CN113387724A - 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 - Google Patents
一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 Download PDFInfo
- Publication number
- CN113387724A CN113387724A CN202110648462.4A CN202110648462A CN113387724A CN 113387724 A CN113387724 A CN 113387724A CN 202110648462 A CN202110648462 A CN 202110648462A CN 113387724 A CN113387724 A CN 113387724A
- Authority
- CN
- China
- Prior art keywords
- coating
- sic
- temperature
- composite material
- carbon
- 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.)
- Granted
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
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
- C04B41/5059—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
- C04B35/515—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
-
- 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
-
- 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
- C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
-
- 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
- C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
-
- 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
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
-
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
-
- 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
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- 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
- C04B2235/3804—Borides
- C04B2235/3813—Refractory metal borides
-
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Products (AREA)
Abstract
本发明涉及一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法,采用料浆浸涂结合气相渗硅工艺制备了一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si/SiC‑Si复合抗氧化涂层,SiC‑Si内涂层用于缓解涂层与基体之间的热失配,外层为(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si,通过在外涂层中引入高熵陶瓷,氧化后生成多元金属氧化物,进而提高SiO2在高温下的稳定性,最终实现涂层在高温下对C/C复合材料的长时有效防护。本发明所制备的(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si/SiC‑Si复合抗氧化涂层试样在1500℃下氧化2000h后涂层试样增重1.12%,在1700℃下500h后涂层试样增重1.05%。
Description
技术领域
本发明属于抗氧化涂层制备技术领域,涉及一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法,具体涉及一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层及其制备方法。
背景技术
碳/碳(C/C)复合材料具有比强度高、热膨胀系数低、耐高温等优异性能,特别是在超高温下仍能保持高强度的特性,使其广泛应用于航空航天领域中的高温结构部件。然而,C/C复合材料在超过370℃有氧环境中易氧化会导致其力学性能及各项物理化学性能迅速下降,稳定持久的抗氧化防护已成为保证C/C复合材料应用于新一代尖端武器装备及严酷环境工程化应用的关键。
抗氧化涂层被认为是解决C/C复合材料高温氧化防护问题的有效方法。为防止C/C复合材料在高温下氧化,国内外研究人员进行了大量的理论和试验研究,开发出多种抗氧化涂层体系。
在众多涂层体系中,陶瓷涂层是目前研究的热点。在陶瓷涂层体系里,一般采用SiC为内涂层的复合涂层结构,复合涂层的外涂层则采用不同种类的高温陶瓷。目前研究较多的一类是硅基陶瓷涂层,如SiCn[J.F.Huang,M.Liu,B.Wang,L.Y.Cao,C.K.Xia,J.P.Wu,SiCn/SiC oxidation protective coating for carbon/carbon composites,Carbon47(2009)1198-1201.]、Si-Mo-Cr/SiC[J.C.Ren,Y.L.Zhang,H.Hu,P.F.Zhang,T.Fei,L.L.Zhang,HfC nanowires to improve the toughness and oxidation resistance ofSi-Mo-Cr/SiC coating for C/C composites,Ceram.Int.42(2016)14518-14525]等硅基陶瓷涂层。其主要的氧化防护机理是利用高温下涂层氧化所产生的SiO2来愈合涂层中的裂纹等缺陷,利用其低的氧渗透率来阻止氧气的扩散,进而实现对C/C复合材料的氧化防护。但是,在高温氧化气氛或烧蚀环境中长期使用后,SiO2玻璃不可避免地大量挥发,从而在涂层中产生许多缺陷,从而失去了对C/C复合材料的保护能力。此外,一旦氧化温度超过1650℃,SiC就会发生主动氧化,这也会加速涂层的消耗。随着氧化时间的延长会逐渐挥发,使得玻璃层下面的涂层材料暴露在空气中。由于涂层材料的高透氧率,氧气在涂层中迅速扩散,导致C/C复合材料基体呈现快速氧化失重。此外,非晶态SiO2会在1700℃快速晶化,且伴随着体积收缩,导致玻璃层开裂和剥落。因此,设计出满足1700℃以上长寿命服役的涂层成分,并实现裂纹和孔隙的快速修复,是硅基陶瓷涂层成功应用于C/C复合材料1700℃长时间防氧化的前提,也是该方向研究需要突破的关键。
发明内容
要解决的技术问题
为了避免现有技术的不足之处,本发明提出一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法,首先采用料浆浸涂法在C/C复合材料表面制备SiC内涂层和(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si外涂层,随后采用气相渗硅工艺制得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合涂层。
技术方案
一种碳/碳复合材料表面耐高温长寿命复合涂层,其特征在于C/C复合材料表面涂层为内涂层和外涂层组成,其中内涂层组份为SiC-Si涂层,外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。
一种制备所述碳/碳复合材料表面耐高温长寿命复合涂层的方法,其特征在于步骤如下:
步骤1:将酚醛树脂与无水乙醇超声处理后搅拌均匀得到酚醛树脂溶液A,其中乙醇的质量分数为70-90wt%,酚醛树脂的质量分数为10-30wt%;
步骤2:向酚醛树脂溶液A中加入SiC粉体,搅拌均匀后得料浆B,其中SiC的质量分数为30-40wt%;
向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体,搅拌均匀后得料浆C,其中SiC的质量分数为10-20wt%,(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30-40wt%;
步骤3:将C/C复合材料浸到料浆B中进行预涂层浸涂,取出后在烘箱中干燥,该过程重复多次后,得到SiC内涂层;将带有SiC内涂层的C/C复合材料浸到料浆C中进行浸涂,取出后在烘箱中干燥,该过程重复多次后,得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC/SiC涂层;
步骤4:再置于管式气氛炉中温度为150-200℃,固化时间为2-4h进行固化;然后在温度为900-1100℃,碳化时间为2-4h进行碳化后得到预涂层;
步骤5:置于石墨坩埚中,坩埚底部放置一定量的硅块,得到预涂层的材料与硅块之间采用多孔石墨板隔开;密封坩埚后将石墨坩埚放入高温石墨化炉中在氩气保护下,温度为1800-2000℃,时间为15-30min进行气相渗硅,之后随炉冷却,在碳/碳复合材料表面得到耐高温长寿命复合涂层:(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si。
所述步骤3的重复多次为3次。
所述步骤3的浸涂时间为3-5s。
所述步骤3的干燥温度为50-80℃,干燥时间为10-30min。
有益效果
本发明提出的一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法,C/C复合材料表面涂层为内涂层和外涂层组成,其中内涂层组份为SiC-Si涂层,外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。本发明采用料浆浸涂结合气相渗硅工艺制备了一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层,SiC-Si内涂层用于缓解涂层与基体之间的热失配,外层为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si,通过在外涂层中引入高熵陶瓷,氧化后生成多元金属氧化物,进而提高SiO2在高温下的稳定性,最终实现涂层在高温下对C/C复合材料的长时有效防护。本发明所制备的(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层试样在1500℃下氧化2000h后涂层试样增重1.12%,在1700℃下500h后涂层试样增重1.05%。
本发明的涂层避免了在高温氧化气氛或烧蚀环境中长期使用后,SiO2玻璃不可避免地大量挥发,从而在涂层中产生许多缺陷,从而失去了对C/C复合材料的保护能力的缺陷。同时,在一旦氧化温度超过1650℃,SiC就会发生主动氧化,这也会加速涂层的消耗。随着氧化时间的延长会逐渐挥发,使得玻璃层下面的涂层材料暴露在空气中的问题。以及由于涂层材料的高透氧率,氧气在涂层中迅速扩散,导致C/C复合材料基体呈现快速氧化失重,非晶态SiO2会在1700℃快速晶化,且伴随着体积收缩,导致玻璃层开裂和剥落的问题。本发明满足1700℃以上长寿命服役的涂层成分,并实现裂纹和孔隙的快速修复,是硅基陶瓷涂层成功应用于C/C复合材料1700℃长时间防氧化的前提,也是该方向研究需要突破的关键。
附图说明
图1(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样的SEM照片:(a)表面SEM照片,(b)截面SEM照片
图2(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样在不同温度下的的氧化质量变化曲线:(a)1500℃,(b)1700℃
具体实施方式
现结合实施例、附图对本发明作进一步描述:
实施例1:
(1)称取一定量的酚醛树脂于烧杯中,向其中加入一定量的无水乙醇,其中酚醛树脂与无水乙醇的质量比为2:8,将其超声处理后搅拌均匀得到酚醛树脂溶液A;
(2)向酚醛树脂溶液A中加入SiC粉体,搅拌均匀后得料浆B,其中SiC的质量分数为40wt%;向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体,其中SiC的质量分数为10wt%,(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30wt%,搅拌均匀后得料浆C;
(3)将C/C复合材料浸到料浆B中浸涂3s,取出后在烘箱中于50℃干燥30min,该过程重复3次后,得到SiC内涂层;将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂3s,取出后在烘箱中于50℃干燥30min,该过程重复3次后,得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层;
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在150℃中保温4h,随即升温至900℃,热处理4h后得到预涂层试样;
(5)将(4)所得的预涂层试样置于自制的石墨坩埚中,坩埚底部放置一定量的硅块,试样与硅块通过多孔石墨板隔开,密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅,渗硅温度为1900℃,保温时间20min,之后随炉冷却,即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
实施例2:
(1)称取一定量的酚醛树脂于烧杯中,向其中加入一定量的无水乙醇,其中酚醛树脂与无水乙醇的质量比为1:9,将其超声处理后搅拌均匀得到酚醛树脂溶液A;
(2)向酚醛树脂溶液A中加入SiC粉体,搅拌均匀后得料浆B,其中SiC的质量分数为35wt%;向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体,其中SiC的质量分数为15wt%,(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为35wt%,搅拌均匀后得料浆C;
(3)将C/C复合材料浸到料浆B中浸涂4s,取出后在烘箱中于70℃干燥15min,该过程重复3次后,得到SiC内涂层;将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂4s,取出后在烘箱中于70℃干燥15min,该过程重复3次后,得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层;
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在200℃中保温2h,随即升温至1200℃,热处理2h后得到预涂层试样;
(5)将(4)所得的预涂层试样置于自制的石墨坩埚中,坩埚底部放置一定量的硅块,试样与硅块通过多孔石墨板隔开,密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅,渗硅温度为1800℃,保温时间30min,之后随炉冷却即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
实施例3:
(1)称取一定量的酚醛树脂于烧杯中,向其中加入一定量的无水乙醇,其中酚醛树脂与无水乙醇的质量比为2:8,将其超声处理后搅拌均匀得到酚醛树脂溶液A;
(2)向酚醛树脂溶液A中加入SiC粉体,搅拌均匀后得料浆B,其中SiC的质量分数为30wt%;向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体,其中SiC的质量分数为20wt%,(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为40wt%,搅拌均匀后得料浆C;
(3)将C/C复合材料浸到料浆B中浸涂5s,取出后在烘箱中于80℃干燥10min,该过程重复3次后,得到SiC内涂层;将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂5s,取出后在烘箱中于80℃干燥10min,该过程重复3次后,得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层;
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在180℃中保温3h,随即升温至1000℃,热处理3h后得到预涂层试样;
将(4)所得的预涂层试样置于自制的石墨坩埚中,坩埚底部放置一定量的硅块,试样与硅块通过多孔石墨板隔开,密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅,渗硅温度为2000℃,保温时间15min,之后随炉冷却,即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
Claims (5)
1.一种碳/碳复合材料表面耐高温长寿命复合涂层,其特征在于C/C复合材料表面涂层为内涂层和外涂层组成,其中内涂层组份为SiC-Si涂层,外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。
2.一种制备权利要求1所述碳/碳复合材料表面耐高温长寿命复合涂层的方法,其特征在于步骤如下:
步骤1:将酚醛树脂与无水乙醇超声处理后搅拌均匀得到酚醛树脂溶液A,其中乙醇的质量分数为70-90wt%,酚醛树脂的质量分数为10-30wt%;
步骤2:向酚醛树脂溶液A中加入SiC粉体,搅拌均匀后得料浆B,其中SiC的质量分数为30-40wt%;
向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体,搅拌均匀后得料浆C,其中SiC的质量分数为10-20wt%,(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30-40wt%;
步骤3:将C/C复合材料浸到料浆B中进行预涂层浸涂,取出后在烘箱中干燥,该过程重复多次后,得到SiC内涂层;将带有SiC内涂层的C/C复合材料浸到料浆C中进行浸涂,取出后在烘箱中干燥,该过程重复多次后,得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC/SiC涂层;
步骤4:再置于管式气氛炉中温度为150-200℃,固化时间为2-4h进行固化;然后在温度为900-1100℃,碳化时间为2-4h进行碳化后得到预涂层;
步骤5:置于石墨坩埚中,坩埚底部放置一定量的硅块,得到预涂层的材料与硅块之间采用多孔石墨板隔开;密封坩埚后将石墨坩埚放入高温石墨化炉中在氩气保护下,温度为1800-2000℃,时间为15-30min进行气相渗硅,之后随炉冷却,在碳/碳复合材料表面得到耐高温长寿命复合涂层:(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si。
3.根据权利要求2所述的方法,其特征在于:所述步骤3的重复多次为3次。
4.根据权利要求2所述的方法,其特征在于:所述步骤3的浸涂时间为3-5s。
5.根据权利要求2所述的方法,其特征在于:所述步骤3的干燥温度为50-80℃,干燥时间为10-30min。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110648462.4A CN113387724B (zh) | 2021-06-10 | 2021-06-10 | 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110648462.4A CN113387724B (zh) | 2021-06-10 | 2021-06-10 | 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113387724A true CN113387724A (zh) | 2021-09-14 |
CN113387724B CN113387724B (zh) | 2022-09-02 |
Family
ID=77620249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110648462.4A Active CN113387724B (zh) | 2021-06-10 | 2021-06-10 | 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113387724B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113735629A (zh) * | 2021-09-23 | 2021-12-03 | 沈阳先进涂层材料产业技术研究院有限公司 | 一种碳材料宽温域防氧化抗冲刷复相陶瓷涂层及其制备方法 |
CN114394844A (zh) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | 一种废料3d打印制备碳化硅陶瓷的方法及碳化硅陶瓷 |
CN115784761A (zh) * | 2022-12-02 | 2023-03-14 | 无锡博智复合材料有限公司 | 一种高熵陶瓷涂层与基体协同改性碳/碳复合材料及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02129366A (ja) * | 1988-11-08 | 1990-05-17 | Sumitomo Electric Ind Ltd | 被覆構造材料 |
CN1903790A (zh) * | 2005-07-28 | 2007-01-31 | 西北工业大学 | 碳/碳复合材料基二硅化钽/碳化硅涂层及其制备方法 |
CN106242642A (zh) * | 2016-07-28 | 2016-12-21 | 航天材料及工艺研究所 | 一种耐1700℃低密度碳瓦表面抗氧化涂层及其制备方法 |
CN108530109A (zh) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | 一种碳/碳复合材料表面1500~1700℃抗氧化涂层及制备方法 |
CN109735789A (zh) * | 2019-01-25 | 2019-05-10 | 航天材料及工艺研究所 | 一种多元Zr/Hf基超高熔点碳化物抗氧化涂层及其制备方法 |
CN110078512A (zh) * | 2019-05-17 | 2019-08-02 | 淄博星澳新材料研究院有限公司 | 超高温高熵碳化物粉体及其制备方法 |
CN110903107A (zh) * | 2018-09-18 | 2020-03-24 | 付红 | 一种提高碳/碳复合材料抗氧化性能的复合涂层 |
-
2021
- 2021-06-10 CN CN202110648462.4A patent/CN113387724B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02129366A (ja) * | 1988-11-08 | 1990-05-17 | Sumitomo Electric Ind Ltd | 被覆構造材料 |
CN1903790A (zh) * | 2005-07-28 | 2007-01-31 | 西北工业大学 | 碳/碳复合材料基二硅化钽/碳化硅涂层及其制备方法 |
CN106242642A (zh) * | 2016-07-28 | 2016-12-21 | 航天材料及工艺研究所 | 一种耐1700℃低密度碳瓦表面抗氧化涂层及其制备方法 |
CN108530109A (zh) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | 一种碳/碳复合材料表面1500~1700℃抗氧化涂层及制备方法 |
CN110903107A (zh) * | 2018-09-18 | 2020-03-24 | 付红 | 一种提高碳/碳复合材料抗氧化性能的复合涂层 |
CN109735789A (zh) * | 2019-01-25 | 2019-05-10 | 航天材料及工艺研究所 | 一种多元Zr/Hf基超高熔点碳化物抗氧化涂层及其制备方法 |
CN110078512A (zh) * | 2019-05-17 | 2019-08-02 | 淄博星澳新材料研究院有限公司 | 超高温高熵碳化物粉体及其制备方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113735629A (zh) * | 2021-09-23 | 2021-12-03 | 沈阳先进涂层材料产业技术研究院有限公司 | 一种碳材料宽温域防氧化抗冲刷复相陶瓷涂层及其制备方法 |
CN113735629B (zh) * | 2021-09-23 | 2023-03-10 | 沈阳先进涂层材料产业技术研究院有限公司 | 一种碳材料宽温域防氧化抗冲刷复相陶瓷涂层及其制备方法 |
CN114394844A (zh) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | 一种废料3d打印制备碳化硅陶瓷的方法及碳化硅陶瓷 |
CN115784761A (zh) * | 2022-12-02 | 2023-03-14 | 无锡博智复合材料有限公司 | 一种高熵陶瓷涂层与基体协同改性碳/碳复合材料及其制备方法 |
CN115784761B (zh) * | 2022-12-02 | 2023-09-19 | 无锡博智复合材料有限公司 | 一种高熵陶瓷涂层与基体协同改性碳/碳复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113387724B (zh) | 2022-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113387724B (zh) | 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 | |
CN109293383B (zh) | 一种纤维增强碳-碳化硅陶瓷基复合材料及其制备方法 | |
CN110922191B (zh) | 一种碳化硅聚合物先驱体陶瓷缺陷愈合方法 | |
CN110963799B (zh) | 一种液相硅辅助成形热防护类Z-pins硅化物陶瓷棒结构的制备方法 | |
CN113716977B (zh) | 一种碳/碳复合材料表面宽温域复合抗氧化涂层及制备方法 | |
CN114524674B (zh) | 一种防热-隔热-承载一体化轻质碳-陶复合材料及其制备方法 | |
CN109851381B (zh) | 一种C/SiC-ZrC-TiC-Cu复合材料及其制备方法 | |
CN105541416A (zh) | 一种C/C复合材料表面HfC-SiC涂层的制备方法 | |
CN113045326B (zh) | 一种改性碳/碳复合材料的制备方法 | |
CN103936464A (zh) | HfC-SiC改性炭/炭复合材料的制备方法 | |
CN112142486A (zh) | 抗烧蚀碳化硅纤维增强陶瓷基复合材料的制备方法 | |
CN115894039B (zh) | 一种分区改性的异形碳纤维增强复合材料构件及制备方法 | |
CN112299865A (zh) | 一种改性C/SiC复合材料及其制备方法 | |
US5660880A (en) | Anti-oxidation protection of carbon-based materials | |
CN112374901B (zh) | 一种耐烧蚀改性C/SiC复合材料及其制备方法 | |
CN115784761B (zh) | 一种高熵陶瓷涂层与基体协同改性碳/碳复合材料及其制备方法 | |
CN105669231B (zh) | 一种碳纤维增强MoSi2-SiC陶瓷基复合材料的制备方法 | |
CN115784776B (zh) | 碳/碳复合材料表面大范围均匀分布富MoSi2-ZrB2抗氧化涂层及制备方法 | |
KR100520436B1 (ko) | 탄소/탄소 복합재료의 내산화 복합코팅방법 | |
CN111410560A (zh) | 一种高致密SiC涂层的硅化石墨制备方法 | |
JP2968477B2 (ja) | 非酸化物系セラミック繊維強化セラミックス複合材料の製造方法 | |
CN116803953B (zh) | 一种耐高温长寿命抗烧蚀陶瓷改性碳/碳复合材料及其制备方法和应用 | |
CN111320475A (zh) | 一种Si-B-C三组元相的高通量制备方法 | |
CN110453495B (zh) | 一种碳纤维表面镀碳化硼的方法 | |
KR20040069835A (ko) | 탄소/탄소 복합재료의 내산화 코팅방법 |
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 |