CN1189430C - 复合碳质隔热材料及其制造方法 - Google Patents

复合碳质隔热材料及其制造方法 Download PDF

Info

Publication number
CN1189430C
CN1189430C CNB008095264A CN00809526A CN1189430C CN 1189430 C CN1189430 C CN 1189430C CN B008095264 A CNB008095264 A CN B008095264A CN 00809526 A CN00809526 A CN 00809526A CN 1189430 C CN1189430 C CN 1189430C
Authority
CN
China
Prior art keywords
carbonaceous
carbonaceous heat
insualtor
thermally decomposed
insulating component
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.)
Expired - Lifetime
Application number
CNB008095264A
Other languages
English (en)
Other versions
CN1358162A (zh
Inventor
有本嘉裕
渋谷幸广
小林正则
岩本茂树
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.)
Kureha Corp
Original Assignee
Kureha Corp
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 Kureha Corp filed Critical Kureha Corp
Publication of CN1358162A publication Critical patent/CN1358162A/zh
Application granted granted Critical
Publication of CN1189430C publication Critical patent/CN1189430C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped 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
    • C04B35/52—Shaped 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/008—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/38—Fiber or whisker reinforced
    • C04B2237/385—Carbon or carbon composite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/61—Joining two substrates of which at least one is porous by infiltrating the porous substrate with a liquid, such as a molten metal, causing bonding of the two substrates, e.g. joining two porous carbon substrates by infiltrating with molten silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992—Density or compression of components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Thermal Insulation (AREA)

Abstract

本发明的目的是提供使用时消耗、劣化、粉化少，隔热特性优良的隔热材料及其制造方法。所述隔热材料具有堆积密度0.1～0.4g/cm3的碳质隔热构件，和在碳纤维结构体中浸透了热分解碳的堆积密度0.3～2.0g/cm3的碳质保护层，以及比碳质保护层堆积密度大的热分解碳覆层，上述碳质隔热构件的表面至少一部分与上述碳质保护层接合形成接合体，该接合体表面中至少在上述碳质隔热构件表面上形成热分解碳覆层。

Description

复合碳质隔热材料及其制造方法
技术领域
本发明属于碳质隔热材料技术领域，特别涉及作为单晶拉晶装置或陶瓷烧结炉等中的炉内材料适用的复合碳质隔热材料及其制造方法。
背景技术
碳纤维隔热材料，由于其优秀的隔热性能、低热容量等特性，作为单晶拉晶炉、真空气相沉积炉、陶瓷烧结炉等高温炉用隔热材料被广泛使用。
这种碳纤维隔热材料渐渐成为成型隔热材料的主流(参照特公昭50-35930号公报)。该成型隔热材料，以碳纤维毡作为基材，在该基材中含浸碳化率高的树脂，将其层合压缩，形成成型物，进一步碳化处理得到具有形状自持性的产品。
碳纤维类隔热材料在惰性气氛中，由于高耐热性和低蒸气压，直到3000℃左右的高温都可使用。但是，在实际的使用环境中，构成碳纤维隔热材料的碳纤维，由于与炉内产生的氧化性气体或气化的金属反应等引起消耗、劣化。例如，在陶瓷烧结炉或硅单晶拉晶炉中，碳纤维与炉内产生的SiO等气体反应，伴随着碳纤维表面附着金属，不断消耗、脆化、粉化。如果这样的话，碳纤维隔热材料不仅隔热特性降低，寿命变短，而且产生的细微碳尘释放到炉内，成为污染炉内制成的产品的原因。
因此，在硅单晶拉晶炉等中，有人采用将隔热材料用石墨制的壳包围，避免炉内产生的气体直接与隔热材料接触的方法。但是，由于石墨制的壳热容量很大，存在炉的热效率、开工率小的问题。
作为解决这种问题的手段，有人提出在具有通气性的碳毡表面形成热分解碳覆层或(和)由在内部浸透热分解碳的碳毡形成碳纤维隔热材料的方法(参见特开平1-167210号公报)。
但是，在上述特开平1-167210的方法中，对于将热分解碳浸透到内部的碳纤维隔热材料，如果热分解碳的浸透量过大，则隔热性能降低，对于在表面形成热分解碳覆层的物质，热分解碳由于只浸透表面，其浸透量小，因此存在隔热材料的消耗、粉化加剧的问题。
本发明的目的是提供解决这些问题，使使用时消耗、劣化、粉化减弱，隔热特性优良的碳质隔热材料及其制造方法。
发明的公开
按照本发明，上述目的可通过如下达到，所涉及的复合碳质隔热材料是，具有堆积密度0.1～0.4g/cm3的碳质隔热构件，和在碳纤维结构体中浸透了热分解碳的堆积密度0.3～2.0g/cm3的碳质保护层，和具有比碳质保护层堆积密度大的热分解碳覆层，上述碳质隔热构件的表面至少一部分与上述碳质保护层接合形成接合体，该接合体表面中至少在上述碳质隔热构件表面中形成热分解碳覆层。
在本发明的复合碳质隔热材料中，优选碳质隔热构件与碳质保护层通过致密碳质中间层接合。
另外，在本发明的复合碳质隔热材料中，优选热分解碳覆层通过致密碳质表面层设置在碳质隔热构件中。
该致密碳质中间层和致密碳质表面层，例如可通过将鳞片状石墨和通过加热碳化的粘合剂成分形成的致密碳形成用组合物加热、碳化而容易地形成。
本发明的复合碳质隔热材料的制造方法是，在碳纤维成型体形成的碳质隔热构件表面的至少一部分上，碳纤维结构体中接合在浸透了热分解碳的碳质保护层上一体化形成接合体后，在该接合体表面的至少上述碳质隔热构件的表面，换句话说，在碳质隔热构件的表面和/或碳质保护层的表面可形成热分解碳覆层。此时，对于碳质隔热构件的表面，可在致密碳质表面层形成后，形成热分解碳覆层。
另外，本发明的复合碳质隔热材料，可通过从碳纤维成型体形成的碳质隔热构件与碳纤维结构体接合一体化形成接合体后，在碳质隔热构件的表面形成致密碳质表面层，然后在碳质隔热构件表面形成热分解碳覆层的同时，在碳纤维结构体内部浸透热分解碳来制造。
本发明的复合碳质隔热材料，用堆积密度小的碳质隔热构件维持隔热性的同时，通过堆积密度大的碳质保护层抑制碳质隔热构件在使用时的消耗、劣化和粉化。由于在碳质保护层中浸透了热分解碳，反应气体很难侵入而且耐反应性优良。另外，由于表面被热分解碳覆层覆盖，复合碳质隔热材料的总体消耗、劣化变少，防止了碳粉末的飞散。
发明实施的最佳方式
本发明的复合碳质隔热材料，具有碳质隔热构件，和在碳纤维结构体中浸透了热分解碳的碳质保护层，以及比碳质保护层堆积密度大的热分解碳覆层，上述碳质隔热构件的表面至少一部分与上述碳质保护层接合形成接合体，该接合体表面中至少在上述碳质隔热基材表面上形成热分解碳覆层。
虽然碳质隔热构件与碳质保护层可以通气状态接合，但是优选通过气体透过性小的致密碳质中间层接合。
本发明中使用的碳质隔热构件，只要是堆积密度小的多孔碳质材料均可，对此没有特别的限制，例如可适当地使用碳纤维成型隔热材料等作为碳质隔热构件。
碳纤维成型隔热材料，可通过在沥青系碳纤维、人造丝系碳纤维、聚丙烯腈碳纤维等碳纤维毡基材中，含浸酚树脂、呋喃树脂等粘合剂成型、固化后，将粘合剂碳化，碳纤维彼此之间通过粘合剂碳化物结合制造。
碳质隔热层构件，从隔热特性、强度和形状保持性等观点考虑，其堆积密度应在0.1～0.4g/cm3范围。堆积密度比该范围的值小得多，则强度和形状保持性变差，如果比该范围的值大得多，则隔热性降低。从隔热性以及热容量的观点考虑，优选在0.13～0.3g/cm3的范围。
构成本发明复合碳质隔热材料的碳质保护层，可通过在碳纤维结构体内部浸透热分解碳制造。在本说明书中，“碳纤维结构体”是指以碳纤维为主构成的多孔质结构体。作为碳纤维结构体，可列举碳纤维毡、碳纤维布、碳纤维毡或碳纤维布中含浸酚树脂等粘合剂，使碳纤维彼此之间通过树脂粘合剂结合形成的成型体，将这些成型体加热，粘合剂碳化，碳纤维彼此之间通过粘合剂碳化物结合的成型体等，但是并不限于这些。作为构成碳纤维结构体的碳纤维，可适宜地使用与构成上述碳纤维类成型隔热材料的碳纤维同样的碳纤维。在碳纤维结构体内部浸透热分解碳是如下进行的：将碳纤维结构体加热至800～2000℃，与碳原子数1～6左右的直链或环状烃气体接触，使碳纤维结构体内部的碳纤维表面用气相通过热分解生成的碳气相沉积。这种方法作为所谓的化学气相沉积法(CVD)法是众所周知的。
碳质保护层优选堆积密度0.3～2.0g/cm3。堆积密度在0.3g/cm3以下时，由于热分解碳的浸透量少，防止碳质隔热构件与炉内气体的反应等的作用小，堆积密度在2.0g/cm3以上时，由于制造时热分解碳的浸透需要很长时间，而且，使用时在碳质保护层中会产生裂缝。碳质保护层的堆积密度更优选为0.4～1.5g/cm3。
碳质保护层的厚度优选在0.5～15mm范围内。厚度如果比该范围值小得多，则不能发挥作为保护层的效果，如果过大，隔热特性降低，同时隔热材料的总体重量变大，炉升温/降温时热效率变差。碳质保护层的厚度优选在1～10mm。
本发明的复合碳质隔热材料是上述碳质隔热构件与碳质保护层一体接合的。优选碳质隔热构件与碳质保护层通过不透气的致密碳质中间层接合。致密碳质中间层，例如可通过鳞片状石墨和通过加热碳化的粘合剂成分形成的致密碳形成用组合物的碳化形成。具体地说，在碳质隔热构件和碳质保护层的接合面上，涂布上述致密碳形成用组合物，两者接合后进行加热，使粘合剂成分碳化，在碳质隔热构件和碳质保护层之间形成致密碳质中间层。碳质隔热构件与碳质保护层可用酚树脂或呋喃树脂等粘合剂接合后，加热，使粘合剂碳化，以具有通气性的状态接合。
作为致密碳形成用组合物可以使用的、通过加热碳化的粘合剂成分，优选碳化率大的酚树脂和呋喃树脂。为了容易涂布致密碳形成用组合物，也可含有溶解粘合剂成分的醇类、酮类等溶剂。另外，致密碳形成用组合物还可含有鳞片状石墨以外的碳质粉末。致密碳形成用组合物中的鳞片状石墨，在向碳质隔热构件表面涂布的工序中，促进与该表面平行取向的致密化，提高致密碳质中间层的隔热性和不透气性。鳞片状石墨的粒径优选1～200μm，通常相对于粘合剂成分100重量份混合20～300重量份，优选30～200重量份。
本发明的复合碳质隔热材料，如上所述，在碳质隔热构件和碳质保护层通过致密碳质中间层接合形成接合体后，在该接合体表面至少碳质隔热构件的表面上，通过上述化学气相沉积法形成热分解碳覆层。热分解碳覆层，可在碳质隔热构件和/或碳质保护层表面直接形成，但优选在碳质隔热构件表面涂布上述致密碳形成用组合物，碳化形成致密碳质表面层，在该致密碳质表面层上形成热分解碳覆层。为了防止热分解碳浸透到碳质隔热构件内部，致密碳质表面层只在表面有效形成热分解碳覆层。
本发明的复合碳质隔热材料，可通过将碳质隔热构件和碳纤维结构体接合·一体化形成接合体后，在碳质隔热构件表面形成热分解覆层的同时在碳纤维结构体内部浸透热分解碳形成保护层来制备。该方法由于利用化学气相沉积法，生成热分解碳的操作进行1次就完成了，因此是有利的。
热分解碳覆层厚优选50～500μm。
在本发明的复合碳质隔热材料中，致密碳质表面层和致密碳质中间层的作用是在热分解碳形成时阻止热分解碳浸透到碳质隔热构件的内部。为了阻止热分解碳浸透到碳质隔热构件内部，致密碳质表面层和致密碳质中间层的堆积密度越大越好，至少在1.5g/cm3以上。
在本发明的复合碳质隔热材料中碳质隔热构件表面全部被热分解碳覆层覆盖时，使用真空炉时，为了容易进行真空操作，或者为了防止由于隔热材料温度升降引起的隔热材料内部气体的膨胀·收缩导致的隔热材料的变形，可在复合碳质隔热材料表面设置达到碳质隔热构件的孔。
实施例
将沥青系碳纤维毡作为基材，将堆积密度0.16g/cm3的成型隔热材料(碳质隔热构件)(宽100mm×长100mm×厚35mm)，和厚度5mm的碳纤维毡中相对于作为固形成分的毡100重量份含有10重量份酚树脂的含浸物(碳纤维结构体)，与鳞片状石墨、呋喃树脂和溶剂形成的致密碳形成用组合物接合，制造接合体。在该接合体的成型隔热材料部分的全体表面上，涂布与上述接合时使用的致密碳形成用组合物同样的致密碳形成用组合物，固化后，进行碳化灼烧，形成致密碳质中间层和致密碳质表面层。
接着，通过化学气相沉积法在致密碳质表面层上形成热分解碳覆层的同时，在碳纤维毡内部浸透热分解碳，形成碳质保护层，制造复合碳质隔热材料。
所得复合碳质隔热材料，在5mm的毡层(保护层)内部浸透热分解碳，在构成的碳纤维总体上以同心圆状形成层压的10～20μm的覆层。该毡层(保护层)的堆积密度是0.8g/cm3。另外，由成型隔热材料形成的碳质隔热构件内部几乎没有浸透热分解碳，在表层形成30～50μm的热分解碳覆层。
将该隔热材料在600℃的电炉内通入空气(流量2L/min)，评价耐氧化性。
作为比较，使用
隔热材料(a)：与碳质隔热构件中使用的相同的成型隔热材料，和
隔热材料(b)：在隔热材料(a)的全部表面涂布制造上述复合碳质隔热材料使用的致密碳形成用组合物，固化后，进行碳化焚烧，得到只形成致密碳质表面层的隔热材料，
进行评价。
其结果，本发明的复合碳质隔热材料显示10重量％氧化减量的时间，是隔热材料(a)的约10倍，隔热材料(b)的约5倍，确认本发明的复合碳质隔热材料具有高耐氧化性。
产业上的可利用性
本发明的复合碳质隔热材料，如上所述，具有堆积密度0.1～0.4g/cm3的碳质隔热构件，和在碳纤维结构体中浸透了热分解碳的堆积密度0.3～2.0g/cm3的碳质保护层，以及比碳质保护层堆积密度大的热分解碳覆层，上述碳质隔热构件的表面至少一部分与上述碳质保护层接合形成接合体，该接合体表面中至少在上述碳质隔热基材表面上形成热分解碳覆层，因此，用堆积密度小的碳质隔热材料维持隔热特性的同时，还具有利用堆积密度大的碳质保护层抑制碳质隔热构件使用时的消耗、劣化和粉化的效果。另外，由于表面被热分解碳覆层覆盖，复合碳质隔热材料的总体消耗、劣化减少，获得防止碳粉末飞散的效果。

Claims (9)

1、复合碳质隔热材料，其特征在于，具有堆积密度0.1～0.4g/cm3的碳质隔热构件，和在碳纤维结构体中浸透了热分解碳的堆积密度0.3～2.0g/cm3的碳质保护层，以及比该碳质保护层堆积密度大的热分解碳覆层，上述碳质隔热构件的表面的一部分与上述碳质保护层接合形成接合体，该接合体表面中至少在上述碳质隔热构件表面上形成热分解碳覆层。
2、权利要求1中记载的复合碳质隔热材料，其中，接合体的碳质隔热构件和碳质保护层通过致密碳质中间层接合形成。
3、权利要求1或2中记载的复合碳质隔热材料，其中，热分解碳覆层经由致密碳质表面层设置于碳质隔热构件上。
4、权利要求2中记载的复合碳质隔热材料，其中，致密碳质中间层是通过形成由鳞片状石墨和加热碳化的粘合剂成分构成的致密碳形成用组合物，然后将该组合物碳化得到的。
5、权利要求3中记载的复合碳质隔热材料，其中，致密碳质表面层是通过形成由鳞片状石墨和加热碳化的粘合剂成分构成的致密碳形成用组合物，然后将该碳化物碳化得到的。
6、权利要求1、2、4的任一项记载的复合碳质隔热材料，其中，碳质保护层的厚度是0.5～15mm。
7、权利要求1、2、4的任一项记载的复合碳质隔热材料，其中，热分解碳覆层的厚度是50～500μm。
8、权利要求1的复合碳质隔热材料的制造方法，其特征在于，碳质隔热构件是碳质多孔体，在该碳质多孔体的表面上形成致密碳质表面层后，形成热分解碳覆层。
9、权利要求8中记载的复合碳质隔热材料的制造方法，其中，将接合体加工成规定形状，然后形成热分解碳覆层。
CNB008095264A 1999-05-26 2000-05-24 复合碳质隔热材料及其制造方法 Expired - Lifetime CN1189430C (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP146247/99 1999-05-26
JP14624799A JP4361636B2 (ja) 1999-05-26 1999-05-26 複合炭素質断熱材及びその製造方法
JP146247/1999 1999-05-26

Publications (2)

Publication Number Publication Date
CN1358162A CN1358162A (zh) 2002-07-10
CN1189430C true CN1189430C (zh) 2005-02-16

Family

ID=15403429

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB008095264A Expired - Lifetime CN1189430C (zh) 1999-05-26 2000-05-24 复合碳质隔热材料及其制造方法

Country Status (7)

Country Link
US (1) US6686048B1 (zh)
EP (1) EP1184356A4 (zh)
JP (1) JP4361636B2 (zh)
KR (1) KR100634935B1 (zh)
CN (1) CN1189430C (zh)
TW (1) TW539612B (zh)
WO (1) WO2000073243A1 (zh)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800364B2 (en) * 2002-06-28 2004-10-05 Ucar Carbon Company Inc. Isotropic pitch-based materials for thermal insulation
FR2857660B1 (fr) 2003-07-18 2006-03-03 Snecma Propulsion Solide Structure composite thermostructurale a gradient de composition et son procede de fabrication
US7959783B2 (en) 2003-09-30 2011-06-14 The Boeing Company Electrochemical deposition process for composite structures
JP2005231982A (ja) 2004-02-23 2005-09-02 Kobe Steel Ltd 二相型ガラス状炭素部材及びその製造方法
WO2006114897A1 (ja) * 2005-04-22 2006-11-02 Kureha Corporation 断熱材用コーティング剤及びそれを用いてなる断熱材用積層体
JP4883805B2 (ja) * 2005-04-22 2012-02-22 株式会社クレハ 断熱材用コーティング層、断熱材用積層体、断熱材用コーティング剤、並びに、断熱材用コーティング剤の製造方法
JP5120585B2 (ja) * 2006-03-16 2013-01-16 株式会社Ｉｈｉ 基板アニール装置用の遮熱板
JP5352893B2 (ja) * 2008-04-14 2013-11-27 東洋炭素株式会社 炭素繊維炭素複合成形体及び炭素繊維強化炭素複合体材料並びにその製造方法
JP5392236B2 (ja) * 2010-10-27 2014-01-22 株式会社デンソー 炭化珪素単結晶の製造装置および製造方法
JP5671375B2 (ja) * 2011-03-04 2015-02-18 大阪ガスケミカル株式会社 成形断熱材及びその製造方法
KR101253205B1 (ko) 2011-03-08 2013-04-09 오씨아이 주식회사 불융화 탄소질 섬유를 이용한 단열재의 제조방법
CN103373014B (zh) * 2012-04-25 2016-05-18 嘉兴启晟碳材料有限公司 一种保温材料及其制备方法
CN103193495A (zh) * 2013-03-01 2013-07-10 辽阳金谷碳纤维科技有限公司 拉晶炉用保温材料的生产方法
CN103448309A (zh) * 2013-09-03 2013-12-18 苏州天脉导热科技有限公司 一种热扩散复合材料
TWI604655B (zh) 2014-08-08 2017-11-01 Kureha Corp Non-aqueous electrolyte secondary battery negative carbonaceous material
TWI599092B (zh) 2014-08-08 2017-09-11 Kureha Corp Non-Aqueous Electrolyte Secondary Battery Negative Carbonaceous Material
TWI565654B (zh) 2014-08-08 2017-01-11 Kureha Corp Production method of carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery and carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery
KR101575989B1 (ko) * 2014-12-24 2015-12-09 고영신 팽창흑연을 이용한 경량화된 흡음내화 단열재 및 그 제조방법
JP6546489B2 (ja) * 2015-09-16 2019-07-17 大阪ガスケミカル株式会社 表面処理された成形断熱材及びその製造方法
JP6764317B2 (ja) * 2016-03-18 2020-09-30 大阪ガスケミカル株式会社 表面層付き成形断熱材及びその製造方法
JP6742855B2 (ja) * 2016-08-10 2020-08-19 大阪ガスケミカル株式会社 成形断熱材及びその製造方法
WO2019087846A1 (ja) * 2017-10-30 2019-05-09 大阪ガスケミカル株式会社 表面層付き成形断熱材及びその製造方法
KR102279605B1 (ko) 2018-06-06 2021-07-22 가부시끼가이샤 구레하 비수 전해질 이차전지 음극용 탄소질 재료의 제조방법 및 제조장치
JP7174094B2 (ja) * 2021-03-17 2022-11-17 大阪ガスケミカル株式会社 表面層付き成形断熱材及びその製造方法
JP2023019719A (ja) * 2021-07-29 2023-02-09 イビデン株式会社 断熱材および断熱材の製造方法
JP2024078024A (ja) * 2022-11-29 2024-06-10 イビデン株式会社 断熱材
JP2024078023A (ja) * 2022-11-29 2024-06-10 イビデン株式会社 断熱材及び断熱材の製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54152073A (en) * 1978-05-22 1979-11-29 Toho Rayon Co Ltd Method of forming low-density, high-elasticity composite material
JPS6025540B2 (ja) * 1981-09-29 1985-06-19 イソライト・バブコツク耐火株式会社 膨張性セラミツクフアイバ−フエルト
JP2603087B2 (ja) * 1987-11-07 1997-04-23 イビデン株式会社 炭素成形体
JPH0365580A (ja) * 1989-07-31 1991-03-20 Fuji Denpa Kogyo Kk 複合体断熱材
JPH03248838A (ja) * 1990-02-27 1991-11-06 Osaka Gas Co Ltd 断熱材
US5766745A (en) * 1996-02-09 1998-06-16 Smith; W. Novis Fire blocking textile insulation
JP3653647B2 (ja) * 1996-05-31 2005-06-02 イビデン株式会社 シリコン単結晶引き上げ装置用の保温筒
JPH1072292A (ja) * 1996-08-30 1998-03-17 Ibiden Co Ltd シリコン単結晶引き上げ装置用の保温筒

Also Published As

Publication number Publication date
JP4361636B2 (ja) 2009-11-11
TW539612B (en) 2003-07-01
JP2000327441A (ja) 2000-11-28
KR100634935B1 (ko) 2006-10-17
WO2000073243A1 (fr) 2000-12-07
EP1184356A4 (en) 2006-04-05
EP1184356A1 (en) 2002-03-06
KR20020025875A (ko) 2002-04-04
CN1358162A (zh) 2002-07-10
US6686048B1 (en) 2004-02-03

Similar Documents

Publication Publication Date Title
CN1189430C (zh) 复合碳质隔热材料及其制造方法
US5707471A (en) Method for making ceramic matrix composites
US4476178A (en) Composite silicon carbide coatings for carbon-carbon materials
CN110423119B (zh) 一种耐烧蚀C/SiC陶瓷基复合材料的制备方法
JP2009513805A (ja) 炭化ケイ素前駆体とその使用
US5837364A (en) Ceramic matrix composites using modified hydrogen silsesquioxane resin
EP0549224B1 (en) Ceramic matrix composites and method for making same
JP4539014B2 (ja) 耐酸化性ｃ／ｃ複合材及びその製造方法
CN101555164B (zh) 提高碳化硅泡沫陶瓷高温抗氧化性能的表面涂层制备方法
KR100520436B1 (ko) 탄소/탄소 복합재료의 내산화 복합코팅방법
JP3749268B2 (ja) Ｃ／ｃ複合材の耐酸化被覆層
US5411762A (en) Method of obtaining a sialon-based ceramic material by reducing an aluminosilicate material, and use thereof in forming a ceramic coating on a refractory substrate
JP2002104892A (ja) セラミックス複合材料
CN112142499A (zh) 在碳/碳复合材料表面制备SiO2-SiC镶嵌结构微孔抗氧化涂层的方法
CA2105584A1 (en) Coatings for composite articles
JPH0291270A (ja) 耐酸化性炭素繊維強化炭素材料およびその製造方法
KR102368368B1 (ko) 실리콘 잉곳 성장로 Spill Tray용 내화단열재
JPH08119741A (ja) 炭素−炭化ホウ素焼結体及び炭素−炭化ホウ素−炭化ケイ素焼結体
JPH0826859A (ja) 耐酸化性ｃ／ｃ複合材とその製造法
RU2276661C2 (ru) Способ обработки изделий из керамических материалов на основе карбида кремния и/или углерода
JPH0274671A (ja) 耐酸化性炭素繊維強化炭素材料およびその製造方法
JP2000219584A (ja) 炭化ケイ素被覆した炭素繊維強化炭素複合材料及びその製造方法
KR20210152785A (ko) 실리콘 잉곳 성장로 Spill Tray용 내화단열재의 제조방법
JPH04325481A (ja) 炭素繊維強化炭素複合材の耐酸化処理法
CN117125991A (zh) 一种混合一体式制备硼化物超高温陶瓷涂层的方法

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: KUREHA CORP.

Free format text: FORMER NAME OR ADDRESS: KUREHA CHEMICAL INDUSTRY CO., LTD.

CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: Kureha Corp.

Address before: Tokyo, Japan

Patentee before: Kureha Chemical Industry Co., Ltd.

CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20050216