WO2023072613A1 - Verfahren zur herstellung von carbonisierten oder graphitierten 3d-gegenständen - Google Patents

Verfahren zur herstellung von carbonisierten oder graphitierten 3d-gegenständen Download PDF

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Publication number
WO2023072613A1
WO2023072613A1 PCT/EP2022/078542 EP2022078542W WO2023072613A1 WO 2023072613 A1 WO2023072613 A1 WO 2023072613A1 EP 2022078542 W EP2022078542 W EP 2022078542W WO 2023072613 A1 WO2023072613 A1 WO 2023072613A1
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WIPO (PCT)
Prior art keywords
blank
temperature
objects
furnace
graphitized
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2022/078542
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German (de)
English (en)
French (fr)
Inventor
Torsten Kornmeyer
David Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kornmeyer Carbon Group GmbH
Original Assignee
Nippon Kornmeyer Carbon Group GmbH
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 Nippon Kornmeyer Carbon Group GmbH filed Critical Nippon Kornmeyer Carbon Group GmbH
Priority to EP22803190.2A priority Critical patent/EP4426662A1/de
Priority to US18/704,995 priority patent/US20250270143A1/en
Priority to JP2024525584A priority patent/JP2024541038A/ja
Priority to CN202280073296.2A priority patent/CN118201893A/zh
Publication of WO2023072613A1 publication Critical patent/WO2023072613A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522Graphite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/573Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • C04B35/65Reaction sintering of free metal- or free silicon-containing compositions
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83Carbon fibres in a carbon matrix
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40Metallic constituents or additives not added as binding phase
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428Silicon
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602Making the green bodies or pre-forms by moulding
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562Heating rate
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567Treatment time
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
    • C04B2235/6581Total pressure below 1 atmosphere, e.g. vacuum

Definitions

  • the invention relates to a method for producing carbonized or graphitized 3D objects.
  • Such carbonized or graphitized 3D objects which are also suitable for high-temperature applications, can be various components, such as linings for furnaces, structural components or any type of hollow body, container or crucible.
  • a suitable carbonaceous and malleable mass must generally be made.
  • a suitable binder such as a thermoplastic binder.
  • Pitch based on coal tar or petroleum pitch, or even synthetic resins, can also be considered as binders.
  • the green molded part can also be arranged as a resistance element in a furnace between electrodes and heated by current flow.
  • the difficulty in carbonizing or graphitizing a such a molded part is that at the high temperatures required here, volatile substances outgas more or less violently, which can lead to disruptions in the structure, such as cracks or gas inclusions.
  • the object of the invention is to create a method for producing carbonized or graphitized 3D objects which is particularly easy to implement and which also allows more complex 3D objects to be produced without disrupting the structure.
  • bamboo, cotton, hemp, sisal or graphite fibers can be added to the carbonizable or graphitizable material while retaining the kneadability be mixed in.
  • the 3D blank is shaped by hand using suitable templates.
  • the 3D blank is produced by molding in a mold.
  • Argon or helium is preferably used as the protective gas.
  • the 3D blank can be subjected to a stabilization and homogenization process at a stabilization temperature of 170°C in air or up to a maximum of 450°C in air, with a temperature of 250°C being preferred, so that a 3D molded part arises.
  • the stabilization and homogenization process can also be carried out under an inert gas such as argon.
  • the 3D blank can also be stabilized and homogenized while the furnace is being heated up.
  • the 3D shaped part is carbonized at a constant temperature of approx. 1,000° C. to form a 3D object until pure carbon with a different crystal structure is formed.
  • the 3D molded part is graphitized at a constant temperature of 2,000° C. and above.
  • the 3D molded part can be fully graphitized at a temperature of over 2,500°C.
  • the graphitization preferably takes place with a heating ramp of about 1° C./min until the target temperature has been reached, followed by tempering over approx. 30 min, depending on the size of the 3D molded parts.
  • a metal or silicon powder can be added to the kneadable mass, so that during a high-temperature treatment of the 3D molded part at >1. 000 °C under protective gas metal carbides or silicon carbides can be formed.
  • the graphitized foamy 3D objects can also be baked in an oven at a temperature of >1. 200 ° C with supply of gaseous SiO with argon as carrier gas at a pressure of approx . 30 mbar can be converted into 3D objects made of SiC.
  • a kneadable, largely dimensionally stable mass is produced by mixing a carbonizable or graphitizable material with a free-flowing organic adhesive, or a flowable thermoplastic organic material, followed by molding the mass into a 3D blank.
  • the 3D blank is then freed from moisture and gas inclusions in particular in a drying and outgassing process at elevated temperature and thereby converted into a 3D molded part. This can prevent cracks from forming during the subsequent carbonization or graphitization of the 3D molded part in a furnace under vacuum or inert gas, such as argon or helium, to produce a 3D object be avoided.
  • Carbon black, graphite dust, natural graphite and starch, e.g. corn or potato starch or the like, or a mixture of some or all of these materials can preferably be used as carbonizable or graphitizable organic material.
  • the carbonized or graphitizable organic material can be supplemented with bamboo, cotton, hemp, sisal, or other suitable vegetable fibers, or graphite fibers while maintaining the clay Ability to be blended, adding more flowable adhesive or flowable organic if necessary, until the desired consistency is achieved.
  • the 3D blank can be shaped by hand, for example using templates, or by shaping in a mold, with the 3D blank being removed from the mold before the drying process.
  • a mold made of Teflon, silicone or another material with limited elasticity can be used to enable easier demolding of the 3D blank.
  • the 3D molded part can be subjected to the drying process at room temperature or at a maximum of 100°C in order to remove any water present.
  • a subsequent stabilization and homogenization process at a stabilization temperature of 140°C in air or up to a maximum of 450°C, under protective gas or vacuum, with a temperature of 250°C being preferred, a Outgassing to avoid cracking during later carbonization or graphitization.
  • the 3D molded part can remain in a suitable shape during the stabilization or homogenization process.
  • the 3D molded part can also be stabilized and homogenized while the furnace is being heated up.
  • the 3D molded part is heated at a constant temperature of approx. 1 . 000 ° C to a 3D object carbonized in the oven until pure carbon with different crystal structure is formed.
  • the 3D molded part is then formed at a constant temperature to form a 3D object from 2 . 000 ° C graphitized in the furnace .
  • the 3D molded part can be processed at a temperature above 2 . 500 ° C to form a 3D object in the furnace to be fully graphitized.
  • the carbonization or graphitization preferably takes place with a heating ramp of about 1° C./min until the target temperature has been reached, followed by tempering over approx. 30 min, although tempering for several hours is also possible.
  • a metal or silicon powder can be added to the kneadable mass, so that during a high-temperature treatment of the 3D molded part at >1. 000 °C under protective gas metal carbides or silicon carbides can be formed.
  • the graphitized foamy 3D objects can also be baked in an oven at a temperature of >1. 200 ° C with supply of gaseous SiO with argon as carrier gas at a pressure of approx . 30 mbar can be converted into 3D objects made of SiC.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/EP2022/078542 2021-11-01 2022-10-13 Verfahren zur herstellung von carbonisierten oder graphitierten 3d-gegenständen Ceased WO2023072613A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP22803190.2A EP4426662A1 (de) 2021-11-01 2022-10-13 Verfahren zur herstellung von carbonisierten oder graphitierten 3d-gegenständen
US18/704,995 US20250270143A1 (en) 2021-11-01 2022-10-13 Method for producing carbonised or graphitised 3D objects
JP2024525584A JP2024541038A (ja) 2021-11-01 2022-10-13 炭化または黒鉛化された3d物体の製造方法
CN202280073296.2A CN118201893A (zh) 2021-11-01 2022-10-13 制造碳化或石墨化的三维物体的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021128414.7A DE102021128414A1 (de) 2021-11-01 2021-11-01 Verfahren zur Herstellung von karbonisierten oder graphitierten 3D-Gegenständen
DE102021128414.7 2021-11-01

Publications (1)

Publication Number Publication Date
WO2023072613A1 true WO2023072613A1 (de) 2023-05-04

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US (1) US20250270143A1 (https=)
EP (1) EP4426662A1 (https=)
JP (1) JP2024541038A (https=)
CN (1) CN118201893A (https=)
DE (1) DE102021128414A1 (https=)
WO (1) WO2023072613A1 (https=)

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CN120329009A (zh) * 2025-06-18 2025-07-18 安徽省萧县华龙耐火材料有限责任公司 一种纳米钢包镁碳砖及其制备工艺

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DE102021130581A1 (de) * 2021-11-23 2023-05-25 Nippon Kornmeyer Carbon Group Gmbh Verfahren zur Herstellung von porösem Karbon oder Graphit
CN119390473B (zh) * 2024-11-12 2025-07-22 成都方大炭炭复合材料股份有限公司 一种多孔石墨材料及其制备方法

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JP2007145665A (ja) * 2005-11-29 2007-06-14 Tokai Konetsu Kogyo Co Ltd 多孔質SiC焼結体の製造方法
WO2015040064A1 (fr) * 2013-09-20 2015-03-26 Universite De Lorraine Matrices carbonees composites poreuses pour le stockage d'energie thermique
JP2016179923A (ja) * 2015-03-24 2016-10-13 株式会社神戸製鋼所 炭素材料の製造方法及び炭素材料
CN108675790A (zh) * 2018-06-20 2018-10-19 三峡大学 一种石墨/碳化硅隔热背衬及其制备方法
CN111138207A (zh) * 2020-01-14 2020-05-12 大同新成新材料股份有限公司 一种直拉单晶硅炉用石墨热场材料制备方法
EP3789367A1 (en) * 2019-08-27 2021-03-10 Southwest Jiaotong University Method of preparing high-conductivity pantograph carbon contact strip

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WO2001098207A1 (en) 2000-06-19 2001-12-27 Corning Incorporated Plasticizable mixture and method of using
EP1741687B1 (de) 2005-07-05 2011-10-12 MANN+HUMMEL Innenraumfilter GmbH & Co. KG Poröser beta-SIC-haltiger keramischer Formkörper und Verfahren zu dessen Herstellung aus einem Kohlenstoff-haltigen Formkörper
DE102013114628B4 (de) 2013-12-20 2018-11-22 Deutsches Zentrum Für Luft- Und Raumfahrt Verfahren zum Herstellen von endkonturnah geformten Siliciumcarbid-Keramiken
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GB1415089A (en) * 1972-05-30 1975-11-26 Valley Co Inc Methods of producing carbonaceous bodies and the products thereof
JP2007145665A (ja) * 2005-11-29 2007-06-14 Tokai Konetsu Kogyo Co Ltd 多孔質SiC焼結体の製造方法
WO2015040064A1 (fr) * 2013-09-20 2015-03-26 Universite De Lorraine Matrices carbonees composites poreuses pour le stockage d'energie thermique
JP2016179923A (ja) * 2015-03-24 2016-10-13 株式会社神戸製鋼所 炭素材料の製造方法及び炭素材料
CN108675790A (zh) * 2018-06-20 2018-10-19 三峡大学 一种石墨/碳化硅隔热背衬及其制备方法
EP3789367A1 (en) * 2019-08-27 2021-03-10 Southwest Jiaotong University Method of preparing high-conductivity pantograph carbon contact strip
CN111138207A (zh) * 2020-01-14 2020-05-12 大同新成新材料股份有限公司 一种直拉单晶硅炉用石墨热场材料制备方法

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