CN114853476B - 一种基于无机物质的超高性能碳基材料及其制备方法 - Google Patents
一种基于无机物质的超高性能碳基材料及其制备方法 Download PDFInfo
- Publication number
- CN114853476B CN114853476B CN202210420325.XA CN202210420325A CN114853476B CN 114853476 B CN114853476 B CN 114853476B CN 202210420325 A CN202210420325 A CN 202210420325A CN 114853476 B CN114853476 B CN 114853476B
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon
- parts
- based material
- temperature
- 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
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000498 ball milling Methods 0.000 claims description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 4
- 239000011856 silicon-based particle Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000013590 bulk material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002490 spark plasma sintering Methods 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000004697 Polyetherimide Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229920001601 polyetherimide Polymers 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003257 polycarbosilane Polymers 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZQOBAJVOKBJPEE-UHFFFAOYSA-N [B].[C].[N].[Si] Chemical compound [B].[C].[N].[Si] ZQOBAJVOKBJPEE-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- -1 borides Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
-
- 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
- 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
- C04B2235/422—Carbon
- C04B2235/425—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
- 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
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
本发明公开了一种基于无机物质的超高性能碳基材料及其制备方法，属于碳基材料领域。本发明主要解决现有以石墨烯为原料制备的块体碳基材料力学性能较差，耐高温性能差的问题。本发明将石墨烯与非碳元素成键物质均匀混合，经高温处理，石墨烯与非碳元素发生化学反应，形成高强度、高热稳定性的化学键(如B‑C、Ti‑C等)，能有效实现石墨烯层间的连接，抑制石墨层间滑移，显著提升石墨烯为原料制备的块体材料的力学性能；同时非碳元素的引入，可赋予碳基材料耐高温等综合性能。本发明可用作火箭高温构件、热防护构件、超高功率电极、高导热散热构件、高性能坩埚、高温高性能模具、金属结晶器、刹车盘、研磨和切割用材料等。
Description
技术领域
本发明属于碳基材料领域，具体地说，涉及一种基于无机物质的超高性能碳基材料，及基于无机物质的超高性能碳基材料的制备方法。
背景技术
石墨烯(Graphene)是一种碳原子以sp2杂化形式组成六角型呈蜂巢晶格的二维碳纳米材料，具有超高的机械性能和超强的导电、导热等优异性能。以化学气相沉积等方法宏观制备大尺寸石墨烯薄膜材料成本高昂，从粉体制备石墨烯块体材料是更优的选择，但小尺寸石墨烯片层间主要以范德华力连接，力学性能较差。因此目前的石墨烯使用的状态主要是薄膜或粉体，制备高性能大尺寸块体材料非常困难。此外石墨烯在高温含氧气氛中易于氧化，其耐高温抗氧化性能差。
目前报道的碳基材料块体材料主要制备方法如下：
杨全红等(CN101993056A)将氧化石墨烯水溶液和聚乙烯醇溶液混合后，水热反应一定时间，冷冻干燥，在氩气气氛保护的条件下经高温热处理后，得到了多孔石墨烯块体材料。凭借此方法制备的石墨烯材料具有发达的孔隙结构，比表面积大，其力学性能差。
Han等(ACS.NANO,2017,11:3189-97)利用冷压成型技术制备了石墨烯块体材料，研究显示，石墨烯片层间只存在范德华作用，其拉伸强度仅为18MPa，力学性能差。
Tian等(ADVANCED MATERIALS,2013,25)将氧化石墨烯表面包覆多巴胺。再将其分散于PEI(聚醚酰亚胺)溶液中，调节pH值使得聚醚酰亚胺的胺基与多巴胺上的羟基反应，获得PGO+PEI薄膜。随着聚醚酰亚胺含量的增加，复合薄膜的拉伸强度由116MPa提升至178MPa，共价交联作用提升石墨烯膜的拉伸强度。
Gong等(J.Mater.Chem.A,2016,4:17073–17079)通过Zn2+离子作用和PCDO(10,12-二十五碳二炔-1-醇)酯化交联连接氧化石墨烯，提升石墨烯膜力学强度，拉伸强度最优达到439MPa。
通过范德华力、离子键、氢键等作用力连接石墨烯片层，能够提升石墨烯基材料力学性能，但是提升幅度有限。而且，上述材料的耐高温性能较差，在温度800℃的空气气氛中，材料氧化烧蚀严重。。
发明内容
本发明主要解决现有石墨烯为原料的碳基块体材料力学性能较差，耐高温性能差的问题；而提供了一种基于无机物质的超高性能碳基材料及其制备方法。本发明利用非碳无机元素与石墨烯发生反应生成高强度、高热稳定性的化学键连接石墨烯片层，抑制石墨烯层间滑移，显著提升石墨烯为原料的碳基块体材料力学性能。该方法操作较简单，易于进行批量化生产，制备的材料兼具高强、耐高温、导电、导热和轻质等优势。
为了实现上述技术问题，本发明采取了以下的技术方案：
本发明的目的在于提供一种一种基于无机物质的超高性能碳基材料是利用非碳元素和石墨烯的碳组成的化学键连接石墨烯片，是将与石墨烯反应生成高强度稳定化学键成键物质与石墨烯粉体均匀混合，经过高温处理制备而成的。
进一步地限定，石墨烯片的层数为1～10层，片径尺寸5nm～20000nm。
进一步地限定，石墨烯片采用机械剥离、电化学剥离、高压电极放电法、燃烧合成法石墨烯或化学氧化法制成的。
进一步地限定，化学键成键物质，包括：(a)下列元素的单质纳米粉体：硼、钛、铬、锰、铁、镍、钇、锆、铌、钼、钌、铪、钽、钨、铼、铱；(b)化合物纳米粉体：硼、硅、钪、钛、钒、铬、锰、铁、钴、镍、钇、锆、铌、钼、钌、镧系元素、铪、钽、钨、铼、铱中一种元素与H、O、N、B、Si五中一种或几种元素组成的无机化合物(例如，上述元素的氢化物、硼化物、氮化物和硅化物，硼酸，硼酸盐，硅酸盐，硼氮烷，硅氮烷，Si-O-C-N，TiCxNy，硅硼碳氮陶瓷等)，MAX材料(化学通式为Mn+1AXn，A为主族元素，M代表过渡金属；X为C或者N)；(c)硼、硅、钪、钛、钒、铬、锰、铁、钴、镍、钇、锆、铌、钼、钌、镧系元素、铪、钽、钨、铼、铱中任意两种或者多种物质的纳米合金粉或混合物。(d)含有硼、硅、钪、钛、钒、铬、锰、铁、钴、镍、钇、锆、铌、钼、钌、镧系元素、铪、钽、钨、铼、铱等元素的有机物质：例如，有机硼烷、有机硅烷、有机硼酸酯、聚碳硅烷、硅树脂、金属有机化合物等。
进一步地限定，无机粉体直径：1-100nm；有机物质分子量：100-1000000。
基于无机物质的超高性能碳基材料的制备的制备方法是按下述步骤进行的：按配比称取石墨烯粉和化学键成键物质；将上述原料混合均匀，然后进行高温热处理，制成复合材料。
进一步地限定，高温处理温度：1000～3000℃，高温处理总时间1毫秒～500h，可梯度升温；
进一步地限定，热处理压力：0-200MPa；
进一步地限定，所用实现高温的设备为放电等离子烧结、真空炉、真空热压烧结炉、热等静压烧结设备、激光3D打印设备和气体保护炉。
本专利将石墨烯与非碳元素成键物质均匀混合，经高温处理，石墨烯与非碳元素发生化学反应，形成高强度、高热稳定性的化学键(如B-C、Ti-C等)，能有效实现石墨烯层间的连接，抑制石墨层间滑移，显著提升石墨烯为原料制备的块体材料的力学性能；同时非碳元素的引入，可赋予碳基材料耐高温等综合性能。该方法操作较简单，易于进行批量化生产，制备的碳基材料兼具高强、耐高温、导电、导热和轻质等优点，可用作火箭高温构件、热防护构件、超高功率电极、高导热散热构件、高性能坩埚、高温高性能模具、金属结晶器、刹车盘、研磨和切割用材料等。
为了能够更进一步了解本发明的特征及技术内容，请参阅以下有关本发明详细说明与附图，然而所附的附图仅提供参考和说明之用，并非用来对本发明加以限制。
附图说明
图1为实施例1中得到的石墨烯基材料XPS C1S谱图；
图2为实施例1中得到的石墨烯基材料XPS B1S谱图；
图3为实施例1中得到的石墨烯基材料力学性能测试结果；
图4为实施例1中得到的石墨烯基材料在空气气氛中热重测试结果；
图5为实施例2中得到的石墨烯基材料在压缩强度测试结果；
图6为实施例3中得到的石墨烯基材料在力学性能测试结果，左图是弯曲强度，右图是压缩强度；
图7是本专利制备的石墨烯基材料与碳基材料压缩强度对比结果。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1
按重量称取粒径为80nm硼粉5份(或10、20份)、燃烧合成法制备的石墨烯95份(或90、80份)。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨完成后，蒸除乙醇，既得到硼/石墨烯复合粉体。在1600℃的温度下，进行放电等离子体(SPS)烧结1分钟，得到了碳基材料。XPS结果表明该材料中石墨烯与硼之间形成了稳定的B-C键(图1、图2)，所制得的碳基材料弯曲强度如图3所示，其中含10％B的碳材料的最大弯曲强度为309MPa，最大压缩强度487MPa，在空气气氛中，从室温升温至1000℃，重量损失仅为0.2％(如图4所示)，材料表现出了优异的力学性能和抗氧化性能。
实施例2
称取重量为90份燃烧合成石墨烯和10份粒径为80nm钨粉。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨后，蒸出乙醇，得到钨/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。测试其压缩强度，如图5所示。相同制备条件获得的纯石墨烯块体材料压缩强度仅为28MPa，纳米钨与石墨烯成键后，压缩强度达到116MPa，石墨烯基块体材料压缩强度得到显著提升。
实施例3
称取重量为90份燃烧合成石墨烯和10份粒径为80nm金属钼粉。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，设置球磨时间为6h。球磨后，蒸出乙醇，得到钼/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。其压缩强度达到130MPa，如图5所示，显著高于相同条件下纯石墨烯为原料制备的块体材料。
实施例4
称取重量为90份燃烧合成石墨烯和10份粒径为80nm金属铪粉。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨后，蒸出乙醇，得到铪/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。其压缩强度达到106MPa，如图5所示，显著高于相同条件下纯石墨烯为原料制备的块体材料。
实施例5
称取重量为90份燃烧合成石墨烯和10份粒径为100nm锆粉。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨后，蒸出乙醇，得到锆/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。其压缩强度达到102MPa，如图5所示，显著高于相同条件下纯石墨烯为原料制备的块体材料。
实施例6
称取重量为90份燃烧合成石墨烯和10份粒径为100nm钛粉。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨后，蒸出乙醇，得到钛/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。其压缩强度达到98MPa，如图5所示，显著高于相同条件下纯石墨烯为原料制备的块体材料。
实施例7
称取重量为60份燃烧合成石墨烯、10份(或20份、30份、40份)粒径为80nm硼颗粒和40份粒径为80nm硅颗粒。与氧化锆球一同放入陶瓷罐中，球料比30:1。加入500份乙醇。球磨转速为300转每分钟，球磨6h。球磨完成后，蒸出乙醇，得到硅/硼/石墨烯复合粉体。在1600℃的温度下，SPS烧结1min，得到了碳基材料。测试其力学性能，如图6所示。弯曲强度最高达到574MPa，压缩强度最高达到2200MPa，该压缩强度远大于碳碳复合材料(C/C)、碳纤维增强碳化硅陶瓷基复合材料(C/C-SiC)，如图7所示。
实施例8
取2.5份聚碳硅烷，2.5份邻碳硼烷溶于100份二甲苯，加入20份石墨烯，超声搅拌1h。完成后，去除多余的二甲苯，再经过600℃高温热处理。随后在1800℃的温度下，进行真空热压烧结，得到碳基材料。
Claims (1)
1.一种基于无机物质的超高性能碳基材料，其特征在于，称取重量为 60 份燃烧合成石墨烯、30 份粒径为 80nm 硼颗粒和 40 份粒径为 80nm 硅颗粒，与氧化锆球一同放入陶瓷罐中，球料比 30:1，加入 500 份乙醇，球磨转速为 300 转每分钟，球磨 6h，球磨完成后，蒸出乙醇，得到硅/硼/石墨烯复合粉体，在 1600℃的温度下，SPS 烧结1min，得到了碳基材料，弯曲强度达到574MPa，压缩强度达到2200MPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210420325.XA CN114853476B (zh) | 2022-04-21 | 2022-04-21 | 一种基于无机物质的超高性能碳基材料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210420325.XA CN114853476B (zh) | 2022-04-21 | 2022-04-21 | 一种基于无机物质的超高性能碳基材料及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114853476A CN114853476A (zh) | 2022-08-05 |
| CN114853476B true CN114853476B (zh) | 2023-11-28 |
Family
ID=82631010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210420325.XA Active CN114853476B (zh) | 2022-04-21 | 2022-04-21 | 一种基于无机物质的超高性能碳基材料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114853476B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857221A (zh) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | 高效率制备石墨烯复合物或氧化石墨烯复合物的方法 |
| US20150246851A1 (en) * | 2012-09-20 | 2015-09-03 | The Penn State Research Foundation | Process For Production Of Graphene/Silicon Carbide Ceramic Composites |
| CN106784828A (zh) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 一种层铸成型石墨烯‑金属复合材料及制备方法 |
| CN110257663A (zh) * | 2019-07-09 | 2019-09-20 | 上海帛汉新材料科技有限公司 | 一种石墨烯增强铜基复合材料的制备方法 |
| CN111348915A (zh) * | 2020-03-18 | 2020-06-30 | 东华大学 | 一种缺碳型ZrC1-x/C复相陶瓷材料及其制备方法 |
-
2022
- 2022-04-21 CN CN202210420325.XA patent/CN114853476B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857221A (zh) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | 高效率制备石墨烯复合物或氧化石墨烯复合物的方法 |
| US20150246851A1 (en) * | 2012-09-20 | 2015-09-03 | The Penn State Research Foundation | Process For Production Of Graphene/Silicon Carbide Ceramic Composites |
| CN106784828A (zh) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 一种层铸成型石墨烯‑金属复合材料及制备方法 |
| CN110257663A (zh) * | 2019-07-09 | 2019-09-20 | 上海帛汉新材料科技有限公司 | 一种石墨烯增强铜基复合材料的制备方法 |
| CN111348915A (zh) * | 2020-03-18 | 2020-06-30 | 东华大学 | 一种缺碳型ZrC1-x/C复相陶瓷材料及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 李杰.碳化硅/石墨烯复合材料制备及其性能研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2020,B020-501. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114853476A (zh) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102603271B (zh) | 石墨烯和氧化物陶瓷复合材料及制备方法 | |
| Han et al. | A review on the processing technologies of carbon nanotube/silicon carbide composites | |
| JP5057327B2 (ja) | 炭化ホウ素セラミックスおよびその製造方法 | |
| KR101537942B1 (ko) | 파괴인성이 우수한 그래핀-세라믹 복합체의 제조방법 | |
| CN100503513C (zh) | SiC-BN-C复合材料及其制备方法 | |
| CN110157931B (zh) | 一种具有三维网络结构的纳米碳增强金属基复合材料及其制备方法 | |
| CN103724014A (zh) | 一种高热导金刚石掺杂SiC陶瓷的制备方法 | |
| WO2014098370A1 (ko) | 탄소나노튜브를 포함하는 초경합금의 제조방법, 이에 의해 제조된 초경합금 및 초경합금을 포함하여 이루어지는 초경 절삭공구 | |
| Hu et al. | Electrostatic self-assembly preparation of reduced graphene oxide-encapsulated alumina nanoparticles with enhanced mechanical properties of alumina nanocomposites | |
| CN110436928A (zh) | 高性能纳米孪晶碳化硼陶瓷块体材料及其制备方法 | |
| CN103214264A (zh) | 一种氮化硅纳米线增强氮化硅多孔陶瓷的方法 | |
| JP2004339048A (ja) | Ｃ−ＳｉＣ焼結体およびその製造方法 | |
| Ikram et al. | Enhanced physical properties of γ-Al 2 O 3–rGO hybrids prepared by solvothermal and hot-press processing | |
| CN114853476B (zh) | 一种基于无机物质的超高性能碳基材料及其制备方法 | |
| CN113773090A (zh) | 一种ZrB2-ZrC-SiC纳米复合陶瓷材料的制备方法 | |
| CN111747748B (zh) | 超高温防/隔热一体化ZrC/Zr2C复相材料及其制备方法 | |
| CN110642233B (zh) | 一种c掺杂氮化硼纳米管与碲化铋复合薄膜的制备方法 | |
| CN111484017A (zh) | 一种基于二氧化硅微球@C制备SiC纳米颗粒的方法 | |
| CN111348915A (zh) | 一种缺碳型ZrC1-x/C复相陶瓷材料及其制备方法 | |
| CN115259874B (zh) | 增韧、导电MXene-氧化锆复合陶瓷及其制备方法 | |
| KR20110016776A (ko) | 지르코늄실리사이드들을 전구체로 하는 나노크기를 갖는 ＺｒＢ２－ＳｉＣ 조성물 및 그 제조방법 | |
| JP2008074667A (ja) | 炭化ケイ素焼結体シート及びその製造方法 | |
| Dyatkin et al. | Synthesis, structure, and properties of polymer‐derived, metal‐reinforced boron carbide cermet composites | |
| Chen et al. | Recent advances in precursor-derived ceramics integrated with two-dimensional materials | |
| CN111732436A (zh) | 易烧结钛和钨共掺杂碳化锆粉体及其制备方法 |
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 |