CN112479717B - 一种自愈合基体改性SiC/SiC复合材料及其制备方法 - Google Patents

一种自愈合基体改性SiC/SiC复合材料及其制备方法 Download PDF

Info

Publication number
CN112479717B
CN112479717B CN202011306589.XA CN202011306589A CN112479717B CN 112479717 B CN112479717 B CN 112479717B CN 202011306589 A CN202011306589 A CN 202011306589A CN 112479717 B CN112479717 B CN 112479717B
Authority
CN
China
Prior art keywords
sic
sample
composite material
chemical vapor
vapor deposition
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.)
Active
Application number
CN202011306589.XA
Other languages
English (en)
Other versions
CN112479717A (zh
Inventor
宋环君
于艺
刘伟
金鑫
王鹏
李晓东
于新民
刘俊鹏
裴雨辰
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.)
Aerospace Research Institute of Materials and Processing Technology
Original Assignee
Aerospace Research Institute of Materials and Processing Technology
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 Aerospace Research Institute of Materials and Processing Technology filed Critical Aerospace Research Institute of Materials and Processing Technology
Priority to CN202011306589.XA priority Critical patent/CN112479717B/zh
Publication of CN112479717A publication Critical patent/CN112479717A/zh
Application granted granted Critical
Publication of CN112479717B publication Critical patent/CN112479717B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
    • C04B35/571—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 carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • 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
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/6286—Carbides
    • C04B35/62863—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
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/62865—Nitrides
    • C04B35/62868—Boron nitride
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62884—Coating the powders or the macroscopic reinforcing agents by gas phase techniques
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62894—Coating the powders or the macroscopic reinforcing agents with more than one coating layer
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
    • 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
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/386—Boron nitrides
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

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

Abstract

本发明涉及一种自愈合基体改性SiC/SiC复合材料及其制备方法，属于航空航天材料制备工艺领域，所述制备方法包括如下步骤：选用SiC纤维编织成预制体，通过化学气相沉积工艺在纤维表面沉积一层BN界面层，厚度为200～1000nm，然后在BN界面层外层沉积一层SiC层，厚度为2～5μm。最后再配制特定料浆，经过8～12个周期的浸渍‑固化‑烧结循环操作，得到目标SiC/SiC复合材料。相比于具有传统的陶瓷前驱体烧结基体，新型自愈合基体将有效提高SiC/SiC循环应力氧化性能。

Description

一种自愈合基体改性SiC/SiC复合材料及其制备方法
技术领域
本发明涉及航空航天材料制备工艺技术领域，尤其涉及一种自愈合基体改性SiC/SiC复合材料制备方法。
背景技术
SiC/SiC复合材料具有轻质、高强度、高模量和优异的高温抗氧化性能，是未来航空发动机取代镍基高温合金提高推重比的关键材料。从二十世纪八十年代开始，美国和法国等西方发达国家对SiC/SiC复合材料进行了大量研究，已经打通了材料攻关、构件验证和装备应用完整的产业链。与国外发达国家相比，我国对于SiC/SiC复合材料的研究仍处于材料攻关阶段。
SiC/SiC复合材料通常由纤维预制体、界面层和陶瓷基体等部分组成。其中纤维是复合材料的骨架，对于力学性能至关重要，通常根据不同的应用环境，可选择2D、2.5D和3D等多种编织方法。陶瓷基体是SiC/SiC复合材料抗热冲击和高温抗氧化部分，其在应力条件下，尤其是高温氧化应力条件下的失效机理是基体微裂纹的产生，氧化气氛通过裂纹进入复合材料内部，腐蚀界面和纤维，导致复合材料破坏。
前驱体浸渍裂解是制备SiC/SiC复合材料常用工艺，其具有工艺简单、稳定的优点。传统的SiC前驱体制备的SiC/SiC复合材料基体内部微孔较多，在高温氧化应力条件下容易产生微裂纹，影响复合材料的力学性能和抗氧化性能。而传统的SiC前驱体制备的SiC陶瓷基体不具有自愈合能力，因此急需对基体进行改性，使基体具备修复裂纹的能力，提高SiC/SiC复合材料在高温应力氧化环境下的使用寿命。
因此，针对以上不足，需要提供一种自愈合基体改性SiC/SiC复合材料的制备方法。
发明内容
(一)要解决的技术问题
本发明要解决的技术问题是现有SiC/SiC复合材料基体在高温应力氧化环境使用寿命不足的问题。
(二)技术方案
为了解决上述技术问题，本发明在第一方面提供了一种自愈合基体改性SiC/SiC复合材料的制备方法，所述制备方法包括如下步骤：
(1)采用SiC纤维制备SiC纤维预制体，得到第一试样；
(2)采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；
(3)采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；
(4)配制料浆；
(5)将第三试样放入料浆中浸渍，得到第四试样；
(6)对第四试样进行固化反应，得到第五试样；
(7)对第五试样进行烧结反应，得到第六试样；
(8)重复步骤(4)至步骤(7)至少一次，得到自愈合基体改性SiC/SiC复合材料。
本发明在第二方面提供了一种自愈合基体改性SiC/SiC复合材料，所述复合材料按照本发明第一方面所述的制备方法制备得到。
(三)有益效果
本发明的上述技术方案具有如下优点：
(1)本发明采用了宽温域范围具有高温应力氧化环境使用寿命的陶瓷基体。
(2)本发明所述自愈合基体能实现700～1400℃基体自愈合能力，其原因是在传统SiC/SiC复合材料中引入了多种粉体，粉体自身或其氧化产物分别在700～1100℃、1100～1250℃、1250～1400℃宽温度范围内变为流动相，能良好填充基体裂纹，实现700～1400℃宽温域基体自愈合。
(3)本发明所述自愈合基体能明显提高复合材料氧化环境中高温力学性能，也能明显提高SiC/SiC复合材料循环应力氧化性能。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明在第一方面提供了一种自愈合基体改性SiC/SiC复合材料的制备方法，所述制备方法包括如下步骤：
(1)采用SiC纤维制备SiC纤维预制体，得到第一试样；
(2)采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；
(3)采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；
(4)配制料浆；
(5)将第三试样放入料浆中浸渍，得到第四试样；
(6)对第四试样进行固化反应，得到第五试样；
(7)对第五试样进行烧结反应，得到第六试样；
(8)重复步骤(4)至步骤(7)至少一次，得到自愈合基体改性SiC/SiC复合材料。
根据一些优选的实施方式，在步骤(1)中，所述SiC纤维为一代纤维或二代纤维；
所述制备SiC纤维预制体的方式为编织方式；
优选的是，所述编织方式为缝合、2.5D和三维四向编织；和/或
所述SiC纤维预制体的纤维体积分数为25％～45％，例如，25％，27％，30％，32％，35％，37％，40％，42％，45％。
根据一些优选的实施方式，在步骤(2)中，所述化学沉积法在化学气相沉积炉中进行；
所述化学沉积法采用的前驱体气体包含硼源、氮气和氢气，所述硼源选自由三氯化硼、三氟化硼和硼吖嗪组成的组的一种或多种；
所述化学沉积法的沉积温度为800℃～1200℃(例如，800℃，900℃，1000℃，1100℃，1200℃)，真空度为-0.1～0MPa，沉积时间为0.5h～10h(例如，0.5h，1h，2h，3h，4h，5h，6h，7h，8h，9h，10h)；和/或
所述BN界面层的厚度为200～1000nm(例如，200nm，250nm，300nm，350nm，400nm，450nm，500nm，550nm，600nm，700nm，800nm，900nm，1000nm)。
根据一些优选的实施方式，在步骤(3)中，所述化学气相沉积法采用的前驱体可以选择氯代甲基硅烷、氟代甲基硅烷、硅烷、甲基硅烷等；
所述化学气相沉积法采用的沉积温度为800～1200℃(例如，800℃，900℃，1000℃，1100℃，1200℃)，真空度-0.09～-0.01MPa，沉积时间为10-20h(例如为10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h)；
所述SiC界面层厚度为2～5μm。
根据一些优选的实施方式，在步骤(4)中，所述料浆由粉末材料和前驱体溶液配制；
优选的是，所述粉末材料包含选自由碳化锗(GeC)、氧化锗(GeO2)、SiC、SiO2、BN、B2O3、CuO组成的组的两种或者三种；和/或
所述前驱体溶液的溶质可以选择聚碳硅烷(PCS)、全氢聚碳硅烷(AHPCS)、液态聚碳硅烷(LPCS)等；所述前驱体溶液的溶剂可以选择丁酮、二甲苯、甲苯等。
根据一些优选的实施方式，在步骤(5)中，所述浸渍的浸渍温度为60～130℃(例如，60℃，70℃，80℃，90℃，100℃，110℃，120℃，130℃)，浸渍压力为1～5MPa(例如，1MPa，2MPa，3MPa，4MPa，5MPa)，浸渍时间为0.5～4h(例如，0.5h，1h，1.5h，2h，2.5h，3h，3.5h，4h)。
根据一些优选的实施方式，在步骤(6)中，所述固化反应在高压罐中进行；
所述固化反应的固化温度为100～320℃(例如100℃，150℃，200℃，250℃，300℃，320℃)，固化时间为1～5h，固化压力为3～5MPa。
根据一些优选的实施方式，在步骤(7)中，所述烧结反应在高温烧结炉中进行；
优选的是，所述烧结反应的烧结温度为700～1400℃(例如，700℃，800℃，900℃，1000℃，1100℃，1200℃，1300℃，1400℃)，烧结真空为-0.09～-0.1MPa，烧结时间为2～4h。
根据一些优选的实施方式，在步骤(8)中，所述重复的次数为8到12次。
本发明在第二方面提供了一种自愈合基体改性SiC/SiC复合材料，所述复合材料按照本发明第一方面所述的制备方法制备得到。
实施例1
(1)将二代SiC纤维编织为2.5D预制体，得到纤维体积分数为32％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在1000℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积1h，得到500nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在1200℃、-0.05MPa真空度条件下沉积20h，得到含有厚度为2μm SiC界面层的第三试样；
(4)选取等摩尔比的GeC、BN和SiC粉体与聚碳硅烷二甲苯溶液配制成固含量为30％的前驱体料浆，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在150℃、3MPa压力条件下，将第四试样放入高压罐中进行固化3h，得到第五试样；
(6)在850℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结3h，取出得到第六试样；
(7)重复步骤(4)至步骤(6)，重复次数为8次；
将步骤(7)所得样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为274MPa，拉伸强度为159MPa。1200℃、100MPa、1h循环拉伸次数为9次；具体见表1。
实施例2
本实施例2与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的SiO2、B2O3和CuO。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为293MPa，拉伸强度为170MPa。1200℃、100MPa、1h循环拉伸次数为13次；具体见表1。
实施例3
本实施例3与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的BN和GeC。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为295MPa，拉伸强度为168MPa。1200℃、100MPa、1h循环拉伸次数为16次；具体见表1。
实施例4
本实施例4与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的GeC和SiC。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为287MPa，拉伸强度为154MPa。1200℃、100MPa、1h循环拉伸次数为12次；具体见表1。
实施例5
(1)将一代SiC纤维通过三维四向编织制备为预制体，得到纤维体积分数为45％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在800℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积10h，得到1000nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在800℃、-0.05MPa真空度条件下沉积10h，得到含有厚度为5μm SiC界面层的第三试样；
(4)选取等摩尔比的GeC、CuO、SiC粉体与全氢聚碳硅烷甲苯溶液配制成固含量为30％的前驱体料浆，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在320℃、3MPa压力条件下，将第四试样放入高压罐中进行固化5h，得到第五试样；
(6)在1400℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结4h，取出得到第六试样；
(7)重复步骤4至步骤6，重复次数为8次。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为151MPa，拉伸强度为107MPa。1200℃、100MPa、1h循环拉伸次数为3次；具体见表1。
实施例6
(1)将二代SiC纤维编织为2.5D预制体，得到纤维体积分数为32％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在1000℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积1h，得到500nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在1200℃、-0.05MPa真空度条件下沉积20h，得到含有厚度为2μm SiC界面层的第三试样；
(4)选取聚碳硅烷二甲苯溶液配制成前驱体溶液，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在150℃、3MPa压力条件下，将第四试样放入高压罐中进行固化3h，得到第五试样；
(6)在850℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结3h，取出得到第六试样；
(7)重复步骤4至步骤6，重复次数为8次。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为257MPa，拉伸强度为131MPa。1200℃、100MPa、1h循环拉伸次数为1次；具体见表1。
Figure BDA0002788033660000101
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

1.一种自愈合基体改性SiC/SiC复合材料的制备方法，其特征在于，所述制备方法包括如下步骤：
（1）采用SiC纤维制备SiC纤维预制体，得到第一试样；所述SiC纤维预制体的纤维体积分数为25%~45%；
（2）采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；所述BN界面层的厚度为500nm；
（3）采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；所述SiC界面层的厚度为2μm；所述化学气相沉积法采用的前驱体为氯代甲基硅烷；所述化学气相沉积法采用的沉积温度为1200℃，真空度-0.05MPa，沉积时间为20h；
（4）配制料浆；选取等摩尔比的GeC、BN粉体与前驱体溶液配制成固含量为30％的前驱体料浆；所述前驱体溶液的溶质选自由聚碳硅烷PCS、全氢聚碳硅烷AHPCS、液态聚碳硅烷LPCS组成的组的一种或多种；
（5）将第三试样放入料浆中浸渍，得到第四试样；
（6）对第四试样进行固化反应，得到第五试样；
（7）对第五试样进行烧结反应，得到第六试样；所述烧结反应的烧结温度为700~1400℃，烧结真空度为-0.09~-0.1MPa，烧结时间为2~4h；
（8）重复步骤（4）至步骤（7）至少一次，得到自愈合基体改性SiC/SiC复合材料。
2.根据权利要求1所述的制备方法，其特征在于：
在步骤（1）中，所述SiC纤维为一代纤维或二代纤维；
所述制备SiC纤维预制体的方式为编织方式；所述编织方式为缝合、2.5D和三维四向编织。
3.根据权利要求1所述的制备方法，其特征在于：
在步骤（2）中，所述化学气相沉积法在化学气相沉积炉中进行；
所述化学气相沉积法采用的前驱体气体包含硼源、氮气和氢气，所述硼源选自由三氯化硼、三氟化硼和硼吖嗪组成的组的一种或多种；
所述化学气相沉积法的沉积温度为800℃~1200℃，真空度为-0.1~0MPa，沉积时间为0.5h~10h。
4.根据权利要求1所述的制备方法，其特征在于：
在步骤（4）中，所述前驱体溶液的溶剂选自由丁酮、二甲苯、甲苯组成的组一种或多种。
5.根据权利要求1所述的制备方法，其特征在于：
在步骤（5）中，所述浸渍的浸渍温度为60~130℃，浸渍压力为1~5MPa，浸渍时间为0.5~4h。
6.根据权利要求1所述的制备方法，其特征在于：
在步骤（6）中，所述固化反应在高压罐中进行。
7.根据权利要求6所述的制备方法，其特征在于：
在步骤（6）中，所述固化反应的固化温度为100~320℃，固化时间为1~5h，固化压力为3~5MPa。
8.根据权利要求1所述的制备方法，其特征在于：
在步骤（7）中，所述烧结反应在高温烧结炉中进行。
9.根据权利要求1所述的制备方法，其特征在于：
在步骤（8）中，所述重复的次数为8到12次。
10.一种自愈合基体改性SiC/SiC复合材料，其特征在于：
所述复合材料按照权利要求1-9任一项所述的制备方法制备得到。
CN202011306589.XA 2020-11-19 2020-11-19 一种自愈合基体改性SiC/SiC复合材料及其制备方法 Active CN112479717B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011306589.XA CN112479717B (zh) 2020-11-19 2020-11-19 一种自愈合基体改性SiC/SiC复合材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011306589.XA CN112479717B (zh) 2020-11-19 2020-11-19 一种自愈合基体改性SiC/SiC复合材料及其制备方法

Publications (2)

Publication Number Publication Date
CN112479717A CN112479717A (zh) 2021-03-12
CN112479717B true CN112479717B (zh) 2022-10-14

Family

ID=74932533

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011306589.XA Active CN112479717B (zh) 2020-11-19 2020-11-19 一种自愈合基体改性SiC/SiC复合材料及其制备方法

Country Status (1)

Country Link
CN (1) CN112479717B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113800915B (zh) * 2021-09-07 2023-05-26 航天特种材料及工艺技术研究所 一种高致密SiC/SiC复合材料及其制备方法
CN113979752B (zh) * 2021-11-09 2023-02-21 航天特种材料及工艺技术研究所 一种莫来石纤维增强陶瓷基复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945166A (en) * 1997-12-30 1999-08-31 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for forming fiber reinforced composite bodies with graded composition and stress zones
EP1594816A1 (fr) * 2003-02-17 2005-11-16 Snecma Propulsion Solide Procede de siliciuration de materiaux composites thermostructuraux et pieces telles qu obtenues par le procede
US10590044B1 (en) * 2012-06-01 2020-03-17 United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Engineered matrix self-healing composites
US10654756B1 (en) * 2012-06-01 2020-05-19 United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Formulations for engineered ceramic matrix composites for high temperature applications

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10601049B2 (en) * 2015-08-31 2020-03-24 The Board Of Trustees Of The Leland Stanford Junior University High performance battery anodes with polymeric coatings including molecules cross-linked through dynamic bonds
CN106966738B (zh) * 2016-11-25 2018-02-23 北京航空航天大学 自愈合陶瓷基复合材料燃烧室火焰筒及其制备方法与应用
CN109553430A (zh) * 2019-01-16 2019-04-02 苏州宏久航空防热材料科技有限公司 一种具有复合界面的SiCf/SiC陶瓷基复合材料及其制备方法
CN110041091B (zh) * 2019-04-02 2022-08-09 上海交通大学 一种高发射率耐烧蚀隔热微球填料的制备方法
CN110343351A (zh) * 2019-07-25 2019-10-18 中国科学院合肥物质科学研究院 一种自修复高分子导热材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945166A (en) * 1997-12-30 1999-08-31 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for forming fiber reinforced composite bodies with graded composition and stress zones
EP1594816A1 (fr) * 2003-02-17 2005-11-16 Snecma Propulsion Solide Procede de siliciuration de materiaux composites thermostructuraux et pieces telles qu obtenues par le procede
US10590044B1 (en) * 2012-06-01 2020-03-17 United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Engineered matrix self-healing composites
US10654756B1 (en) * 2012-06-01 2020-05-19 United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Formulations for engineered ceramic matrix composites for high temperature applications

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SiC_SiC复合材料制备技术研究进展;王洋;《飞航导弹》;20190417(第6期);92-97 *
熔融改性修复剂制备自修复环氧树脂复合材料及其性能;袁新华等;《江苏大学学报(自然科学版)》;20130310;第34卷(第02期);217-221 *

Also Published As

Publication number Publication date
CN112479717A (zh) 2021-03-12

Similar Documents

Publication Publication Date Title
CN112479717B (zh) 一种自愈合基体改性SiC/SiC复合材料及其制备方法
CN105254320B (zh) 连续氧化物纤维增强氧化物陶瓷基复合材料的制备方法
US8894918B2 (en) Methods for producing high-performance silicon carbide fibers, architectural preforms, and high-temperature composite structures
US20120076927A1 (en) Method of improving the thermo-mechanical properties of fiber-reinforced silicon carbide matrix composites
CN112341235B (zh) 超高温自愈合陶瓷基复合材料的多相耦合快速致密化方法
CN108863418B (zh) 长纤维增强碳化硅构件、其制造方法及核反应堆结构构件
RU2668431C2 (ru) Способ получения деталей из композитного материала путем пропитки композицией с низкой температурой плавления
CN112479718B (zh) 一种Ti3SiC2 MAX相界面层改性SiC/SiC复合材料及其制备方法
CN101503305A (zh) 一种自愈合碳化硅陶瓷基复合材料的制备方法
CN104261850A (zh) 一种耐高温透波氮化硅纤维增强复合材料及其制备方法
US10662117B2 (en) Method of fabricating a part out of ceramic matrix composite material
CN113800915B (zh) 一种高致密SiC/SiC复合材料及其制备方法
CN108840694B (zh) 一种透波型Si3N4f/Si3N4复合材料表面涂层的制备方法
Wang et al. Effects of ZrO2 coating on the strength improvement of 2.5 D SiCf/SiO2 composites
CN109293367B (zh) 一种磷酸铈改性碳化硅纤维增强碳化硅复合材料及其制备方法
CN106966742A (zh) 含界面相的氧化铝纤维增强莫来石陶瓷及其制备方法
BOCCACCINI Glass and glass-ceramic matrix composite materials
CN115028456A (zh) 碳化硅纤维废丝增强碳化硅陶瓷基复合材料的制备方法
CN112521156B (zh) 一种混杂基体SiCf/SiC复合材料及其制备方法
KR101101244B1 (ko) 고밀도 탄화규소 섬유강화 탄화규소 복합체(ＳｉＣｆ/ＳｉＣ)의 제조방법
CN114853492B (zh) 一种深海高致密碳纤维陶瓷基耐压壳及制备方法
Wang et al. Fabrication, microstructures and properties of SiCf/SiC composites prepared with two kinds of SiC fibers as reinforcements
CN113135740B (zh) 一种陶瓷基复合材料及其制备方法和应用
CN112110733B (zh) 一种陶瓷纤维混编织物增强陶瓷基复合材料及其制备方法
CN112430111A (zh) 一种自愈合改性SiC/SiC复合材料及其制备方法

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
GR01 Patent grant
GR01 Patent grant