3

Abstract

The application relates to a low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method, which comprises the following steps: drying micron-level cubic antimony trioxide in a vacuum drying box; adding the dried cubic antimony trioxide into a ball mill tank according to a ball-to-material ratio of 30:1, grinding the ball mill tank at a rotating speed of 580r / min-700r / min and a temperature of-80 DEG C--60 DEG C for 8-10h to obtain milled antimony trioxide; and screening the milled antimony trioxide to obtain orthorhombic nanometer antimony trioxide, wherein the mesh number of the screen is 100-400 meshes; the low-temperature ball milling realizes preparation of the orthorhombic nanometer antimony trioxide, the raw material source is rich, the preparation process is simple, the method has the characteristics of green environmental protection and low cost, is suitable for large-scale production, the obtained product has the advantages of narrow particle size distribution, small average particle size and good dispersity, not only has excellent characteristics of nanometer particles, but also has unique optical characteristics, and effectively meets the application of photosensitive materials and semiconductor materials.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of nanometer antimony trioxide, in particular to a low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method. BACKGROUND

[0002] As an important antimony oxide, antimony trioxide has unique physical and chemical properties and is widely used in the fields of catalysis, flame retardation, semiconductor materials, photosensitive materials, pigments, porcelain, polymers and synthetic rubber. Antimony trioxide is often used as a white pigment, a flame retardant in oil paint, plastic and synthetic rubber, and a catalyst and a decoloring agent in the chemical industry. Antimony trioxide has cubic and orthorhombic crystal forms, and the crystal form structure has an important influence on the performance of antimony trioxide. Generally, antimony trioxide exists in the form of cubic crystal. In recent years, with the development of nanotechnology, orthorhombic nanometer antimony trioxide has attracted much attention in the photosensitive material and semiconductor material industries due to its unique optical properties.

[0003] At present, there are two kinds of methods for preparing nanometer antimony trioxide, namely dry method and wet method, including coprecipitation method, alcohol salt hydrolysis method and gamma ray oxidation method. However, these preparation methods have complex processes, require expensive raw materials for hydrolysis, pollute the environment, and the prepared nanometer antimony trioxide is in the form of cubic crystal structure and does not have nanometer antimony trioxide in the form of orthorhombic crystal structure.

[0004] In order to prepare the orthorhombic crystal structure, a preparation method of orthorhombic nanometer antimony trioxide is disclosed at present. SbCl3 is used as a raw material to prepare granular orthorhombic Sb2O3 nano through a Sb(OH)3-TEA (triethanolamine) precursor. The average particle size of the orthorhombic Sb2O3 nanocrystal prepared after crystallization of the precursor precipitate at 60 DEG C for 4 hours is about 41 nm. However, the preparation method has a complex process, harsh preparation conditions, strict pH value control, involves chemical reactions in the preparation process, seriously pollutes the environment, and cannot be mass-produced.

[0005] Chinese patent CN112678869A discloses a preparation method of spherical antimony trioxide. The invention uses traditional antimony trioxide as a raw material, adds a dispersing agent, performs ultrasonic dispersion, uses a sand mill for fine grinding, filters and dries to prepare antimony trioxide seeds, and then uses a blowing oxygen pipe and a reverberatory furnace in cooperation to obtain spherical antimony trioxide by adjusting the pure oxygen flow rate and the amount of seed addition. The preparation process is complex and requires some special equipment. The crystal form of the obtained nanometer antimony trioxide is uncertain.

[0006] Chinese patent CN105540664B discloses a preparation method of coarse particle, high cubic crystal content of antimony trioxide, which hydrolyzes antimony trichloride aqueous solution, filters to obtain antimony oxychloride, then adjusts pH value to neutralize antimony oxychloride, controls particle size, and obtains coarse particle, high cubic crystal content of antimony trioxide, cubic crystal content of antimony trioxide obtained by the method is greater than or equal to 99.0%, and particle size can be controlled between 5 and 25 microns; the method mainly realizes preparation of cubic crystal antimony trioxide, particle size is in micron level, excellent characteristics of nano particles are not possessed, and batch production is not facilitated.

[0007] Based on the above analysis, the method for preparing orthorhombic crystal structure nano antimony trioxide has harsh preparation conditions, strict pH value control, involves chemical reaction in the preparation process, is seriously harmful to the environment, and cannot be mass produced. SUMMARY

[0008] The purpose of the present application is to provide an efficient preparation method of orthorhombic antimony trioxide nanocrystals, which is based on low-temperature mechanical ball milling, and the obtained orthorhombic nano antimony trioxide has uniform particle size distribution and high purity. The preparation method has the characteristics of simple operation process, rich raw material sources, green environmental protection and low cost, is suitable for large-scale production, and effectively meets the low-temperature ball milling orthorhombic nano antimony trioxide preparation method of photosensitive materials and semiconductor materials.

[0009] To achieve the above purpose, the present application provides a low-temperature ball milling orthorhombic nano antimony trioxide preparation method, which comprises the following steps:

[0010] Step 1. Dry the micron-sized cubic crystal antimony trioxide in a vacuum drying box;

[0011] Step 2. Add the dried cubic crystal antimony trioxide in step 1 into a ball mill jar at a ball-to-material ratio of 30:1, the grinding speed of the ball mill jar is 580 r / min-700 r / min, the temperature is-80℃--60℃, and the grinding time is 8-10 h to obtain ground antimony trioxide;

[0012] Step 3. Screen the ground antimony trioxide to obtain orthorhombic nano antimony trioxide, and the mesh size of the screen is 100-400 mesh.

[0013] Preferably, the average particle size of the cubic crystal antimony trioxide in step 1 is 3 microns.

[0014] Preferably, the drying time in step 1 is 12 h, and the drying temperature is 80℃.

[0015] Preferably, the diameter of the grinding balls in the ball mill jar in step 2 is 6 mm and 3 mm, and the number of 6 mm grinding balls to 3 mm grinding balls is 2:1.

[0016] Preferably, the grinding rotation speed of the ball mill tank in step 2 is 590 r / min, the temperature is -70℃, and the grinding time is 9h.

[0017] Preferably, the rhombic nanometer antimony trioxide obtained in step 3 is sealed in the dark.

[0018] Preferably, the average particle size of the rhombic nanometer antimony trioxide is 35-40nm.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] The present application realizes the preparation of rhombic nanometer antimony trioxide by low-temperature ball milling, the raw material source is abundant, the preparation process is simple, has the characteristics of green environmental protection and low cost, is suitable for large-scale production, the obtained product has narrow particle size distribution, small average particle size and good dispersity, not only has excellent characteristics of nanometer particles, but also has unique optical characteristics, effectively meets the application of photosensitive materials and semiconductor materials, and has important significance for improving the performance of materials; the process is simple, the cost is low, the efficiency is high, the preparation effect is good, and good economic benefits are obtained. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 X-ray diffraction contrast diagram of cubic antimony trioxide and rhombic antimony trioxide prepared in the present application;

[0022] Figure 2 Electron microscope diagram of cubic antimony trioxide;

[0023] Figure 3 Electron microscope diagram of rhombic antimony trioxide prepared in the present application. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in combination with the drawings of the embodiments of the present application. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0025] A low-temperature ball milling rhombic nanometer antimony trioxide preparation method, comprising:

[0026] 120g of micro-sized cubic antimony trioxide with an average particle size of about 3μm is obtained, and the micro-sized cubic antimony trioxide is divided into 4 equal parts, each part being 30g, and each part is marked as A part, B part, C part and D part.

[0027] Example 1

[0028] A low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method comprises the following steps:

[0029] Step 1. A portion of micron-sized cubic antimony trioxide is placed in a vacuum drying oven for drying for 12 hours, and the temperature is set to 80 DEG C to obtain dried micron-sized cubic antimony trioxide;

[0030] Step 2. The dried micron-sized cubic antimony trioxide obtained in step 1 is placed in a 0.5L stainless steel ball mill tank, the grinding balls are stainless steel balls with diameters of 6mm and 3mm, the number of the balls is 2:1, the ball-to-material ratio in each ball mill tank is 30:1, the ball milling is implemented by a planetary ball mill, the ball milling speed is set to 580r / min, the low temperature is obtained by introducing liquid nitrogen, the temperature is controlled to be-60 DEG C, and the ball milling time is more than 10 hours to obtain milled antimony trioxide;

[0031] Step 3. The milled antimony trioxide is screened to obtain orthorhombic nanometer antimony trioxide, and the mesh number of the screen is 100-400 meshes; in this embodiment, a 200-mesh screen is used;

[0032] The obtained orthorhombic nanometer antimony trioxide is stored in a light-proof manner, and the average particle size is about 35nm.

[0033] Embodiment 2

[0034] A low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method comprises the following steps:

[0035] Step 1. A portion of micron-sized cubic antimony trioxide is placed in a vacuum drying oven for drying for 12 hours, and the temperature is set to 80 DEG C to obtain dried micron-sized cubic antimony trioxide;

[0036] Step 2. The dried micron-sized cubic antimony trioxide obtained in step 1 is placed in a 0.5L stainless steel ball mill tank, the grinding balls are stainless steel balls with diameters of 6mm and 3mm, the number of the balls is 2:1, the ball-to-material ratio in each ball mill tank is 30:1, the ball milling is implemented by a planetary ball mill, the ball milling speed is set to 580r / min, the low temperature is obtained by introducing liquid nitrogen, the temperature is controlled to be-60 DEG C, and the ball milling time is more than 10 hours to obtain milled antimony trioxide;

[0037] Step 3. The milled antimony trioxide is screened to obtain orthorhombic nanometer antimony trioxide, and the mesh number of the screen is 100-400 meshes; in this embodiment, a 200-mesh screen is used;

[0038] Embodiment 3

[0039] A low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method comprises the following steps:

[0040] Step 1. C parts of micron-sized cubic antimony trioxide are placed in a vacuum drying box for drying for 12 hours, and the temperature is set to 80 DEG C to obtain dried micron-sized cubic antimony trioxide;

[0041] Step 2. The dried micron-sized cubic antimony trioxide obtained in step 1 is placed in a 0.5L stainless steel ball mill tank, the diameter of the grinding ball is φ6mm and φ3mm, the number of the stainless steel balls is 2:1, the ball-to-material ratio in each ball mill tank is 30:1, the ball milling is implemented by a planetary ball mill, the ball milling speed is set to 600r / min, the low temperature is obtained by introducing liquid nitrogen, the temperature is controlled at-80 DEG C, and the ball milling time is more than 8 hours to obtain milled antimony trioxide;

[0042] Step 3. The milled antimony trioxide is screened to obtain orthorhombic nanometer antimony trioxide, and the mesh number of the screen is 100-400 meshes; in this embodiment, a 400-mesh screen is used; the obtained orthorhombic nanometer antimony trioxide is stored in a light-proof manner, and the average particle size is about 40nm.

[0043] Example 4

[0044] A low-temperature ball-milling orthorhombic nanometer antimony trioxide preparation method comprises the following steps:

[0045] Step 1. D parts of micron-sized cubic antimony trioxide are placed in a vacuum drying box for drying for 12 hours, and the temperature is set to 80 DEG C to obtain dried micron-sized cubic antimony trioxide;

[0046] Step 2. The dried micron-sized cubic antimony trioxide obtained in step 1 is placed in a 0.5L stainless steel ball mill tank, the diameter of the grinding ball is φ6mm and φ3mm, the number of the stainless steel balls is 2:1, the ball-to-material ratio in each ball mill tank is 30:1, the ball milling is implemented by a planetary ball mill, the ball milling speed is set to 600r / min, the low temperature is obtained by introducing liquid nitrogen, the temperature is controlled at-80 DEG C, and the ball milling time is more than 8 hours to obtain milled antimony trioxide;

[0047] Step 3. The milled antimony trioxide is screened to obtain orthorhombic nanometer antimony trioxide, and the mesh number of the screen is 100-400 meshes; in this embodiment, a 400-mesh screen is used; the obtained orthorhombic nanometer antimony trioxide is stored in a light-proof manner, and the average particle size is about 40nm.

[0048] The orthorhombic nanometer antimony trioxide and cubic antimony trioxide prepared in any one of examples 1-4 are selected at random for X-ray diffraction, and the X-ray diffraction patterns are as shown inFigure 1 The X-ray diffraction control chart shown in the figure is completely consistent with the standard PDF #43-1071 card of the cubic crystal antimony trioxide, and 2θ at 13.74°, 27.69°, 32.08°, 35.05°, 46.00°, 54.54° respectively corresponds to (111), (222), (400), (331), (440), (622) crystal face of the cubic crystal antimony trioxide. After being refined by low-temperature ball milling, the cubic crystal antimony trioxide is converted into the rhombic crystal antimony trioxide, which is completely consistent with the standard PDF #11-0689 card, and 2θ at 19.40°, 25.47°, 28.38°, 33.80°, 50.54°, 54.78° respectively corresponds to (110), (111), (121), (012), (161), (170) crystal face of the rhombic crystal antimony trioxide.

[0049] Figure 2 is a transmission electron microscope graph of the cubic crystal antimony trioxide, Figure 3 is a transmission electron microscope graph of the rhombic crystal nano antimony trioxide prepared by any one of examples 1-4, and Figure 2 and Figure 3 The transmission electron microscope graphs of the cubic crystal antimony trioxide and the rhombic crystal nano antimony trioxide can be seen that the raw material selected is the cubic crystal antimony trioxide with an average particle size of about 3 μm, and the particle agglomeration phenomenon is serious. After being refined by low-temperature ball milling, the rhombic crystal antimony trioxide with an average particle size of about 40 nm is obtained, and the dispersion is good.

[0050] The transmission electron microscope graph of the rhombic crystal nano antimony trioxide prepared by the method can be seen that the method can be used to prepare the rhombic crystal antimony trioxide with good dispersion. The method mainly uses low-temperature mechanical ball milling to obtain the rhombic crystal nano antimony trioxide, and the rhombic crystal nano antimony trioxide prepared by the method has uniform particle size distribution and high purity. Meanwhile, the method has the characteristics of simple operation process, rich raw material source, green environmental protection and low cost, and is suitable for large-scale production, and effectively meets the preparation of the rhombic crystal antimony trioxide required by the photosensitive material and the semiconductor material.

[0051] The above examples are only illustrative of the present application, and do not constitute a limitation on the protection scope of the present application. Any design identical or similar to the present application belongs to the protection scope of the present application.

Claims

1. A method for preparing rhombic nanometer-sized antimony trioxide by low-temperature ball milling, characterized in that, The application relates to a preparation method of rhombic crystal type nano antimony trioxide. Step 1: micron-sized cubic crystal type antimony trioxide is dried in a vacuum drying box; Step 2: the dried cubic crystal type antimony trioxide in step 1 is added into a ball mill tank according to a ball-material ratio of 30:1, the grinding rotating speed of the ball mill tank is 580 r / min-700 r / min, the temperature is-80 DEG C--60 DEG C, and the grinding time is 8-10h, so that ground antimony trioxide is obtained; Step 3: the ground antimony trioxide is screened to obtain rhombic crystal type nano antimony trioxide, and the mesh number of the screen is 100-400 meshes.

2. The method according to claim 1, wherein the method is characterized by: The average particle size of the cubic crystal type antimony trioxide in step 1 is 3um.

3. The method according to claim 1, wherein the method is characterized by: The drying time in step 1 is 12h, and the drying temperature is 80 DEG C.

4. The method according to claim 1, wherein the method is characterized by: The diameters of the grinding balls in the ball mill tank in step 2 are 6mm and 3mm, and the number of the 6mm grinding balls is 2 times that of the 3mm grinding balls.

5. The method according to claim 1, wherein the method is characterized by: The grinding rotating speed of the ball mill tank in step 2 is 590 r / min, the temperature is-70 DEG C, and the grinding time is 9h.

6. The method according to claim 1, wherein the method is characterized by, The rhombic crystal type nano antimony trioxide obtained in step 3 is sealed in the dark.

7. The method according to claim 1 or 6, wherein the low-temperature ball milling is used to prepare the orthorhombic nanometer-sized Sb203. The average particle size of the rhombic crystal type nano antimony trioxide is 35-40nm.

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