CN108147817B - 一种块状碳化硼-碳化硅复合气凝胶的制备方法 - Google Patents
一种块状碳化硼-碳化硅复合气凝胶的制备方法 Download PDFInfo
- Publication number
- CN108147817B CN108147817B CN201810003764.4A CN201810003764A CN108147817B CN 108147817 B CN108147817 B CN 108147817B CN 201810003764 A CN201810003764 A CN 201810003764A CN 108147817 B CN108147817 B CN 108147817B
- Authority
- CN
- China
- Prior art keywords
- boron carbide
- silicon carbide
- hours
- solution
- composite aerogel
- 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
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 46
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 46
- 239000004964 aerogel Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000352 supercritical drying Methods 0.000 claims abstract description 13
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 11
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XJZNCUDTWKPVBJ-UHFFFAOYSA-N 3-triethylsilylpropan-1-amine Chemical compound CC[Si](CC)(CC)CCCN XJZNCUDTWKPVBJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000011278 co-treatment Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
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
- C04B35/56—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
- C04B35/563—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 boron 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
- C04B35/56—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
- C04B35/624—Sol-gel processing
-
- 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
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0605—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances by sublimating
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/026—Semi-liquids, gels, pastes
-
- 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
- C04B2235/3821—Boron 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
- C04B2235/50—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
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- 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
- C04B2235/6023—Gel casting
-
- 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
- C04B2235/6567—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
-
- 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
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
-
- 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
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Ceramic Products (AREA)
Abstract
本发明涉及一种块状碳化硼‑碳化硅复合气凝胶的制备方法。通过将纳米碳化硼粉末、间苯二酚、甲醛、3‑氨丙基三乙基硅烷、无水乙醇、去离子水按摩尔比例进行搅拌，得到溶液为淡黄色复合溶胶溶液，静置后得到湿凝胶。湿凝胶经过溶剂置换，再采用CO2超临界干燥技术对湿凝胶进行干燥处理得到碳化硼‑碳化硅前驱体，在惰性气氛保护下经过碳热还原技术得到块状碳化硼‑碳化硅复合气凝胶。本发明制备出的块状碳化硼‑碳化硅复合气凝胶不仅具有高比面积、低密度、高孔隙率以及耐高温性能优异等优点，而且工艺过程简单易操作。块状碳化硼‑碳化硅复合气凝胶的制备有望在化工设备以及高温窑炉等领域拥有广阔的应用前景。
Description
技术领域
本发明属于复合材料制备工艺，具体涉及一种块状碳化硼-碳化硅复合气凝胶的制备方法。尤其是采用溶胶-凝胶法结合CO2超临界干燥和碳热还原技术制备块状碳化硼-碳化硅复合气凝胶方法。
背景技术
随着科学技术的进步，我国核事业正在蓬勃发展。预计至2020年，每年核反应堆卸下的乏燃料将达到千吨以上，若在储存和运输时发生事故，就会产生极强的核辐射，这就需要有对应的核事故应急快速防护设备来预防和紧急救援。目前核辐射屏蔽材料只要是集中为防辐射混凝土和纤维类高分子复合材料。防辐射混凝土虽然具有耐高温和良好的结构性能，但是其体积大限制了其在应急运输方面的使用。纤维类高分子屏蔽材料虽然具有质轻、体积小及便于搬运等优点，但是其在高温下的性能会大大降低。碳化物气凝胶是一种具有高比面积、低密度、机械性能好及耐高温性能好等优异的物理化学性能的高效隔热材料，可以广泛应用在1000℃及以上的高温场所。块状碳化硼-碳化硅复合气凝胶不仅具有碳化物气凝胶低密度、高比表面积及耐温性好等优点，更是结合碳化硼高中子俘获截面、高硬度和高温稳定性等优势。开发出的块状碳化硼-碳化硅复合气凝胶不仅具有质轻、高比面积等优异特性，更是一种兼具耐高温和中子屏蔽效果的核事故应急修复材料。
发明内容
本发明的目的是为了克服现有技术的不足，提供一种块状碳化硼-碳化硅复合气凝胶的制备方法。该方法工艺简单易操作，安全系数高。
本发明的技术方案为：一种块状碳化硼-碳化硅复合气凝胶的制备方法，其具体步骤如下：
(1)将间苯二酚、甲醛、去离子水和无水乙醇按摩尔比为1：2：(5～20)：(13.5～26)混合均匀搅拌，得到溶液A；
(2)将3-氨丙基三乙基硅烷、纳米碳化硼粉、无水乙醇按摩尔比例为1：(0.05～1)：(5～20)超声混合均匀，得到溶液B；
(3)将溶液B加入溶液A中，混合均匀搅拌得到淡黄色复合溶胶溶液；
(4)将步骤(3)中得到的淡黄色溶液倒入模具中，静置后，进行溶剂置换；
(5)将步骤(4)中置换后的复合湿凝胶进行CO2超临界干燥处理，得到碳化硼-碳化硅前驱体；
(6)将步骤(5)中得到的碳化硼-碳化硅前驱体在惰性气氛保护下加热至1400～1600℃，保温时间为3～10小时，然后将温度降至550～750℃，把惰性气体换成空气，继续保温1～4小时进行除炭处理，冷却；
(7)把步骤(6)中得到样品放在氢氟酸中浸泡，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。
优选步骤(2)中纳米碳化硼的粒径为20nm～50nm。
优选步骤(3)中间苯二酚与3-氨丙基三乙基硅烷的摩尔比为1：(0.5～1.5)。
优选步骤(4)中静置时间为30～70min；溶剂置换的溶剂为无水乙醇；溶剂置换每8～24小时更换一次，置换次数为3～6次。
优选步骤(5)中CO2超临界干燥参数为釜体压力控制在8～12MPa，温度控制在45～55℃，干燥时间为8～14小时。
优选步骤(6)中惰性气氛为氦气或氩气的一种。优选步骤(6)加热的升温速率为2～4℃/min。
优选步骤(7)中氢氟酸的质量分数为10～30％；浸泡时间为1～3小时。
制备出的块状碳化硼-碳化硅复合气凝胶密度在0.25～0.35g/cm3，压缩强度在0.95～1.25Mpa，耐1000℃高温和良好中子屏蔽效果等优势。
有益效果：
(1)工艺简单易操作，产品性能优异。本方法采用溶胶-凝胶法结合CO2超临界干燥技术和碳热还原技术制备块状碳化硼-碳化硅复合气凝胶，其中溶胶-凝胶法工艺简单且易重复，超临界干燥技术可制备出具有孔隙均匀，高比表面积的块状碳化硼-碳化硅复合气凝胶。
(2)性能优异，应用范围广。相比较于防辐射混凝土和纤维高分子复合材料，块状碳化硼-碳化硅复合气凝胶不仅具有质轻、高比面积等优异特性，更是一种兼具耐高温和中子屏蔽效果的核事故应急修复材料。其应用范围极其广泛。
附图说明
图1为实施例1制备的块状碳化硼-碳化硅复合气凝胶材料的实物照片。
具体实施方式
实施例1
将1mol间苯二酚、2mol甲醛、15mol去离子水和18mol无水乙醇混合均匀搅拌，得到溶液A。将0.5mol粒度为30nm纳米碳化硼粉末、1mol 3-氨丙基三乙基硅烷和5mol无水乙醇超声混合均匀，得到溶液B。把溶液B加入溶液A中混合均匀搅拌，得到淡黄色复合溶胶溶液。倒入模具中，静置70min后，加入无水乙醇进行溶剂置换，每8小时更换一次，总共置换4次。将置换后的复合湿凝胶进行CO2超临界干燥处理，其中釜体压力控制在10MPa、温度控制在45℃，反应时间为10小时，得到碳化硼-碳化硅前驱体。将得到的碳化硼-碳化硅前驱体在氩气气氛保护下以3℃/min的升温速率加热至1500℃，保温时间为5小时，然后将温度降至600℃，把氩气换成空气，继续保温3小时进行除炭处理，冷却至室温后，把样品放在质量分数为10％氢氟酸中浸泡3小时，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。制备得到的块状碳化硼-碳化硅复合气凝胶实物照片如图1所示，为黑色块状物体。经过测试发现：制得的块状碳化硼-碳化硅复合气凝胶密度为0.25g/cm3，压缩强度为1.08MPa，可在1000℃有氧环境下使用和良好的中子屏蔽性能。
实施例2
将1mol间苯二酚、2mol甲醛、5mol去离子水和26mol无水乙醇混合均匀搅拌，得到溶液A。将0.1mol粒度为20nm纳米碳化硼粉末、1.5mol 3-氨丙基三乙基硅烷和8mol无水乙醇超声混合均匀，得到溶液B。把溶液B加入溶液A中混合均匀搅拌，得到淡黄色复合溶胶溶液。倒入模具中，静置60min后，加入无水乙醇进行溶剂置换，每12小时更换一次，总共置换3次。将置换后的复合湿凝胶进行CO2超临界干燥处理，其中釜体压力控制在9MPa、温度控制在48℃，反应时间为13小时，得到碳化硼-碳化硅前驱体。将得到的碳化硼-碳化硅前驱体在氦气气氛保护下以2℃/min的升温速率加热至1550℃，保温时间为6小时，然后将温度降至650℃，把氦气换成空气，继续保温3小时进行除炭处理，冷却至室温后，把样品放在质量分数为15％氢氟酸中浸泡2小时，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。经过测试发现：制得的块状碳化硼-碳化硅复合气凝胶密度为0.29g/cm3，压缩强度为0.98MPa，可在1000℃有氧环境下使用和良好的中子屏蔽性能。
实施例3
将1mol间苯二酚、2mol甲醛、10mol去离子水和20mol无水乙醇混合均匀搅拌，得到溶液A。将0.3mol粒度为40nm纳米碳化硼粉末、0.5mol 3-氨丙基三乙基硅烷和10mol无水乙醇超声混合均匀，得到溶液B。把溶液B加入溶液A中混合均匀搅拌，得到淡黄色复合溶胶溶液。倒入模具，静置50min后，加入无水乙醇进行溶剂置换，每15小时更换一次，总共置换4次。将置换后的复合湿凝胶进行CO2超临界干燥处理，其中釜体压力控制在11MPa、温度控制在50℃，反应时间为12小时，得到碳化硼-碳化硅前驱体。将得到的碳化硼-碳化硅前驱体在氩气气氛保护下以4℃/min的升温速率加热至1450℃，保温时间为7小时，然后将温度降至700℃，把氩气换成空气，继续保温2小时进行除炭处理，冷却至室温后，把样品放在质量分数为25％氢氟酸中浸泡1.5小时，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。经过测试发现：制得的块状碳化硼-碳化硅复合气凝胶密度为0.30g/cm3，压缩强度为1.15MPa，可在1000℃有氧环境下使用和良好的中子屏蔽性能。
实施例4
将1mol间苯二酚、2mol甲醛、18mol去离子水和15mol无水乙醇混合均匀搅拌，得到溶液A。将0.8mol粒度为45nm纳米碳化硼粉末、0.8mol 3-氨丙基三乙基硅烷和7mol无水乙醇超声混合均匀，得到溶液B。把溶液B加入溶液A中混合均匀搅拌，得到淡黄色复合溶胶溶液。倒入模具，静置40min后，加入无水乙醇进行溶剂置换，每20小时更换一次，总共置换5次。将置换后的复合湿凝胶进行CO2超临界干燥处理，其中釜体压力控制在10MPa、温度控制在53℃，反应时间为11小时，得到碳化硼-碳化硅前驱体。将得到的碳化硼-碳化硅前驱体在氦气气氛保护下以3℃/min的升温速率加热至1400℃，保温时间为10小时，然后将温度降至550℃，把氦气换成空气，继续保温4小时进行除炭处理，冷却至室温后，把样品放在质量分数为20％氢氟酸中浸泡1.5小时，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。经过测试发现：制得的块状碳化硼-碳化硅复合气凝胶密度为0.31g/cm3，压缩强度为0.96MPa，可在1000℃有氧环境下使用和良好的中子屏蔽性能。
实施例5
将1mol间苯二酚、2mol甲醛、20mol去离子水和13.5mol无水乙醇混合均匀搅拌，得到溶液A。将1mol粒度为50nm纳米碳化硼粉末、1.3mol 3-氨丙基三乙基硅烷和10mol无水乙醇超声混合均匀，得到溶液B。把溶液B加入溶液A中混合均匀搅拌，得到淡黄色复合溶胶溶液。倒入模具，静置30min后，加入无水乙醇进行溶剂置换，每24小时更换一次，总共置换6次。将置换后的复合湿凝胶进行CO2超临界干燥处理，其中釜体压力控制在12MPa、温度控制在55℃，反应时间为9小时，得到碳化硼-碳化硅前驱体。将得到的碳化硼-碳化硅前驱体在氩气保护下以2℃/min的升温速率加热至1600℃，保温时间为3小时，然后将温度降至750℃，把氩气换成空气，继续保温2小时进行除炭处理，冷却至室温后，把样品放在质量分数为30％氢氟酸中浸泡1小时，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。经过测试发现：制得的块状碳化硼-碳化硅复合气凝胶密度为0.28g/cm3，压缩强度为1.23MPa，可在1000℃有氧环境下使用和良好的中子屏蔽性能。
Claims (6)
1.一种块状碳化硼-碳化硅复合气凝胶的制备方法，其具体步骤如下：
(1)将间苯二酚、甲醛、去离子水和无水乙醇按摩尔比为1：2：(5～20)：(13.5～26)混合均匀搅拌，得到溶液A；
(2)将3-氨丙基三乙基硅烷、纳米碳化硼粉、无水乙醇按摩尔比例为1：(0.05～1)：(5～20)超声混合均匀，得到溶液B；其中纳米碳化硼的粒径为20nm～50nm；
(3)将溶液B加入溶液A中，混合均匀搅拌得到淡黄色复合溶胶溶液；其中间苯二酚与3-氨丙基三乙基硅烷的摩尔比为1：(0.5～1.5)；
(4)将步骤(3)中得到的淡黄色溶液倒入模具中，静置后，进行溶剂置换；
(5)将步骤(4)中置换后的复合湿凝胶进行CO2超临界干燥处理，得到碳化硼-碳化硅前驱体；
(6)将步骤(5)中得到的碳化硼-碳化硅前驱体在惰性气氛保护下加热至1400～1600℃，保温时间为3～10小时，然后将温度降至550～750℃，把惰性气体换成空气，继续保温1～4小时进行除炭处理，冷却；
(7)把步骤(6)中得到样品放在氢氟酸中浸泡，经过水洗、过滤、烘干后得到块状碳化硼-碳化硅复合气凝胶。
2.根据权利要求1所述的制备方法，其特征在于步骤(4)中静置时间为30～70min；溶剂置换的溶剂为无水乙醇；溶剂置换每8～24小时更换一次，置换次数为3～6次。
3.根据权利要求1所述的制备方法，其特征在于步骤(5)中CO2超临界干燥参数为釜体压力控制在8～12MPa，温度控制在45～55℃，干燥时间为8～14小时。
4.根据权利要求1所述的制备方法，其特征在于步骤(6)中惰性气氛为氦气或氩气的一种。
5.根据权利要求1所述的制备方法，其特征在于步骤(6)加热的升温速率为2～4℃/min。
6.根据权利要求1所述的制备方法，其特征在于步骤(7)中氢氟酸的质量分数为10～30％；浸泡时间为1～3小时。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810003764.4A CN108147817B (zh) | 2018-01-03 | 2018-01-03 | 一种块状碳化硼-碳化硅复合气凝胶的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810003764.4A CN108147817B (zh) | 2018-01-03 | 2018-01-03 | 一种块状碳化硼-碳化硅复合气凝胶的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108147817A CN108147817A (zh) | 2018-06-12 |
| CN108147817B true CN108147817B (zh) | 2020-12-29 |
Family
ID=62460533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810003764.4A Active CN108147817B (zh) | 2018-01-03 | 2018-01-03 | 一种块状碳化硼-碳化硅复合气凝胶的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108147817B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109758988B (zh) * | 2019-03-18 | 2021-10-29 | 南京工业大学 | 一种C-Al2O3-B4C复合气凝胶的制备方法 |
| CN110104619B (zh) * | 2019-04-04 | 2023-07-07 | 南京工业大学 | 一种耐高温轻质bn气凝胶材料的制备方法 |
| CN110511031A (zh) * | 2019-09-17 | 2019-11-29 | 南京工业大学 | 基于纤维增强碳化硼复合气凝胶高发射涂层的制备方法 |
| CN110818423A (zh) * | 2019-11-04 | 2020-02-21 | 江苏一夫新材料产业技术研究院有限公司 | 一种碳化锆-碳化硼复合气凝胶及其制备方法 |
| CN110711543A (zh) * | 2019-11-07 | 2020-01-21 | 南京工业大学 | 一种纤维复合碳化硼-氧化铝气凝胶材料的制备方法 |
| CN112409012A (zh) * | 2020-11-25 | 2021-02-26 | 南京工业大学 | 一种块状碳化钛-碳化硅复合气凝胶材料及其制备方法 |
| CN115583836B (zh) * | 2022-09-09 | 2023-09-19 | 航天特种材料及工艺技术研究所 | 一种耐高温复相陶瓷气凝胶及其制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4524138A (en) * | 1982-05-13 | 1985-06-18 | Elektroschmelzwerk Kempten Gmbh | Substantially pore-free sintered polycrystalline articles of α-silicon carbide, boron carbide and free carbon and process for their manufacture |
| CN102432295A (zh) * | 2011-08-12 | 2012-05-02 | 清华大学 | 一种陶瓷基中子吸收球及制备方法 |
| CN102897764A (zh) * | 2012-10-22 | 2013-01-30 | 南京工业大学 | 一种块状碳化硅气凝胶材料及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110250428A1 (en) * | 2010-02-07 | 2011-10-13 | Aerogel Technologies, Llc | Preparation of cross-linked aerogels and derivatives thereof |
-
2018
- 2018-01-03 CN CN201810003764.4A patent/CN108147817B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4524138A (en) * | 1982-05-13 | 1985-06-18 | Elektroschmelzwerk Kempten Gmbh | Substantially pore-free sintered polycrystalline articles of α-silicon carbide, boron carbide and free carbon and process for their manufacture |
| CN102432295A (zh) * | 2011-08-12 | 2012-05-02 | 清华大学 | 一种陶瓷基中子吸收球及制备方法 |
| CN102897764A (zh) * | 2012-10-22 | 2013-01-30 | 南京工业大学 | 一种块状碳化硅气凝胶材料及其制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| Integration of mineral powders into SiO2 aerogels;J.Kuhn等;《JOURNAL OF NON-CRYSTALLINE SOLIDS》;19950630;第186卷;第291-295页 * |
| Synthesis and microwave dielectric properties of boron doped SiC powder by sol-gel method;Li Zhi-min等;《TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA》;20071130;第17卷;第S656-S659页 * |
| 以RF/SiO2复合气凝胶为前驱体制备介孔α-SiC;孔勇等;《无机化学学报》;20121010;第28卷(第10期);第2071页左栏第1段，第2072页右栏1.2小节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108147817A (zh) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108147817B (zh) | 一种块状碳化硼-碳化硅复合气凝胶的制备方法 | |
| CN108147818B (zh) | 耐高温碳化硼-碳化硅复合气凝胶制备方法 | |
| CN106478105A (zh) | 一种多步反应烧结法制备低残硅的碳化硅陶瓷材料的方法 | |
| CN111925194B (zh) | 一种耐高温高性能气凝胶复合材料及其制备方法 | |
| CN107274936B (zh) | 一种氧化铍增强型二氧化铀核燃料的快速制备方法 | |
| CN102643102B (zh) | 碳化硅微粉填料的石英纤维增强石英吸波陶瓷及其制备方法 | |
| CN108335768B (zh) | 一种基于纳米二氧化铀或其复合物的燃料芯块的制备方法 | |
| CN103553616A (zh) | 原位生长SiC纳米线增强C/SiC复合材料及其制备方法 | |
| CN109553419A (zh) | 一种气压固相烧结碳化硼复相陶瓷及其制备方法 | |
| CN103508437A (zh) | 一种酚醛树脂基玻璃碳微球的制备方法 | |
| CN111943654B (zh) | 一种耐高温抗辐射气凝胶复合材料及其制备方法 | |
| CN109758988B (zh) | 一种C-Al2O3-B4C复合气凝胶的制备方法 | |
| CN107935595A (zh) | 一种高温气冷堆用石墨砖的制备方法 | |
| CN106854086B (zh) | 一种耐高温的莫来石型气凝胶复合材料及其制备方法 | |
| CN112158852A (zh) | 一种高强度超低密度透明二氧化硅气凝胶及其制备方法和应用 | |
| CN101734918A (zh) | 一种致密富10b碳化硼陶瓷及其制备方法 | |
| CN115650728A (zh) | 一种单晶热场用石墨的制备方法 | |
| CN108178533B (zh) | 高强再生胶凝材料制品的制备方法 | |
| CN108439409A (zh) | 一种块状碳化硼气凝胶的制备方法 | |
| CN110303158A (zh) | 一种新型制备泡沫铝的方法 | |
| CN109592981B (zh) | 一种多孔稀土钛酸盐隔热材料及其制备方法和应用 | |
| CN108609606A (zh) | 一种炭气凝胶隔热材料的制备方法 | |
| CN110711543A (zh) | 一种纤维复合碳化硼-氧化铝气凝胶材料的制备方法 | |
| CN104529436A (zh) | 一种高致密度Bi4-xNdxTi3O12铁电陶瓷的制备方法 | |
| CN111704475B (zh) | 短切碳化硅纤维增强ZrC多层包壳材料及其制备方法 |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 210009 Gulou District, Jiangsu, Nanjing new model road, No. 5 Applicant after: NANJING TECH University Address before: 211816 Jiangsu, Nanjing, Pu Pu Road, Pukou District No. 30 Applicant before: NANJING TECH University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |