WO2019027337A1 - Composites de graphène-silice stables et procédé de fabrication associé - Google Patents

Composites de graphène-silice stables et procédé de fabrication associé Download PDF

Info

Publication number
WO2019027337A1
WO2019027337A1 PCT/PL2018/050043 PL2018050043W WO2019027337A1 WO 2019027337 A1 WO2019027337 A1 WO 2019027337A1 PL 2018050043 W PL2018050043 W PL 2018050043W WO 2019027337 A1 WO2019027337 A1 WO 2019027337A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
silica
composite
temperature
flake
Prior art date
Application number
PCT/PL2018/050043
Other languages
English (en)
Inventor
Anna WEDZYNSKA
Yuri GERASYMCHUK
Anna LUKOWIAK
Dariusz HRENIAK
Wieslaw Strek
Original Assignee
Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego filed Critical Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego
Publication of WO2019027337A1 publication Critical patent/WO2019027337A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C01B33/16—Preparation of silica xerogels
    • C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area

Definitions

  • the invention relates to stable graphene-silica composites and the method for manufacturing thereof. More specifically, the invention relates to stable graphene-silica composites, based on expanded graphite oxide and silica or on a silica xerogel and a method for manufacturing thereof.
  • a composite gel is obtained based on graphite oxide with the addition of crosslinking polymer(s) (with those best known being formaldehyde-resorcinol-sodium bicarbonate or polyvinyl alcohol-acrylic acid systems), [M.A. Worsley et al. J. Am. Chem. Soc, 132 (40) (2010) 14067-14069; Ji-Hyun Kim, Young-Seak Lee J. Indust. Engineer. Chem. 30 (2015) 127-133; US patents: 9,437,372; 9,434,620; 9,352,500; 9,012,522], which after drying in the lyophilization process is subjected to pyrolysis at temperatures above 900°C.
  • crosslinking polymer(s) with those best known being formaldehyde-resorcinol-sodium bicarbonate or polyvinyl alcohol-acrylic acid systems
  • porous carbon materials obtained in accordance with the methods disclosed in prior art have significant disadvantages that limit or prevent their use in optics or optoelectronics or in heterogeneous catalysis.
  • the relatively long synthesis duration means that the process of manufacturing thereof is expensive and energy-consuming.
  • the obtained porous carbon/graphene blocks are very light and brittle, which makes it difficult to handle them, for example to place them e.g. in a vacuum chamber; in addition, when a laser beam is directed on such blocks, it results in a partial sublimation of atoms of carbon and the deposition of the latter on the walls of the chamber.
  • the stabilisation of graphene oxide (graphite or graphene oxide) flakes in hybrid materials, hitherto described has been obtained by applying layers of silica onto the flakes or by encapsulating them in a monolithic silica gel.
  • the composite with silica was obtained by way of a colloidal process (mixing the graphene material suspension with a silica suspension) or by milling the graphene suspension with dry silica [H. Porwal et al. In situ reduction of graphene oxide nanoplatelet during spark plasma sintering of a silica matrix composite, J. Eur. Ceram. Soc. 34 (2014) 3357-3364].
  • the object of the invention is therefore to provide a method for the manufacturing of stable graphene-silica composites applicable especially in optics and optoelectronics.
  • the invention relates to a stable graphene-silica composite in the form of a powder or a monolith, characterised in that it consists of a system of graphene flakes and silica, wherein each graphene flake is smaller than 2 ⁇ .
  • the composite preferably is in one of the two forms: a powder consisting of planar single graphene flakes occluded with spherical silica nanoparticles with a diameter of up to 30 nm, or a monolithic silica xerogel with graphene flakes homogeneously dispersed across its volume.
  • uniform and stable suspension of graphene flakes in transparent silica allows for the transmission of light (especially in the visible light region) to the surface of graphene flakes across the volume of the composite for each of its forms (powder, monolith).
  • Graphene flakes do not sublimate when the composite is exposed to light.
  • silica reinforces and stabilises the structure of graphene flakes in the composite of the invention, wherein graphene flakes flake size below 2 ⁇ are occluded with spherical silica nanoparticles with a diameter of up to 30 nm (for powder) or homogeneously dispersed in a silica xerogel (monolith).
  • the invention also relates to a method of manufacturing a stable graphene-silica composite material consisting of graphene flakes and silica, characterised in that it comprises consecutive steps, where:
  • step a) the graphite is subjected four times to oxidation according to the Brodie's method, wherein the oxidation is conducted in a fuming nitric acid medium with addition of potassium chlorate as the oxidiser to yield the compound with a general formula CO0.5H0.2, which is washed off with a hydrochloric acid solution and then with distilled and demineralised water to obtain a neutral pH of the filtrate, after which the resulting graphite oxide is dried;
  • step b) the graphite oxide prepared in step a) is expanded using one of the alternative methods comprising the following: a thermal method by heating the graphite oxide prepared in step a) at a temperature of 400°C to 1100°C under nitrogen with a gas flow rate of 0.015 m 3 /h or a hydrothermal method by placing the graphite oxide prepared in step a) in a pressure reactor under conditions of elevated pressure (approx. 30 bar) in an aqueous medium at a temperature of 220°C for 4 h without adding any reducing substances, to yield flake graphene with flake sizes below 2 ⁇ (linear sizes of the flakes ranging from 0.5 to 3 ⁇ , average size of approx. 1.5-1.7 ⁇ );
  • step c) the graphene flakes prepared in step b) are processed into the form of a graphene-silica composite using the sol-gel method, wherein the further process steps are carried out depending on the final form of the composite to be obtained.
  • a non-polar solvent e.g. cyclohexanol
  • a non-polar solvent e.g. cyclohexanol
  • ultrasounds 900W (22 KHz) for 1 hour
  • the following are added to the resulting suspension: first, water, surfactant and alcohol, (e.g. 1-hexanol, which participates in the formation of micelles and is easily removed from the system), then an alkoxy silica precursor is added dropwise, then ammonia is added, which acts as a catalyst for the basic hydrolysis reaction followed by polycondensation (temperature of approx.
  • an alkoxylated silica precursor is added to the graphene flakes prepared in step b) and mixture is sonicated with ultrasounds of 900W (22 KHz) for 1 hour, after which water and hydrochloric acid are added to the resulting suspension in order to initiate the acid hydrolysis reaction followed by polycondensation resulting in the formation of a gel which is then matured by slow drying first at room temperature for 3 days and then by heating the sample in an dryer at a temperature 50°C for 4-5 days, after which the temperature was gradually raised (at a rate of 0.1°C/min.) to a temperature of 200-350°C, at which the sample is heated in the dryer for 24 hours, after which the dryer is turned off and the sample is freely cooled to yield a composite in the form of a monolithic silica xerogel with graphene flakes of less than 2 ⁇ in size homogeneously dispersed across its volume, wherein the desired shape
  • alkoxysilanes preferably TEOS tetraethoxysilane
  • the surfactant used is preferably a nonionic surfactant of the Triton group, particularly preferably TritonX-lOO (trade name of Union Carbide for Triton X type detergents, CAS No. 9002-93-1; 4-(l, 1,3,3- tetramethylbutyl)phenyl-polyethylene glycol), in particular due to the lack of inorganic constituents and the possibility of easy removal from the system.
  • the microemulsion method reverse micelle method, where polar compounds are emulsified in a non-polar solvent
  • the advantage of this method is the possibility of obtaining silica nanoparticles with very small dimensions of the order of approx. 30 nm and narrow distribution of grain size and also the ability of the resulting silica nanoparticles to agglomerate into layers on a hydrophobic substrate (in this case on graphene flakes), which has not hitherto been used in the synthesis of composites.
  • An important step in the method of manufacturing the composite according to the invention is to obtain a stable suspension of flake graphene with a silica precursor (with optional addition of cyclohexane) and then to form a stable emulsion with water, which is possible by using a high-power disperser (900W, 22 KHz, average dispersing time 1 h). Generally, the dispersing process could be replaced by very vigorous stirring for several days, but the dispersion is much more efficient.
  • a high-power disperser 900W, 22 KHz, average dispersing time 1 h
  • the final product is obtained by way of acid or alkaline hydrolysis of a silica precursor (e.g. an alkoxy precursor, i.e. TEOS) during which polycondensation occurs, which cause the formation of spherical silica nanoparticles that deposits on graphene flakes or the formation of a gel with graphene flakes homogeneously distributed across its volume.
  • a silica precursor e.g. an alkoxy precursor, i.e. TEOS
  • a silica precursor e.g. TEOS
  • a magnetic stirrer e.g. TEOS
  • the stirring is continued for 1.5 h.
  • the sol is left in a sealed mould and as a result, after one or two days, a silica hydrogel is generated with graphene flakes homogeneously distributed across its volume.
  • the water and alcohol present in the system are removed during the drying of the gel.
  • This process also provides the possibility to form the xerogel into a desired shape already at the stage of its manufacturing.
  • the structure of the composite is fixed while removing any residual water and alcohol from the system.
  • the method for preparing the composite of the invention allows stable bonding of graphene flakes with silica and eliminates the disadvantages of the prior art solutions. Moreover, the method of the invention allows for forming the desired shape of the composite already at the manufacturing stage, so that the method of the invention provides a material with the desired shape and requires only finishing processing to be adapted to specific applications (e.g. grinding for optoelectronic applications).
  • Fig. 1 is a SEM image of flake graphene obtained by temperature expansion under nitrogen.
  • Fig. 2 is a SEM image of flake graphene obtained by hydrothermal expansion.
  • Fig. 3 is a SEM image of a composite material in which flake graphene is coated with a layer of silica nanoparticles using the microemulsion method.
  • Fig. 4 is a schematic drawing of a composite system illustrating the relative position of the components a) of the powder and b) of the monolith, respectively.
  • Fig. 5a is a block of the silica xerogel monolith with graphene flakes homogeneously dispersed across its volume directly after thermal treatment, before removal from the vial which was completely filled with gel prior to the thermal treatment.
  • Fig. 5b is a photograph of a finished monolith of silica xerogel with graphene flakes homogeneously dispersed across its volume
  • the flask with the reaction mixture was transferred to a heating jacket, 50 ml of fuming (98- 100%) HNO3 were added, and the mixture was left at reflux at a temperature of 80°C for 72 hours.
  • the obtained formulation was washed with deionised water, then three times with 10% hydrochloric acid solution and again with water, until neutral pH of the filtrate (pH 7) was obtained.
  • the cycle was repeated four times using the formulation obtained in the previous cycle as the starting material in the next cycle, with identical amounts of reagents and identical reaction conditions retained.
  • the precipitate was dried in air at a temperature of 70°C to yield a graphite oxide formulation with a light yellow colour, indicating high oxidation of the product.
  • the reaction mixture was left on the magnetic stirrer for another 5 h.
  • the flask was then placed in the refrigerator at a temperature of -5°C for 3 days.
  • the precipitate was precipitated by adding 15 ml of cooled acetone, and the resulting product was separated using a centrifuge (4000 rpm, 10 min.) and washed three times with water and three times with ethanol.
  • the obtained composite was then dried in a forced air circulation dryer at a temperature of 90°C for 72 h. Finally, the sample was heated under nitrogen at 350°C for 1 h.
  • the vial covered with watch glass was placed in a forced air circulation dryer and dried at a temperature of 50°C for 4-5 days, after which the temperature was slowly raised to 200°C (temperature growth of 0. l°C/min), and left at this temperature for one day. Before the sample was removed, the dryer freely cooled to room temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un composite graphène-silice stable à base d'oxyde de graphite expansé et de silice ou de xérogel de silice, caractérisé en ce qu'il s'agit d'un système de flocons de graphène et de silice, chaque flocon de graphène ayant une taille inférieure à 2 µm. L'invention concerne également un procédé d'obtention de ces composites.
PCT/PL2018/050043 2017-08-04 2018-08-02 Composites de graphène-silice stables et procédé de fabrication associé WO2019027337A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL422455A PL237598B1 (pl) 2017-08-04 2017-08-04 Stabilne kompozyty grafenowo-krzemionkowe i sposób ich wytwarzania
PLP.422455 2017-08-04

Publications (1)

Publication Number Publication Date
WO2019027337A1 true WO2019027337A1 (fr) 2019-02-07

Family

ID=63638273

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/PL2018/050043 WO2019027337A1 (fr) 2017-08-04 2018-08-02 Composites de graphène-silice stables et procédé de fabrication associé

Country Status (2)

Country Link
PL (1) PL237598B1 (fr)
WO (1) WO2019027337A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110204783A (zh) * 2019-07-02 2019-09-06 江苏通用科技股份有限公司 一种石墨烯白炭黑高分散复合材料的制备方法
CN110302397A (zh) * 2019-08-09 2019-10-08 西北工业大学 pH响应性氧化石墨烯纳米片包覆介孔二氧化硅药物双载复合纳米粒子及制备方法
CN111909516A (zh) * 2019-05-09 2020-11-10 深圳光启岗达创新科技有限公司 导热复合材料及其制备方法
CN112645327A (zh) * 2020-12-21 2021-04-13 中国烟草总公司郑州烟草研究院 多孔碳核壳复合材料的制备方法
CN114085654A (zh) * 2020-08-24 2022-02-25 中石化石油工程技术服务有限公司 一种钻井液用改性石墨处理剂及其制备方法
CN114163673A (zh) * 2021-12-14 2022-03-11 广东思泉新材料股份有限公司 一种低介电高导热界面膜及其制备方法
KR102431826B1 (ko) * 2021-11-11 2022-08-11 주식회사 에이비엠 다용도 코팅 조성물 및 그 제조방법
CN114956100A (zh) * 2022-04-25 2022-08-30 齐鲁工业大学 一种片状二氧化硅及其制备方法
CN115181489A (zh) * 2022-08-02 2022-10-14 亚士漆(上海)有限公司 一种吸音涂料及其制备方法和应用
CN115368113A (zh) * 2022-09-29 2022-11-22 湖南华联瓷业股份有限公司 一种废瓷再利用的方法
CN115491263A (zh) * 2022-10-24 2022-12-20 中国人民解放军军事科学院防化研究院 改性纳米氧化石墨烯增稳增效防冻泡沫去污剂的制备及使用方法
CN116002660A (zh) * 2022-12-28 2023-04-25 太原科技大学 一种碳硅复合材料的制备方法、碳硅复合材料及锂电池
CN117025125A (zh) * 2023-07-21 2023-11-10 江苏特丽亮新材料科技有限公司 一种柔性超薄导电胶膜及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112142041A (zh) * 2020-09-30 2020-12-29 南通大学 一种石英光纤固废SiO2的转化利用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2256087A1 (fr) * 2009-05-26 2010-12-01 Belenos Clean Power Holding AG Dispersions stables de couches de graphène simple et multiples dans une solution
US20140323589A1 (en) * 2011-10-28 2014-10-30 Debreceni Egyetem Method for the preparation of composite silica alcogels, aerogels and xerogels, apparatus for carrying out the method continuously, and novel composite silica alcogels, aerogels and xerogels

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2256087A1 (fr) * 2009-05-26 2010-12-01 Belenos Clean Power Holding AG Dispersions stables de couches de graphène simple et multiples dans une solution
US20140323589A1 (en) * 2011-10-28 2014-10-30 Debreceni Egyetem Method for the preparation of composite silica alcogels, aerogels and xerogels, apparatus for carrying out the method continuously, and novel composite silica alcogels, aerogels and xerogels

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HINTZE CORNELIA ET AL: "Facile sol-gel synthesis of reduced graphene oxide/silica nanocomposites", JOURNAL OF THE EUROPEAN CERAMIC SOCIETY, ELSEVIER SCIENCE PUBLISHERS, BARKING, ESSEX, GB, vol. 36, no. 12, 4 December 2015 (2015-12-04), pages 2923 - 2930, XP029555377, ISSN: 0955-2219, DOI: 10.1016/J.JEURCERAMSOC.2015.11.033 *
JINGUI JIANG ET AL: "Sol-gel process-derived rich nitrogen-doped porous carbon through KOH activation for supercapacitors", ELECTROCHIMICA ACTA, 10 March 2015 (2015-03-10), pages 229 - 236, XP055518894, Retrieved from the Internet <URL:https://pdfs.semanticscholar.org/30a6/57a64e03a405af974c18dfe7ef266d7dd380.pdf> DOI: 10.1016/j.electacta.2015.01.144 *
KAIJIE YANG ET AL: "Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water", SCIENTIFIC REPORTS, vol. 5, no. 1, 29 June 2015 (2015-06-29), XP055518825, DOI: 10.1038/srep11641 *
SZABO T ET AL: "Enhanced acidity and pH-dependent surface charge characterization of successively oxidized graphite oxides", CARBON, ELSEVIER, OXFORD, GB, vol. 44, no. 3, 23 September 2005 (2005-09-23), pages 537 - 545, XP025010648, ISSN: 0008-6223, [retrieved on 20060301], DOI: 10.1016/J.CARBON.2005.08.005 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111909516B (zh) * 2019-05-09 2023-05-02 深圳光启岗达创新科技有限公司 导热复合材料及其制备方法
CN111909516A (zh) * 2019-05-09 2020-11-10 深圳光启岗达创新科技有限公司 导热复合材料及其制备方法
CN110204783A (zh) * 2019-07-02 2019-09-06 江苏通用科技股份有限公司 一种石墨烯白炭黑高分散复合材料的制备方法
CN110302397A (zh) * 2019-08-09 2019-10-08 西北工业大学 pH响应性氧化石墨烯纳米片包覆介孔二氧化硅药物双载复合纳米粒子及制备方法
CN110302397B (zh) * 2019-08-09 2022-12-09 西北工业大学 pH响应性氧化石墨烯纳米片包覆介孔二氧化硅药物双载复合纳米粒子及制备方法
CN114085654A (zh) * 2020-08-24 2022-02-25 中石化石油工程技术服务有限公司 一种钻井液用改性石墨处理剂及其制备方法
CN114085654B (zh) * 2020-08-24 2023-07-21 中石化石油工程技术服务有限公司 一种钻井液用改性石墨处理剂及其制备方法
CN112645327A (zh) * 2020-12-21 2021-04-13 中国烟草总公司郑州烟草研究院 多孔碳核壳复合材料的制备方法
KR102431826B1 (ko) * 2021-11-11 2022-08-11 주식회사 에이비엠 다용도 코팅 조성물 및 그 제조방법
CN114163673A (zh) * 2021-12-14 2022-03-11 广东思泉新材料股份有限公司 一种低介电高导热界面膜及其制备方法
CN114956100A (zh) * 2022-04-25 2022-08-30 齐鲁工业大学 一种片状二氧化硅及其制备方法
CN115181489A (zh) * 2022-08-02 2022-10-14 亚士漆(上海)有限公司 一种吸音涂料及其制备方法和应用
CN115368113A (zh) * 2022-09-29 2022-11-22 湖南华联瓷业股份有限公司 一种废瓷再利用的方法
CN115491263A (zh) * 2022-10-24 2022-12-20 中国人民解放军军事科学院防化研究院 改性纳米氧化石墨烯增稳增效防冻泡沫去污剂的制备及使用方法
CN115491263B (zh) * 2022-10-24 2024-03-12 中国人民解放军军事科学院防化研究院 改性纳米氧化石墨烯增稳增效防冻泡沫去污剂的制备及使用方法
CN116002660A (zh) * 2022-12-28 2023-04-25 太原科技大学 一种碳硅复合材料的制备方法、碳硅复合材料及锂电池
CN116002660B (zh) * 2022-12-28 2023-07-18 太原科技大学 一种碳硅复合材料的制备方法、碳硅复合材料及锂电池
CN117025125A (zh) * 2023-07-21 2023-11-10 江苏特丽亮新材料科技有限公司 一种柔性超薄导电胶膜及其制备方法
CN117025125B (zh) * 2023-07-21 2024-02-20 江苏特丽亮新材料科技有限公司 一种柔性超薄导电胶膜及其制备方法

Also Published As

Publication number Publication date
PL237598B1 (pl) 2021-05-04
PL422455A1 (pl) 2019-02-11

Similar Documents

Publication Publication Date Title
WO2019027337A1 (fr) Composites de graphène-silice stables et procédé de fabrication associé
JP4296307B2 (ja) 球状シリカ系メソ多孔体の製造方法
JP4961953B2 (ja) 多孔質カーボン配列体及びその製造方法
US8496871B2 (en) Silica structure and method of producing the same, and heat insulating material
JPWO2007122930A1 (ja) コアシェル型シリカおよびその製造方法
JPH1160232A (ja) 繭型コロイダルシリカの製造方法
EP1885653A1 (fr) Particules poreuses de silicium
KR20100038170A (ko) 구상 유기 폴리머-실리콘 화합물 복합 입자, 중공 입자 및 그들의 제조 방법
Lazareva et al. Synthesis of high-purity silica nanoparticles by sol-gel method
EP0310486B1 (fr) Méthode de préparation
JP4035440B2 (ja) 大きい寸法を有する乾燥ゲルおよびこれによって導かれるガラスを製造するためのゾル−ゲル法
WO2001053225A1 (fr) Procede sol-gel permettant de produire un verre de silice synthetique
JP5603566B2 (ja) 球状メソポーラスカーボン及びその製造方法
EP1905064A2 (fr) Nanoparticules et procede de fabrication
KR101516151B1 (ko) 태양 광전지 커버 유리용 매크로 기공성 반사방지 조성물과 이를 사용한 태양광전지
KR101466095B1 (ko) 중공형 나노 실리카 물질 합성방법.
JP2006027985A (ja) 球状シリカ系メソ多孔体の製造方法
JP6277387B2 (ja) フォルステライト微粒子の製造方法
KR20220060191A (ko) 실리콘 카바이드 입자의 제조방법
JP5435272B2 (ja) 球状シリカ系メソ多孔体の製造方法
JP5646224B2 (ja) 多孔質無機酸化物およびその製法
JPH01183421A (ja) 石英ガラスの製造方法
CN104229804A (zh) 一种多孔硅材料及其制备方法
JP4507499B2 (ja) 球状多孔体の製造方法
CN105366734B (zh) 氧化硅包覆四氧化三铁核壳型纳米复合粒子的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18772926

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18772926

Country of ref document: EP

Kind code of ref document: A1