TWI825956B - Preparation method of ultra-low dielectric loss spherical silica powder - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 76
- 239000000843 powder Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 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
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 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
- 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
- -1 carbon alkane 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
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 101100447665 Mus musculus Gas2 gene Proteins 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000945 filler Substances 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 230000001934 delay Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental 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
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
本發明公開了一種超低介電損耗球形二氧化矽微粉的製備方法。所述方法通過將球形二氧化矽微粉在氧化劑的氛圍中高溫處理，除去水分和碳以及金屬等雜質，然後直接進入非極性氣體環境下冷卻至室溫，最後充惰性氣體包裝。本發明方法能夠有效降低球形二氧化矽微粉的介電損耗，介電損耗降低率達30%以上，最高可達67%，且產品品質穩定可控。The invention discloses a preparation method of ultra-low dielectric loss spherical silicon dioxide powder. The method involves treating spherical silica micropowder at high temperature in an oxidant atmosphere to remove impurities such as moisture, carbon, and metals, then directly entering it into a non-polar gas environment and cooling it to room temperature, and finally filling it with inert gas for packaging. The method of the invention can effectively reduce the dielectric loss of spherical silica powder, the dielectric loss reduction rate reaches more than 30%, up to 67%, and the product quality is stable and controllable.
Description
本發明屬於高性能填料的製備技術領域，涉及一種超低介電損耗球形二氧化矽微粉的製備方法。 The invention belongs to the technical field of preparation of high-performance fillers and relates to a preparation method of ultra-low dielectric loss spherical silicon dioxide powder.
第五代移動通信系統(5G)作為4G的延伸技術，在大幅提升移動互聯網業務體驗的同時，全面支持物聯網業務，實現人與人、人與物、物與物之間的海量智能互聯。這需要更高的資料傳輸速率、更低的資料傳輸延時以及更好的高速通信能力。材料的損耗角正切值(以下稱為介電損耗，Df)越低，功率損耗就越低。因此低介電損耗Df印製電路板才能滿足5G傳輸時更低的訊號損失。氧化矽作為印製電路板中的重要填料，需要滿足以下要求：一是可實現填料高填充；二是降低氧化矽本身的Df值。氧化矽本身的Df值受到其純度的影響，如雜質元素的含量，如Fe/C等，也受到極性分子，如水分/羥基等。如何進一步降低氧化矽的Df值，成為了當前的研究熱點。 As an extension technology of 4G, the fifth generation mobile communication system (5G) not only greatly improves the mobile Internet business experience, but also fully supports the Internet of Things business and realizes massive intelligent interconnection between people, people and things, and things and things. This requires higher data transmission rates, lower data transmission delays and better high-speed communication capabilities. The lower the material's loss tangent (hereinafter referred to as dielectric loss, Df), the lower the power loss. Therefore, low dielectric loss Df printed circuit boards can meet the lower signal loss during 5G transmission. As an important filler in printed circuit boards, silicon oxide needs to meet the following requirements: first, it can achieve high filler filling; second, it can reduce the Df value of silicon oxide itself. The Df value of silicon oxide itself is affected by its purity, such as the content of impurity elements, such as Fe/C, etc., and also by polar molecules, such as moisture/hydroxyl groups, etc. How to further reduce the Df value of silicon oxide has become a current research hotspot.
中國專利申請CN 113614036 A採用將球狀二氧化矽粉末在500~1100℃下加熱，控制圓度在0.85以上以及表面處理和防潮袋保存的方式實現球狀二氧化矽粉末介電損耗角正切的降低。中國專利申請CN1123996A利用聚有機矽氧烷化合物對金屬氧化物 粒子材料進行表面處理，降低其Df值。中國專利申請CN 110938238 A採用對二氧化矽粒子材料在200℃除去水分後，利用矽烷化合物進行表面處理，降低其Df值。上述方法均是先除去材料中的水分，然後使用矽烷化合物進行表面處理，降低材料的介電損耗正切值，存在如下不足：表面改性劑類型選擇不當，工藝處理不當，會導致後續存儲和使用過程中材料重新吸附水分，或表面處理過程中吸附部分水分，造成介電損耗降低波動大，品質不穩定，達不到預期效果。 Chinese patent application CN 113614036 A achieves the dielectric loss tangent of spherical silica powder by heating it at 500~1100°C, controlling the roundness to be above 0.85, surface treatment and storing it in a moisture-proof bag. reduce. Chinese patent application CN1123996A utilizes polyorganosiloxane compounds to treat metal oxides The particle material undergoes surface treatment to reduce its Df value. Chinese patent application CN 110938238 A uses silica particle materials to remove moisture at 200°C, and then uses silane compounds for surface treatment to reduce its Df value. The above methods all first remove the moisture in the material, and then use silane compounds for surface treatment to reduce the dielectric loss tangent value of the material. There are the following shortcomings: improper selection of surface modifier types and improper process processing will lead to subsequent storage and use. During the process, the material re-adsorbs moisture, or part of the moisture is absorbed during the surface treatment process, resulting in large fluctuations in dielectric loss reduction, unstable quality, and failure to achieve the expected results.
中國專利申請CN 113666380 A通過納米水性二氧化矽溶膠溶液與晶種的混合溶液中添加阻隔劑，以水熱反應的方法獲取附著有阻隔劑的二氧化矽粉體，然後通過煆燒工藝製備球形二氧化矽粉體，在保證成球率的同時有效提升產量，製備的球形二氧化矽在介電損耗與細微性分佈窄具有一定的特點。中國專利申請CN 112745529 A也採用控制比表面積範圍窄的方式來改善介電性能。上述方法主要是通過控制窄的粉體的細微性分佈，從而降低介電損耗正切值，但存在以下不足：介電損耗正切值降低的幅度有限，細微性分佈窄對高填充應用不利，從而增加了應用時級配難度，限制其在電子封裝領域的應用。 Chinese patent application CN 113666380 A adds a blocking agent to the mixed solution of nano-aqueous silica sol solution and crystal seeds, obtains silica powder with blocking agent attached by a hydrothermal reaction method, and then prepares spherical shapes through a calcination process Silica powder can effectively increase the yield while ensuring the spherical rate. The prepared spherical silica has certain characteristics in dielectric loss and narrow fineness distribution. Chinese patent application CN 112745529 A also uses a narrow specific surface area control method to improve dielectric properties. The above method mainly reduces the dielectric loss tangent value by controlling the narrow powder fineness distribution, but has the following shortcomings: the range of reduction of the dielectric loss tangent value is limited, and the narrow fineness distribution is unfavorable for high filling applications, thus increasing the This reduces the difficulty of grading during application and limits its application in the field of electronic packaging.
鑒於上述問題，本發明提供一種超低介電損耗球形二氧化矽微粉的製備方法。該方法通過將球形二氧化矽微粉在氧化劑的氛圍中高溫處理，除去水分和碳以及金屬等雜質，然後直接 進入非極性氣體環境下冷卻至室溫，最後充惰性氣體包裝，有效降低其介電損耗，產品品質穩定可控。 In view of the above problems, the present invention provides a method for preparing ultra-low dielectric loss spherical silicon dioxide powder. This method treats spherical silica fine powder at high temperature in an oxidant atmosphere to remove impurities such as moisture, carbon and metal, and then directly It is cooled to room temperature in a non-polar gas environment, and finally filled with inert gas for packaging, which effectively reduces its dielectric loss and ensures stable and controllable product quality.
本發明的技術方案如下：超低介電損耗球形二氧化矽微粉的製備方法，包括以下步驟：步驟1，在乾燥的氧化劑的環境下，將球形二氧化矽微粉先在150~300℃下處理3~24h，再在800~1200℃下處理24~90h，所述的氧化劑選自氧氣或臭氧；步驟2，將步驟1處理後的球形二氧化矽微粉在非極性氣體氛圍下冷卻至室溫；步驟3，將冷卻後的二氧化矽微粉充惰性氣體包裝。 The technical solution of the present invention is as follows: a method for preparing ultra-low dielectric loss spherical silica powder, including the following steps: Step 1, in a dry oxidant environment, first process the spherical silica powder at 150~300°C 3~24h, and then treat at 800~1200°C for 24~90h, the oxidant is selected from oxygen or ozone; step 2, cool the spherical silica powder treated in step 1 to room temperature in a non-polar gas atmosphere ; Step 3, fill the cooled silica powder with inert gas and pack it.
步驟1中，球形二氧化矽微粉的中位粒徑D50為0.1~150μm，球形度>0.99。 In step 1, the median particle size D50 of the spherical silica powder is 0.1~150 μm, and the sphericity is >0.99.
步驟1中，球形二氧化矽微粉採用現有方法製備，例如採用火焰成球法，具體步驟如下：以純度99.9%以上、金屬氧化物總含量在100ppm以下的二氧化矽粉末或矽溶膠為原料，以氧氣作為載氣，1~5個碳的烷烴或H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃的火焰高溫下，粉末經過高溫融化、冷卻成球，形成球形二氧化矽微粉。 In step 1, spherical silica powder is prepared using existing methods, such as flame spherification. The specific steps are as follows: using silica powder or silica sol with a purity of more than 99.9% and a total metal oxide content of less than 100 ppm as raw material, Using oxygen as the carrier gas, 1 to 5 carbon alkanes or H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel and ignited. Under the flame high temperature of 2400 to 3200°C, the powder is melted and cooled at high temperature to form balls to form spherical silica powder.
優選地，步驟1中，球形二氧化矽微粉先在250~300℃下處理10~24h，再在1100~1200℃下處理48~90h。 Preferably, in step 1, the spherical silica micropowder is first treated at 250~300°C for 10~24h, and then at 1100~1200°C for 48~90h.
優選地，步驟2中，非極性氣體選自氬氣、氦氣、氖氣、氮氣、氧氣或二氧化碳。 Preferably, in step 2, the non-polar gas is selected from argon, helium, neon, nitrogen, oxygen or carbon dioxide.
優選地，步驟2中，室溫為10~30℃。 Preferably, in step 2, the room temperature is 10~30°C.
優選地，步驟3中，惰性氣體選自氮氣、氬氣、氦氣或氖氣。 Preferably, in step 3, the inert gas is selected from nitrogen, argon, helium or neon.
本發明從兩個角度出發，實現二氧化矽微粉超低介電損耗。一是去除微粉中的無機碳和金屬，由於無機碳和金屬都會影響二氧化矽微粉的Df，本發明先是在氧化劑的環境下，通過高溫條件下與碳的反應，去除導電材質的無機碳；同時與微粉引入的金屬(如Fe)反應生成金屬氧化物，去除一部分的金屬。二是去除微粉中的極性分子如結合水等，採用分段加熱的方法，先在較低溫度下去除微粉結合水，避免直接升至高溫，造成微粉間的團聚。 The present invention starts from two perspectives to achieve ultra-low dielectric loss of silicon dioxide powder. The first is to remove inorganic carbon and metals in the micropowder. Since inorganic carbon and metals will affect the Df of the silica micropowder, the present invention first removes the inorganic carbon of the conductive material through the reaction with carbon under high temperature conditions in an oxidant environment; At the same time, it reacts with the metal (such as Fe) introduced by the micron powder to generate metal oxide, removing part of the metal. The second is to remove polar molecules such as bound water in the micropowder, using a segmented heating method to first remove the bound water of the micropowder at a lower temperature to avoid directly rising to high temperatures, causing agglomeration between the micropowders.
與現有技術相比，本發明具有以下優點：本發明選擇超高純原料，通過火焰法製備比表面積相對小、球形度高的球形二氧化矽微粉，在氧化劑的氛圍中高溫處理除去水分、金屬和碳，直接進入非極性氣體環境下冷卻至室溫，充惰性氣體包裝，相關工序在惰性氣體保護下進行。本發明製備的產品品質穩定，介電損耗降低率30%以上，最高可達67%。 Compared with the existing technology, the present invention has the following advantages: the present invention selects ultra-high purity raw materials, prepares spherical silica powder with a relatively small specific surface area and high sphericity through flame method, and removes moisture and metals by high-temperature treatment in an oxidant atmosphere. and carbon, directly enter the non-polar gas environment, cool to room temperature, fill with inert gas and package, and the relevant processes are carried out under the protection of inert gas. The quality of the product prepared by the invention is stable, and the dielectric loss reduction rate is more than 30%, up to 67%.
下面結合具體實施例對本發明作進一步詳述。下述實施例中採用的原料或試劑均可商業購買獲得。 The present invention will be further described in detail below in conjunction with specific embodiments. The raw materials or reagents used in the following examples are all commercially available.
實施例1 Example 1
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A依次在200℃處理3h和1100℃處理48h，製得球形二氧化矽微粉B。在非極性氣體氬氣的環境2下冷卻10h至室溫。充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性2.5μm，比表面積3.6m2/g，球形度0.993。 In a dry oxygen environment 1, spherical silica fine powder A was treated at 200°C for 3 hours and 1100°C for 48 hours to prepare spherical silica powder B. Cool to room temperature for 10 h in an environment of non-polar argon gas 2. After being sealed and packed with nitrogen, spherical silica micropowder C was obtained, with an average fineness of 2.5 μm, a specific surface area of 3.6 m 2 /g, and a sphericity of 0.993.
實施例2 Example 2
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A依次在150℃處理10h和800℃處理60h，製得球形二氧化矽微粉B。在非極性氣體氮氣的環境2下冷卻10h至室溫，充氮氣密封包裝，製得球 形二氧化矽微粉C，平均細微性2.2μm，比表面積3.8m2/g，球形度0.995。 In a dry oxygen environment 1, spherical silica fine powder A was treated at 150°C for 10 hours and 800°C for 60 hours to prepare spherical silica powder B. Cool to room temperature for 10 hours in an environment of non-polar nitrogen gas 2, then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 2.2 μm, a specific surface area of 3.8 m 2 /g, and a sphericity of 0.995.
實施例3 Example 3
以平均粒徑8μm、純度99.95%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 8 μm and a purity of 99.95% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A依次在300℃處理24h和1200℃處理90h，製得球形二氧化矽微粉B。在非極性氣體氬氣的環境2下冷卻10h至室溫，充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性9.2μm，比表面積0.86m2/g，球形度0.991。 In a dry oxygen environment 1, spherical silica fine powder A was treated at 300°C for 24 hours and 1200°C for 90 hours to prepare spherical silica powder B. Cool to room temperature for 10 hours in an environment of non-polar argon gas2, then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 9.2 μm, a specific surface area of 0.86 m 2 /g, and a sphericity of 0.991.
實施例4 Example 4
以平均粒徑35μm、純度99.90%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 35 μm and a purity of 99.90% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A依次在250℃處理24h和900℃處理24h，製得球形二氧化矽微粉B。在非極性氣體氮氣的環境2下冷卻10h至室溫，充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性39μm，比表面積0.36m2/g，球形度0.992。 In a dry oxygen environment 1, spherical silica fine powder A was treated at 250°C for 24 hours and 900°C for 24 hours to prepare spherical silica powder B. Cool to room temperature for 10 hours in an environment of non-polar nitrogen gas 2, then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 39 μm, a specific surface area of 0.36 m 2 /g, and a sphericity of 0.992.
對比例1 Comparative example 1
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。球形二氧化矽微粉A不經過處理，直接與聚乙烯樹脂形成固化物，測試介電損耗。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A. Spherical silica micropowder A is directly combined with polyethylene resin to form a cured product without treatment, and the dielectric loss is tested.
對比例2 Comparative example 2
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
敞口條件下，球形二氧化矽微粉A依次在200℃處理3h和1100℃處理48h，製得球形二氧化矽微粉B。在敞口條件下冷卻10h至室溫，充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性2.4μm，比表面積3.7m2/g，球形度0.994。 Under open conditions, spherical silica powder A was treated at 200°C for 3 hours and 1100°C for 48 hours to prepare spherical silica powder B. Cool to room temperature for 10 hours under open conditions, seal and package with nitrogen, and obtain spherical silica powder C with an average fineness of 2.4 μm, a specific surface area of 3.7 m 2 /g, and a sphericity of 0.994.
對比例3 Comparative example 3
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A依次在200℃處理3h和400℃處理48h，製得球形二氧化矽微粉B。在非極性氣體氬氣的環境2冷卻10h至室溫，充氮氣密封包裝，製得球形 二氧化矽微粉C，平均細微性2.4μm，比表面積3.8m2/g，球形度0.993。 In a dry oxygen environment 1, spherical silica fine powder A was treated at 200°C for 3 hours and 400°C for 48 hours to prepare spherical silica powder B. Cool to room temperature for 10 hours in a non-polar argon gas environment, and then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 2.4 μm, a specific surface area of 3.8 m 2 /g, and a sphericity of 0.993.
對比例4 Comparative example 4
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境下，球形二氧化矽微粉A依次在200℃處理3h和1500℃處理96h，製得球形二氧化矽微粉B，粉體團聚為塊料，由於高溫段溫度過高，溫度超過粉體熔點，粉體融化成塊。 In a dry oxygen environment, spherical silica powder A was treated at 200°C for 3 hours and 1500°C for 96 hours to obtain spherical silica powder B. The powder was agglomerated into lumps. Because the temperature in the high-temperature section was too high, the temperature exceeded The melting point of the powder, the powder melts into blocks.
對比例5 Comparative example 5
以平均粒徑8μm、純度99.95%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 8 μm and a purity of 99.95% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥的氧氣環境1下，球形二氧化矽微粉A直接在1200℃下處理90h，製得球形二氧化矽微粉B。在非極性氣體氬氣的環境2下冷卻10h至室溫，充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性15.6μm，細微性分佈有拖尾，說明直接升至高溫，容易造成微粉間的團聚。 In a dry oxygen environment 1, spherical silica fine powder A is directly treated at 1200°C for 90 hours to prepare spherical silica fine powder B. Cool to room temperature for 10 hours in an environment of non-polar argon gas2, then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 15.6 μm and a tail in the fineness distribution, indicating that it is easy to rise directly to high temperature. Causes agglomeration between micro-powders.
對比例6 Comparative example 6
以平均粒徑2μm、純度99.92%的角形二氧化矽微粉為原料，以氧氣作為載氣，H2作為可燃氣體，氧氣為助燃劑，分別導入反應容器中，點燃，在2400~3200℃高溫熔融成球，製得球形二氧化矽微粉A。 Using angular silica micropowder with an average particle size of 2 μm and a purity of 99.92% as the raw material, using oxygen as the carrier gas, H 2 as the combustible gas, and oxygen as the combustion accelerant, they are introduced into the reaction vessel respectively, ignited, and melted at a high temperature of 2400~3200°C. Form into balls to obtain spherical silica fine powder A.
在乾燥氬氣環境下，球形二氧化矽微粉A依次在200℃處理3h和在乾燥的氬氣環境1下1100℃處理48h，製得球形二氧化矽微粉B。在非極性氣體氬氣的環境2下冷卻10h至室溫，充氮氣密封包裝，製得球形二氧化矽微粉C，平均細微性2.6μm，比表面積3.5m2/g，球形度0.993。 In a dry argon atmosphere, spherical silica fine powder A was treated at 200°C for 3 hours and then at 1100°C for 48 hours in a dry argon atmosphere to prepare spherical silica fine powder B. Cool to room temperature for 10 hours in an environment of non-polar argon gas2, then seal and package with nitrogen to obtain spherical silica powder C with an average fineness of 2.6 μm, a specific surface area of 3.5 m 2 /g, and a sphericity of 0.993.
相對於對比例1(未處理)，實施例1~4分別通過兩步熱處理、不同粒徑、不同環境，降低了球形二氧化矽微粉中的極性分子和異物(如C和Fe)，從而降低了Df。當熱處理2的溫度較高(1200℃)時和處理時間較長，環境1為氧氣的前提下，金屬異物和碳含量最低，相應的Df也是最低的，降低幅度67%。對比例2不用環境保護，直接在敞口條件下進行熱處理，金屬個數偏多，同時在冷卻的過程吸附水分，造成Df降低幅度只有22%。對比例3和對比例6分別控制熱處理2的溫度過低和環境1調整為氬氣，對異物的減少程度不夠，因此Df下降不明顯。對比例4和對比例5分別控制熱處理2的溫度過高(1500℃)和去掉熱處理1，直接高溫，都會造成粉體團聚成大顆粒或塊料。 Compared with Comparative Example 1 (untreated), Examples 1 to 4 respectively reduced the polar molecules and foreign matter (such as C and Fe) in the spherical silica powder through two-step heat treatment, different particle sizes, and different environments, thereby reducing Df. When the temperature of heat treatment 2 is higher (1200°C) and the treatment time is longer, and the environment 1 is oxygen, the metal foreign matter and carbon content are the lowest, and the corresponding Df is also the lowest, with a reduction of 67%. Comparative Example 2 does not require environmental protection and directly performs heat treatment under open conditions. The number of metals is too large. At the same time, water is absorbed during the cooling process, resulting in a Df reduction of only 22%. Comparative Examples 3 and 6 respectively controlled the temperature of heat treatment 2 to be too low and the environment 1 to be adjusted to argon. The degree of reduction of foreign matter was not enough, so the decrease in Df was not obvious. Comparative Examples 4 and 5 respectively control the temperature of heat treatment 2 to be too high (1500°C) and remove heat treatment 1. Direct high temperature will cause the powder to agglomerate into large particles or lumps.
表1揭露各實施例和對比例的實驗條件以及製得的球形二氧化矽微粉C的性能 Table 1 discloses the experimental conditions of each embodiment and comparative example and the properties of the prepared spherical silica fine powder C
表1。
無。without.
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