CN111943703A - 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法 - Google Patents

一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法 Download PDF

Info

Publication number
CN111943703A
CN111943703A CN202010795440.6A CN202010795440A CN111943703A CN 111943703 A CN111943703 A CN 111943703A CN 202010795440 A CN202010795440 A CN 202010795440A CN 111943703 A CN111943703 A CN 111943703A
Authority
CN
China
Prior art keywords
graphite
heating
preform
silicon carbide
silicon
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.)
Pending
Application number
CN202010795440.6A
Other languages
English (en)
Inventor
黄英
彭轩懿
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.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
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 Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN202010795440.6A priority Critical patent/CN111943703A/zh
Publication of CN111943703A publication Critical patent/CN111943703A/zh
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C04B35/522—Graphite
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • 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
    • C04B35/6303—Inorganic additives
    • 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
    • C04B35/6303—Inorganic additives
    • C04B35/6316—Binders based on silicon compounds
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5244—Silicon carbide
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6022—Injection moulding
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • 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
    • C04B2235/656—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
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/6565—Cooling rate
    • 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
    • C04B2235/6567—Treatment time
    • 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

Landscapes

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

Abstract

本发明提供了一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，通过硅气凝胶原位固化原料粉末制成生坯，并进行高温处理以获得碳化硅纤维增强的石墨预制体，本发明能够制备出力学强度高、孔隙分布均匀、可近净尺寸成型的碳化硅纤维增强石墨预制体。

Description

一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法
技术领域
本发明属于复合材料领域，涉及一种制备石墨预制体的方法。
背景技术
随着电子器件的集成度越来越高以及能耗越来越大，电子封装领域对热管理材料的需求也在不断增长。铝基石墨复合材料因为具有较高的导热率、与电子元件相匹配的热膨胀系数以及较低的密度，因此具有很好的应用前景。目前石墨增强铝基复合材料的常用制备方法包括挤压浸渗、气压浸渗和无压浸渗，此三种方法均需制备石墨预制体，因此能够快速制备石墨均匀分布并具有一定力学性能的预制体非常重要。
目前常见的石墨预制体制备方法包括模压成型法和注射成型法。模压成型法是指把粘结剂、造孔剂等与石墨颗粒进行均匀混合，压制成型后进行高温造孔的方法。其具有步骤简单、设备要求低、生产周期快、生产成本低等优点。但是通过模压成型法制备的预制体孔隙不能均匀分布于预制体中，铝液浸渍后基体与石墨之间不能均匀间隔，造成复合材料的局部性能有差异，均一性较差。另外，模压成型法制备的石墨在造孔过程中坯体会不受约束的膨胀，不能精确控制预制体的尺寸，需要后期加工才能进行下一步的浸渍过程。注射成型法是指将有机烃类溶剂与原料粉末进行均匀混合后并通过注射机注射进入模具成型的方法。其具有生产速度快、预制体尺寸易控制以及造孔均匀的优点。但是注射成型法制备的预制体需要进行排蜡，排蜡的周期长而且耗能高，排蜡后的预制体强度也比较弱。本发明通过引入硅气凝胶制备石墨预制体，其具有孔隙分布均匀、生产周期短、耗能低以及可近净尺寸成型的特点。
为了提高预制体的力学强度，需要添加第二增强相来提高复合材料的综合性能。碳化硅纤维具有高比强度、高硬度、耐磨性好的特点，因此在预制体中添加碳化硅纤维对于复合材料的力学性能会有显著提升。常见的碳化硅纤维制备方法包括化学气相沉积法、前驱体衍生法和活性炭纤维转化法。此三种方法制备出的碳化硅纤维需要二次添加并与石墨机械混合后制备预制体，不能进行一体化成型，而且碳化硅纤维易团聚，在预制体中不易分散，因此获得的复合材料的均一性较差。
如何采用硅气凝胶原位固化法制备出碳化硅纤维均匀分布于石墨之间的预制体，使其具有力学强度高、孔隙分布均匀、可近净尺寸成型的特点，将是铝基复合材料所面临的挑战。
发明内容
为了克服现有技术的不足，本发明提供一种石墨预制体的制备方法，通过硅气凝胶原位固化原料粉末制成生坯，并进行高温处理以获得碳化硅纤维增强的石墨预制体，本发明能够制备出力学强度高、孔隙分布均匀、可近净尺寸成型的碳化硅纤维增强石墨预制体。
本发明解决其技术问题所采用的方案包括以下步骤：
(1)将氢氧化钠、无水碳酸钠、磷酸钠、鳞片石墨、蒸馏水按照摩尔比1:(0.1～0.3):(0.06～0.18):(0.8～1.6):(7～14)称量后混合，升温至100℃后搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干得到所需石墨；
(2)将步骤(1)中所得的石墨浸没至浓硫酸中，升温至100℃搅拌15min，用蒸馏水稀释至石墨和浓硫酸总体积的10～15倍后进行抽滤，然后用蒸馏水清洗3～5遍，烘干得到所需石墨；
(3)将正硅酸乙酯、异丙醇、N,N-二甲基甲酰胺、去离子水、盐酸、步骤(2)所得的石墨、氨水按照摩尔比1:6:(0.5～1):(2～6):1.8×10-3:(1～2):14.4×10-3依次量取后搅拌均匀得到浆料；
(4)将浆料注射入模具中，凝胶后进行脱模得到预制体；
(5)将预制体在60～200℃条件下加温干燥18～36h；
(6)将硅气凝胶增强的石墨预制体进行分段式加热，在氩气气氛下以3℃/min升温至1300～1500℃，并在最高温度保温2～4h，保温结束后以5℃/min降温至室温，得到碳化硅纤维增强的石墨复合材料。
步骤(1)中所用石墨为500～800目。
步骤(3)中所用盐酸质量浓度为36～38％，氨水质量浓度为25～28％。
步骤(4)中凝胶时间为30～60min。
步骤(5)中将预制体进行分段式加温干燥，升温至80℃保温6～12h，升温至110℃保温6～12h，升温至180℃保温6～12h，得到硅气凝胶增强的石墨预制体。
本发明的有益效果是：通过硅气凝胶原位固化鳞片石墨制成生坯，并进行高温处理以获得碳化硅纤维增强的石墨预制体，相比于传统的制备方法具有以下优点：1)用硅气凝胶所制备的生坯干燥后，孔隙分布均匀，材料的均一性好；2)生坯的制备过程不需要进行脱脂以及排胶，因此生坯的制备耗能少、周期短；3)由于硅气凝胶在生坯中以网络结构均匀的分布，因此高温处理后所获得的碳化硅纤维也可以均匀的分布在预制体中，进行浸渗后所获得的复合材料的性能也会比较均一；4)由于碳化硅纤维具有高模量以及高硬度的特性，因此可以很大程度的提升复合材料的力学性能，并且由于碳化硅纤维网络结构具有比二氧化硅网络结构更高的导热性能，因此也可在一定程度上提高复合材料的导热率；5)硅气凝胶在凝胶时是对鳞片石墨进行原位固化，并且由于干燥时添加了一定量的二甲基丙烯酰胺，因此生坯变形小，而且高温处理生坯时也不发生形变，因此所获得预制体可用于近净尺寸成型。
附图说明
图1是碳化硅纤维增强石墨预制体制备工艺流程图；
图2是S经高温处理后的预制体及其表面元素C、O、Si的分布图。
具体实施方式
下面结合附图和实施例对本发明进一步说明，本发明包括但不仅限于下述实施例。
本发明提供了通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，包括以下步骤：
(1)将氢氧化钠、无水碳酸钠、磷酸钠、鳞片石墨、蒸馏水按照摩尔比1:0.1～0.3:0.06～0.18:0.8～1.6:7～14称量后放入烧杯中，升温至100℃后搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干备用；
(2)将步骤(1)中干燥好的石墨倒入烧杯中，加浓硫酸至没过石墨，升温至100℃搅拌15min，用蒸馏水稀释至原石墨和浓硫酸总体积的10～15倍后进行抽滤，然后用蒸馏水清洗3～5遍，烘干备用；
(3)将正硅酸乙酯、异丙醇、N,N-二甲基甲酰胺、去离子水、盐酸、石墨、氨水按照摩尔比1:6:0.5～1:2～6:1.8×10-3:1～2:14.4×10-3依次量取后添加进入烧杯中，搅拌均匀得到浆料；
(4)将浆料注射入模具中，凝胶后进行脱模；
(5)将预制体置于控温炉中进行分段式加温干燥，即将生坯放入干燥箱中升温至80℃保温6～12h，升温至110℃保温6～12h，升温至180℃保温6～12h，得到硅气凝胶增强的石墨预制体；
(6)将预制体置于管式炉中进行分段式加热，即将预制体放入管式炉中，通入氩气气氛，以3℃/min升温至1300～1500℃，并在最高温度保温2～4h，保温结束后以5℃/min降温至室温，可以得到碳化硅纤维增强的石墨复合材料；
步骤(1)中所用石墨为500～800目。
步骤(3)中所用盐酸质量浓度为36～38％，氨水质量浓度为25～28％。
步骤(4)中凝胶时间为30～60min。
步骤(5)中所述烧结温度为60～200℃，时间为18～36h。
实施例1：
①无水碳酸钠50g、称取氢氧化钠200g、磷酸钠50g、500-800目鳞片石墨50g放入2L烧杯中，加水至2L后升温至100℃搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干备用；②将步骤①中石墨倒入烧杯中，加浓硫酸至没过石墨，升温至100℃搅拌15min，用水稀释后进行抽滤，然后用蒸馏水清洗3～5遍，烘干备用；③依次添加3ml正硅酸乙酯、10ml异丙醇、0.5mlN,N-二甲基甲酰胺、0.6ml去离子水、0.01ml盐酸进入烧杯中，水解2h后加入10g步骤②中的石墨，搅拌均匀；④加入0.04ml氨水进入烧杯中，搅拌均匀后倒入模具中，等待凝胶后进行脱模；⑤将生坯放入干燥箱中升温至80℃保温6h，升温至110℃保温6h，升温至180℃保温6h即得到预制体。⑥将预制体置于管式炉中进行分段式加热，即将预制体放入管式炉中，通入氩气气氛，以3℃/min升温至1300℃，并在最高温度保温2h，保温结束后以5℃/min降温至室温。测量结果：预制体中没有发现碳化硅纤维；预制体的孔隙率为48％。
实施例2：
①无水碳酸钠50g、称取氢氧化钠200g、磷酸钠50g、500-800目鳞片石墨50g放入2L烧杯中，加水至2L后升温至100℃搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干备用；②将步骤①中石墨倒入烧杯中，加浓硫酸至没过石墨，升温至100℃搅拌15min，用水稀释后进行抽滤，然后用蒸馏水清洗3～5遍，烘干备用；③依次添加3ml正硅酸乙酯、10ml异丙醇、0.5mlN,N-二甲基甲酰胺、0.6ml去离子水、0.01ml盐酸进入烧杯中，水解2h后加入10g步骤②中的石墨，搅拌均匀；④加入0.04ml氨水进入烧杯中，搅拌均匀后倒入模具中，等待凝胶后进行脱模；⑤将生坯放入干燥箱中升温至80℃保温6h，升温至110℃保温6h，升温至180℃保温6h即得到预制体。⑥将预制体置于管式炉中进行分段式加热，即将预制体放入管式炉中，通入氩气气氛，以3℃/min升温至1400℃，并在最高温度保温2h，保温结束后以5℃/min降温至室温。测量结果：预制体中发现少量碳化硅纤维，纤维直径可以达到60nm；预制体的孔隙率为46％。
实施例3：
①无水碳酸钠50g、称取氢氧化钠200g、磷酸钠50g、500-800目鳞片石墨50g放入2L烧杯中，加水至2L后升温至100℃搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干备用；②将步骤①中石墨倒入烧杯中，加浓硫酸至没过石墨，升温至100℃搅拌15min，用水稀释后进行抽滤，然后用蒸馏水清洗3～5遍，烘干备用；③依次添加3ml正硅酸乙酯、10ml异丙醇、0.5mlN,N-二甲基甲酰胺、0.6ml去离子水、0.01ml盐酸进入烧杯中，水解2h后加入10g步骤②中的石墨，搅拌均匀；④加入0.04ml氨水进入烧杯中，搅拌均匀后倒入模具中，等待凝胶后进行脱模；⑤将生坯放入干燥箱中升温至80℃保温6h，升温至110℃保温6h，升温至180℃保温6h即得到预制体。⑥将预制体置于管式炉中进行分段式加热，即将预制体放入管式炉中，通入氩气气氛，以3℃/min升温至1500℃，并在最高温度保温2h，保温结束后以5℃/min降温至室温。测量结果：预制体中发现大量碳化硅纤维，纤维直径可以达到130nm；预制体的孔隙率为47％。

Claims (5)

1.一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，其特征在于包括以下步骤：
(1)将氢氧化钠、无水碳酸钠、磷酸钠、鳞片石墨、蒸馏水按照摩尔比1:(0.1～0.3):(0.06～0.18):(0.8～1.6):(7～14)称量后混合，升温至100℃后搅拌15min，抽滤并用蒸馏水清洗3～5遍，烘干得到所需石墨；
(2)将步骤(1)中所得的石墨浸没至浓硫酸中，升温至100℃搅拌15min，用蒸馏水稀释至石墨和浓硫酸总体积的10～15倍后进行抽滤，然后用蒸馏水清洗3～5遍，烘干得到所需石墨；
(3)将正硅酸乙酯、异丙醇、N,N-二甲基甲酰胺、去离子水、盐酸、步骤(2)所得的石墨、氨水按照摩尔比1:6:(0.5～1):(2～6):1.8×10-3:(1～2):14.4×10-3依次量取后搅拌均匀得到浆料；
(4)将浆料注射入模具中，凝胶后进行脱模得到预制体；
(5)将预制体在60～200℃条件下加温干燥18～36h；
(6)将硅气凝胶增强的石墨预制体进行分段式加热，在氩气气氛下以3℃/min升温至1300～1500℃，并在最高温度保温2～4h，保温结束后以5℃/min降温至室温，得到碳化硅纤维增强的石墨复合材料。
2.根据权利要求1所述的通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，其特征在于：步骤(1)中所用石墨为500～800目。
3.根据权利要求1所述的通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，其特征在于：步骤(3)中所用盐酸质量浓度为36～38％，氨水质量浓度为25～28％。
4.根据权利要求1所述的通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，其特征在于：步骤(4)中凝胶时间为30～60min。
5.根据权利要求1所述的通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法，其特征在于：步骤(5)中将预制体进行分段式加温干燥，升温至80℃保温6～12h，升温至110℃保温6～12h，升温至180℃保温6～12h，得到硅气凝胶增强的石墨预制体。
CN202010795440.6A 2020-08-10 2020-08-10 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法 Pending CN111943703A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010795440.6A CN111943703A (zh) 2020-08-10 2020-08-10 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010795440.6A CN111943703A (zh) 2020-08-10 2020-08-10 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法

Publications (1)

Publication Number Publication Date
CN111943703A true CN111943703A (zh) 2020-11-17

Family

ID=73331936

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010795440.6A Pending CN111943703A (zh) 2020-08-10 2020-08-10 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法

Country Status (1)

Country Link
CN (1) CN111943703A (zh)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050133963A1 (en) * 2003-12-18 2005-06-23 The Regents Of The University Of California, A California Corporation Silicon carbide whisker-reinforced ceramics with low rate of grain size increase upon densification
CN102910926A (zh) * 2012-10-22 2013-02-06 南京工业大学 一种耐高温碳化硅气凝胶隔热复合材料的制备方法
JP2013522154A (ja) * 2010-03-16 2013-06-13 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 追加の強化材を使用した非反応性のろう付けによりＳｉＣ系材料製の部品を接合する方法、ろう付け組成物、ならびにそのような方法により得られる接合部および組付体
CN104030716A (zh) * 2014-06-09 2014-09-10 西北工业大学 溶胶凝胶法原位合成SiC纳米线改性碳/碳复合材料预制体的方法
CN104988658A (zh) * 2015-07-13 2015-10-21 浙江理工大学 一种SiC纳米纤维非织造材料的制备方法
CN105503227A (zh) * 2015-12-25 2016-04-20 苏州宏久航空防热材料科技有限公司 一种立体织物增强碳化硅-金刚石复合材料的制备方法
CN106119967A (zh) * 2016-06-21 2016-11-16 浙江理工大学 连续两步制备单晶碳化硅/石墨烯复合纳米纤维的方法
CN106544552A (zh) * 2016-11-07 2017-03-29 西北工业大学 一种表面处理石墨/低硅混杂增强铝基复合材料及其制备工艺
CN109970429A (zh) * 2019-02-18 2019-07-05 西北工业大学深圳研究院 硅气凝胶原位固化制备石墨增强金属基复合材料预制体的方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050133963A1 (en) * 2003-12-18 2005-06-23 The Regents Of The University Of California, A California Corporation Silicon carbide whisker-reinforced ceramics with low rate of grain size increase upon densification
JP2013522154A (ja) * 2010-03-16 2013-06-13 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 追加の強化材を使用した非反応性のろう付けによりＳｉＣ系材料製の部品を接合する方法、ろう付け組成物、ならびにそのような方法により得られる接合部および組付体
CN102910926A (zh) * 2012-10-22 2013-02-06 南京工业大学 一种耐高温碳化硅气凝胶隔热复合材料的制备方法
CN104030716A (zh) * 2014-06-09 2014-09-10 西北工业大学 溶胶凝胶法原位合成SiC纳米线改性碳/碳复合材料预制体的方法
CN104988658A (zh) * 2015-07-13 2015-10-21 浙江理工大学 一种SiC纳米纤维非织造材料的制备方法
CN105503227A (zh) * 2015-12-25 2016-04-20 苏州宏久航空防热材料科技有限公司 一种立体织物增强碳化硅-金刚石复合材料的制备方法
CN106119967A (zh) * 2016-06-21 2016-11-16 浙江理工大学 连续两步制备单晶碳化硅/石墨烯复合纳米纤维的方法
CN106544552A (zh) * 2016-11-07 2017-03-29 西北工业大学 一种表面处理石墨/低硅混杂增强铝基复合材料及其制备工艺
CN109970429A (zh) * 2019-02-18 2019-07-05 西北工业大学深圳研究院 硅气凝胶原位固化制备石墨增强金属基复合材料预制体的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨毅文等: "石墨/铝复合材料制备中的关键问题及其对策", 《材料开发与应用》 *

Similar Documents

Publication Publication Date Title
CN103130525B (zh) 一种高韧性多孔SiC陶瓷复杂零件的制备方法
CN100482614C (zh) 利用胶态成型工艺制备轻质、高强度陶瓷材料的方法
CN111039295B (zh) 一步法制备二氧化硅气凝胶以及自疏水型二氧化硅气凝胶保温毡垫的方法
CN111320484B (zh) 各向同性氮化硅晶须增强氮化物复合材料天线罩的制备方法
CN107602127B (zh) SiC空心球及其制备方法
CN110130530B (zh) 一种建筑连锁砌块及其使用的保温砂浆
CN112011151B (zh) 一种蜂窝状树脂材料的制备方法
CN101698605B (zh) 一种梯度多孔氧化铝陶瓷的制备方法
CN109020469A (zh) 一种SiO2气凝胶/SiC泡沫复合绝热材料及其制备方法
CN113800837B (zh) 连续碳纤维增强磷酸基地质聚合物复合材料及其制备方法
CN109180194B (zh) 一种SiC基复合材料的不同状态前驱体浸渍裂解的复合增密方法
CN108609606B (zh) 一种炭气凝胶隔热材料的制备方法
CN111943703A (zh) 一种通过硅气凝胶制备碳化硅纤维增强石墨预制体的方法
CN109970429B (zh) 硅气凝胶原位固化制备石墨增强金属基复合材料预制体的方法
CN114436674B (zh) 一种网络状碳化硅纤维的制备方法
CN114956848B (zh) 带有石墨高效阻隔层的一体化筒形隔热材料的制备方法
CN113831102B (zh) 连续玄武岩纤维增强磷酸基地质聚合物复合材料及其制备方法
CN203200178U (zh) 带等压回收装置的真空热压罐
CN105904584A (zh) 一种干压成型碳纤维水泥基复合材料的养护方法
CN113698220A (zh) 一种纤维增强碳化硅复合材料的制备方法及纤维增强碳化硅复合材料
CN116354735B (zh) 一种快速制备AlN改性C/C-SiC摩擦材料的方法
CN104250107A (zh) 一种泡沫炭表面原位合成Si3N4涂层的方法
CN116239393B (zh) 一种硬质碳纤维保温毡及其制备方法
CN116730736B (zh) 一种基于激光打印与真空-压力辅助原位浸渗树脂预增密的SiC复合材料的制备方法
CN109265173B (zh) 用于复合材料制动耐磨部件的SiC连续骨架制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201117