CN114702038A - Preparation method of spherical silicon dioxide micropowder with ultralow dielectric loss - Google Patents
Preparation method of spherical silicon dioxide micropowder with ultralow dielectric loss Download PDFInfo
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- CN114702038A CN114702038A CN202210442307.1A CN202210442307A CN114702038A CN 114702038 A CN114702038 A CN 114702038A CN 202210442307 A CN202210442307 A CN 202210442307A CN 114702038 A CN114702038 A CN 114702038A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 82
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 39
- 229910052760 oxygen Inorganic materials 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000005563 spheronization Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- -1 silane compound Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a preparation method of spherical silicon dioxide micro powder with ultralow dielectric loss. The method comprises the steps of carrying out high-temperature treatment on spherical silicon dioxide micropowder in an oxidant atmosphere to remove moisture, carbon, metal and other impurities, then directly entering a nonpolar gas atmosphere to cool to room temperature, and finally filling inert gas for packaging. The method can effectively reduce the dielectric loss of the spherical silicon dioxide micropowder, the dielectric loss reduction rate is more than 30 percent and can reach 67 percent at most, and the product quality is stable and controllable.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance fillers, and relates to a preparation method of spherical silicon dioxide micropowder with ultralow dielectric loss.
Background
The fifth generation mobile communication system (5G) is used as an extension technology of 4G, so that the mobile internet service experience is greatly improved, meanwhile, the internet-of-things service is comprehensively supported, and massive intelligent interconnection among people, objects and things is realized. This requires higher data transmission rates, lower data transmission delays, and better high-speed communication capabilities. The lower the loss tangent (hereinafter referred to as dielectric loss, Df) of the material, the lower the power loss. Therefore, the low dielectric loss Df PCB can satisfy the lower signal loss in 5G transmission. Silicon oxide, as an important filler in printed circuit boards, needs to meet the following requirements: firstly, high filling of the filler can be realized; the second is to reduce the Df value of the silicon oxide itself. The Df value of the silica itself is affected by its purity, e.g., the content of impurity elements such as Fe/C, etc., and also by polar molecules such as moisture/hydroxyl, etc. How to further reduce the Df value of silicon oxide becomes a hot point of current research.
The Chinese patent application CN 113614036A realizes the reduction of the dielectric loss tangent of spherical silicon dioxide powder by heating the spherical silicon dioxide powder at 500-1100 ℃, controlling the roundness to be more than 0.85 and carrying out surface treatment and moisture-proof bag storage. Chinese patent application CN1123996A uses polyorganosiloxane compound to perform surface treatment on metal oxide particle material to reduce the Df value. Chinese patent application CN 110938238A adopts silica particle material to remove moisture at 200 ℃, and then surface treatment is performed with silane compound to reduce the Df value. In all of the above methods, the moisture in the material is removed, and then the surface treatment is performed by using the silane compound, so as to reduce the dielectric loss tangent value of the material, and the following disadvantages exist: improper selection of the type of the surface modifier and improper process treatment can cause the material to adsorb moisture again in the subsequent storage and use processes or adsorb partial moisture in the surface treatment process, thereby causing large fluctuation of dielectric loss reduction and unstable quality, and failing to achieve the expected effect.
The Chinese patent application CN 113666380A adds the blocking agent into the mixed solution of the nano water-based silica sol solution and the crystal seed, obtains the silica powder attached with the blocking agent by a hydrothermal reaction method, and then prepares the spherical silica powder by a calcination process, thereby effectively improving the yield while ensuring the balling rate, and the prepared spherical silica has certain characteristics of narrow dielectric loss and particle size distribution. Chinese patent application CN 112745529 a also adopts a narrow range of specific surface area to improve dielectric properties. The above method is mainly to reduce the dielectric loss tangent value by controlling the particle size distribution of the narrow powder, but has the following disadvantages: the dielectric loss tangent value is reduced in a limited range, and the narrow particle size distribution is unfavorable for high filling application, so that the grading difficulty in application is increased, and the application of the high filling material in the field of electronic packaging is limited.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing a spherical fine silica powder with ultra-low dielectric loss. According to the method, the spherical silicon dioxide micro powder is subjected to high-temperature treatment in the atmosphere of an oxidant to remove moisture, carbon, metal and other impurities, then the spherical silicon dioxide micro powder is directly put into the atmosphere of nonpolar gas to be cooled to room temperature, and finally the spherical silicon dioxide micro powder is filled with inert gas for packaging, so that the dielectric loss of the spherical silicon dioxide micro powder is effectively reduced, and the product quality is stable and controllable.
The technical scheme of the invention is as follows:
the preparation method of the spherical silicon dioxide micropowder with ultralow dielectric loss comprises the following steps:
step 1, treating spherical silicon dioxide micro powder for 3-24 hours at 150-300 ℃ in a dry oxidant atmosphere, and then treating for 24-90 hours at 800-1200 ℃, wherein the oxidant is selected from oxygen, oxygen-enriched air or ozone;
step 2, cooling the spherical silicon dioxide micro powder treated in the step 1 to room temperature in a non-polar gas atmosphere;
and 3, filling inert gas into the cooled silicon dioxide micro powder for packaging.
In the step 1, the median particle diameter D50 of the spherical silicon dioxide micropowder is 0.1-150 μm, and the sphericity is more than 0.99.
In the step 1, the spherical silica micropowder is prepared by the existing method, for example, a flame balling method, and the method comprises the following specific steps:
using silicon dioxide powder or silica sol with the purity of more than 99.9 percent and the total content of metal oxides of less than 100ppm as a raw material, using oxygen as a carrier gas, and using alkane or H with 1-5 carbon atoms2And as combustible gas, oxygen is taken as a combustion improver, the oxygen is respectively introduced into the reaction containers, the ignition is carried out, and the powder is melted at high temperature and cooled into spheres at the flame high temperature of 2400-3200 ℃ to form spherical silicon dioxide micro powder.
Preferably, in the step 1, the spherical silicon dioxide micro powder is firstly treated at 250-300 ℃ for 10-24 h and then treated at 1100-1200 ℃ for 48-90 h.
In step 2, the non-polar gas is selected from argon, helium, neon, nitrogen, oxygen or carbon dioxide.
In the step 2, the room temperature is 10-30 ℃.
In step 3, the inert gas is selected from nitrogen, argon, helium or neon.
The invention realizes the ultralow dielectric loss of the silicon dioxide micropowder from two angles. Firstly, removing inorganic carbon and metal in the micro powder, wherein the inorganic carbon and the metal can influence Df of the silicon dioxide micro powder, and the inorganic carbon of a conductive material is removed by reacting with carbon at a high temperature in the atmosphere of an oxidant; and simultaneously reacts with the metal (such as Fe) introduced by the micro powder to generate metal oxide, and a part of the metal is removed. And secondly, polar molecules such as bound water and the like in the micro powder are removed, the micro powder bound water is removed at a lower temperature by adopting a sectional heating method, and agglomeration among the micro powder caused by direct heating to a high temperature is avoided.
Compared with the prior art, the invention has the following advantages:
the method selects ultra-pure raw materials, prepares spherical silicon dioxide micropowder with relatively small specific surface area and high sphericity by a flame method, removes moisture, metal and carbon by high-temperature treatment in an oxidant atmosphere, directly enters a nonpolar gas atmosphere, cools to room temperature, fills inert gas for packaging, and performs related procedures under the protection of the inert gas. The product prepared by the invention has stable quality, and the dielectric loss reduction rate is more than 30 percent and can reach 67 percent at most.
Detailed Description
The present invention will be described in more detail with reference to specific examples. The starting materials or reagents used in the following examples are commercially available.
Example 1
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2As combustible gas, oxygen is taken as combustion improver, is respectively led into the reaction containers and is ignited, and the temperature is 2400-3200And (3) melting at high temperature to form spheres to obtain the spherical silicon dioxide micropowder A.
Under the dry oxygen atmosphere 1, the spherical silicon dioxide micro powder A is treated for 3 hours at 200 ℃ and for 48 hours at 1100 ℃ in sequence to prepare the spherical silicon dioxide micro powder B. The mixture was cooled for 10h to room temperature under an atmosphere of nonpolar argon 2. Filling nitrogen and hermetically packaging to obtain spherical silicon dioxide micropowder C with average particle size of 2.5 μm and specific surface area of 3.6m2G, sphericity 0.993.
Example 2
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
In a dry oxygen atmosphere 1, the spherical silicon dioxide micro powder A is sequentially treated for 10 hours at 150 ℃ and 60 hours at 800 ℃ to prepare the spherical silicon dioxide micro powder B. Cooling for 10h to room temperature in the atmosphere of nonpolar gas nitrogen 2, charging nitrogen, hermetically sealing and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 2.2 μm and specific surface area of 3.8m2G, sphericity 0.995.
Example 3
Using angular silica micropowder with average particle diameter of 8 μm and purity of 99.95% as raw material, oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
In a dry oxygen atmosphere 1, the spherical silicon dioxide micro powder A is sequentially treated for 24 hours at 300 ℃ and 90 hours at 1200 ℃ to prepare the spherical silicon dioxide micro powder B. Cooling for 10h to room temperature under the atmosphere of nonpolar argon gas 2, charging nitrogen gas, sealing, and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 9.2 μm and specific surface area of 0.86m2G, sphericity 0.991.
Example 4
Using angular silicon dioxide micropowder with average particle size of 35 μm and purity of 99.90% as raw material, using oxygen as carrier gas, and H2As combustible gas, oxygenThe materials are combustion-supporting agents and are respectively led into a reaction container, ignited and melted into balls at the high temperature of 2400-3200 ℃, and the spherical silicon dioxide micro powder A is prepared.
Under the dry oxygen-enriched air atmosphere 1, the spherical silicon dioxide micro powder A is sequentially treated for 24 hours at 250 ℃ and 24 hours at 900 ℃ to prepare the spherical silicon dioxide micro powder B. Cooling in nonpolar gas nitrogen atmosphere 2 for 10 hr to room temperature, charging nitrogen gas, sealing, and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 39 μm and specific surface area of 0.36m2(g), sphericity 0.992.
Comparative example 1
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A. The spherical silica micropowder A directly forms a condensate with polyethylene resin without treatment, and the dielectric loss is tested.
Comparative example 2
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
Under the open condition, the spherical silicon dioxide micro powder A is sequentially treated for 3h at 200 ℃ and 48h at 1100 ℃ to prepare the spherical silicon dioxide micro powder B. Cooling for 10h to room temperature under open condition, charging nitrogen gas, hermetically sealing and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 2.4 μm and specific surface area of 3.7m2G, sphericity 0.994.
Comparative example 3
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
Under a dry oxygen atmosphere 1, spherical silicaThe micro powder A is treated for 3 hours at 200 ℃ and 48 hours at 400 ℃ in sequence to prepare spherical silicon dioxide micro powder B. Cooling in nonpolar argon gas atmosphere 2 for 10h to room temperature, charging nitrogen gas, sealing, and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 2.4 μm and specific surface area of 3.8m2(g), sphericity 0.993.
Comparative example 4
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
Under the dry oxygen atmosphere, the spherical silicon dioxide micro powder A is sequentially treated for 3 hours at 200 ℃ and 96 hours at 1500 ℃ to prepare the spherical silicon dioxide micro powder B, the powder is agglomerated into lump materials, and the powder is melted into lumps due to the fact that the temperature of a high-temperature section is too high and exceeds the melting point of the powder.
Comparative example 5
Using angular silica micropowder with average particle diameter of 8 μm and purity of 99.95% as raw material, oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
Under the dry oxygen atmosphere 1, the spherical silicon dioxide micro powder A is directly treated for 90 hours at 1200 ℃ to prepare the spherical silicon dioxide micro powder B. Cooling for 10h to room temperature in the atmosphere of non-polar gas argon 2, filling nitrogen, sealing and packaging to obtain the spherical silicon dioxide micro powder C with the average particle size of 15.6 mu m and trailing particle size distribution, which indicates that the micro powder is directly heated to high temperature and is easy to cause agglomeration among micro powders.
Comparative example 6
Using angular silicon dioxide micropowder with average particle diameter of 2 μm and purity of 99.92% as raw material, using oxygen as carrier gas, and H2And respectively introducing oxygen as a combustion improver into the reaction container as combustible gas, igniting, and melting at 2400-3200 ℃ to form spheres to obtain the spherical silicon dioxide micropowder A.
Under the dry argon atmosphere, the spherical silicon dioxide micro powderAnd sequentially treating the A at 200 ℃ for 3h and at 1100 ℃ for 48h in a dry argon atmosphere of 1 to obtain the spherical silicon dioxide micro powder B. Cooling for 10h to room temperature under the atmosphere of nonpolar argon gas 2, filling nitrogen gas, sealing and packaging to obtain spherical silicon dioxide micropowder C with average particle size of 2.6 μm and specific surface area of 3.5m2(g), sphericity 0.993.
Compared with the comparative example 1 (untreated), examples 1 to 4 respectively reduce polar molecules and foreign matters (such as C and Fe) in the spherical fine silica powder through two-step heat treatment, different particle sizes and different atmospheres, thereby reducing Df. When the temperature of the heat treatment 2 is higher (1200 ℃) and the treatment time is longer, under the premise that the atmosphere 1 is oxygen, the content of metal foreign matters and carbon is the lowest, the corresponding Df is also the lowest, and the reduction amplitude is 67%. Comparative example 2 without atmosphere protection, the heat treatment was directly performed under the open condition, the number of metals was large, and at the same time, moisture was adsorbed during the cooling process, resulting in a Df reduction of only 22%. Comparative example 3 and comparative example 6, in which the temperature of the heat treatment 2 was controlled to be too low and the atmosphere 1 was adjusted to argon, respectively, the degree of reduction of foreign matters was insufficient, and thus the Df was not significantly decreased. Comparative example 4 and comparative example 5, respectively, controlling the temperature of the heat treatment 2 to be too high (1500 ℃) and removing the heat treatment 1 to directly obtain high temperature can cause the powder to agglomerate into large particles or blocks.
Claims (7)
1. The preparation method of the spherical silicon dioxide micropowder with ultralow dielectric loss is characterized by comprising the following steps:
step 1, treating spherical silicon dioxide micro powder for 3-24 hours at 150-300 ℃ in a dry oxidant atmosphere, and then treating for 24-90 hours at 800-1200 ℃, wherein the oxidant is selected from oxygen, oxygen-enriched air or ozone;
step 2, cooling the spherical silicon dioxide micro powder treated in the step 1 to room temperature in a non-polar gas atmosphere;
and 3, filling inert gas into the cooled silicon dioxide micro powder for packaging.
2. The preparation method according to claim 1, wherein in the step 1, the median particle diameter D50 of the spherical fine silica powder is 0.1-150 μm, and the sphericity is more than 0.99.
3. The preparation method according to claim 1, wherein in the step 1, the spherical silica micropowder is prepared by a flame spheronization method, and the preparation method comprises the following specific steps:
using silicon dioxide powder or silica sol with the purity of more than 99.9 percent and the total content of metal oxides of less than 100ppm as a raw material, using oxygen as a carrier gas, and using alkane or H with 1-5 carbon atoms2And as combustible gas, oxygen is taken as a combustion improver, the oxygen is respectively introduced into the reaction containers, the ignition is carried out, and the powder is melted at high temperature and cooled into spheres at the flame high temperature of 2400-3200 ℃ to form spherical silicon dioxide micro powder.
4. The preparation method according to claim 1, wherein in the step 1, the spherical fine silica powder is treated at 250 to 300 ℃ for 10 to 24 hours and then at 1100 to 1200 ℃ for 48 to 90 hours.
5. The method according to claim 1, wherein in the step 2, the nonpolar gas is selected from the group consisting of argon, helium, neon, nitrogen, oxygen, and carbon dioxide.
6. The method according to claim 1, wherein the room temperature in step 2 is 10 to 30 ℃.
7. The method according to claim 1, wherein in the step 3, the inert gas is selected from nitrogen, argon, helium or neon.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210442307.1A CN114702038B (en) | 2022-04-25 | 2022-04-25 | Preparation method of spherical silicon dioxide micro powder with ultralow dielectric loss |
| KR1020237025831A KR20230153999A (en) | 2022-04-25 | 2022-08-29 | Method for producing ultra-low dielectric loss spherical silica fine powder |
| PCT/CN2022/115380 WO2023206886A1 (en) | 2022-04-25 | 2022-08-29 | Method for preparing spherical silicon dioxide micro powder with ultra-low dielectric loss |
| TW111132564A TWI825956B (en) | 2022-04-25 | 2022-08-29 | Preparation method of ultra-low dielectric loss spherical silica powder |
| DE112022000095.3T DE112022000095T5 (en) | 2022-04-25 | 2022-08-29 | Preparation method for ultra-low dielectric loss spherical silica micropowder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023206886A1 (en) * | 2022-04-25 | 2023-11-02 | 江苏联瑞新材料股份有限公司 | Method for preparing spherical silicon dioxide micro powder with ultra-low dielectric loss |
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| KR20230153999A (en) | 2023-11-07 |
| DE112022000095T5 (en) | 2024-04-25 |
| TW202342371A (en) | 2023-11-01 |
| TWI825956B (en) | 2023-12-11 |
| CN114702038B (en) | 2023-09-29 |
| WO2023206886A1 (en) | 2023-11-02 |
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