CN105693217A - 一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法 - Google Patents
一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法 Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- -1 germanium oxide-barium oxide Chemical compound 0.000 title abstract description 5
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 92
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 88
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 88
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000008595 infiltration Effects 0.000 claims description 16
- 238000001764 infiltration Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012756 surface treatment agent Substances 0.000 claims description 8
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000018109 developmental process Effects 0.000 abstract description 5
- 238000000352 supercritical drying Methods 0.000 abstract description 2
- 238000001879 gelation Methods 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明提供了一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,方法包括将制备好的杂化溶胶浸渗到处理过的无机纤维材料中,经凝胶、充分老化后,再经超临界干燥得杂化气凝胶复合材料。本发明提供的技术方案制备工艺简单、易操作,且首次制备出性能优异的氧化锗和氧化钡杂化气凝胶;本发明提供的技术方案制备出高比表面积、低密度、高孔隙率的氧化锗和氧化钡杂化气凝胶,其优异性能为比表面积300~400m2/g、密度0.13~0.20g/m3、孔隙率80~90%;本发明提供的气凝胶复合材料在1000℃下的热导率小于0.035w/m·k,收缩率小于3.4%;本发明提供的技术方案,拓宽了氧化锗材料的发展和应用。
Description
技术领域
本发明涉及一种气凝胶的制备方法,具体讲,涉及一种氧化锗和氧化钡气凝胶复合材料的制备方法。
背景技术
气凝胶是指以纳米颗粒相互聚集构成的纳米多孔网络为骨架,并在网络骨架孔隙中充满气态分散介质的轻质纳米固态材料。气凝胶作为一种纳米材料,除具有纳米材料的特性外,还具有其他优异性能,如:极高的孔隙率、高比表面积、极低的密度、低的热导率和低的声音传播速率等,在催化、航天、医药、能源、建筑和冶金等方面有着巨大的应用前景。
同时,气凝胶种类也得到了极大丰富,如金属气凝胶,有机气凝胶和碳气凝胶,至此越来越多的新型气凝胶逐步被开发出来。
氧化锗可广泛用于制作高纯金属锗、锗化合物、化工催化剂、医药工业,PET树脂、电子器件等;例如,含氧化锗的玻璃有较高的折射率和色散性能,可作为广角照相机和显微镜镜头。为了进一步拓展气凝胶的发展,本发明将首次阐述具有独特结构和性能的氧化锗和氧化钡杂化气凝胶复合材料的制备方法,能更好的推动该类材料的发展和应用,同时拓宽了气凝胶的种类,推动了气凝胶科技的发展。
发明内容
本发明的目的是提供一种高比表面积、低密度、高孔隙率、低导热及收缩率小的氧化锗和氧化钡杂化气凝胶复合材料的制备方法;本发明提供的技术方案制作工艺简单、易操作,且首次制备出性能优异的氧化锗和氧化钡杂化气凝胶。
实现本发明目的技术方案如下:
一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,所述复合材料包括氧化锗和氧化钡杂化气凝胶、无机纤维材料,所述制备方法包括如下步骤:
1)无机纤维材料的处理:150~200℃下,干燥无机纤维4~6小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:2~4:0.004~0.008:0.012~0.02的比例配制的表面处理剂溶液后,于160~220℃下烘干1~3小时,冷却得表面处理后的无机纤维;
其中,所述无机纤维为玻璃纤维,所述玻璃纤维包括按质量百分比计的下述组份:50~60%,SiO2;12~18%,Al2O3;21~27%,B2O3;0~2%,CaO;0.5~3%,MgO;0.5~4%,ZnO;0.5~4%,TiO2;0.5%~3%,CaF2;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为0.5~1:0.5~2:10~50:10~40:0.05~0.5:10-4~10-2的比例配制混合液,搅拌10~20min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于50~80℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;20~50℃老化20~50h后,经乙醇或二氧化碳超临界干燥后;在惰性气体保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
进一步的,所述步骤4)中惰性气体为氮气、氦气或氖。所述步骤4)中高温煅烧温度为600~1200℃。
进一步的,所述醇类物质为甲醇、乙醇、丙醇或丁醇。所述催化剂为盐酸、硫酸、磷酸、甲酸、乙酸、乙二酸或氢氟酸。所述偶联剂为γ-氨丙基三乙氧基硅烷、N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷、甲基三甲氧基硅烷或乙烯基三甲氧基硅烷。所述表面活性剂为十二烷基二甲基苄基氯化铵、十二烷基苯磺酸钠、十二烷基二甲基氧化胺、十二烷基二甲基胺乙内酯或甘油聚氧乙烯醚。
进一步的,所述方法制备的氧化锗和氧化钡杂化凝胶比表面积300~400m2/g,孔隙率80~90%。所述方法制备出的氧化锗和氧化钡杂化气凝胶复合材料在1000℃下的热导率小于0.035w/m·k,收缩率小于3.4%。
和最接近的现有技术比,本发明提供的技术方案具有以下优异效果:
1、本发明提供的技术方案制备工艺简单、易操作,适合大规模生产,且首次制备出性能优异的氧化锗和氧化钡杂化气凝胶。
2、本发明提供的技术方案制备出高比表面积、低密度、高孔隙率的氧化锗和氧化钡杂化气凝胶,其优异性能为比表面积300~400m2/g以上、密度0.13~0.20g/m3、孔隙率80~90%。
3、本发明提供的技术方案制备出的氧化锗和氧化钡杂化气凝胶复合材料在1000℃下的热导率小于0.035w/m·k,收缩率小于3.4%。
4、本发明提供的技术方案,拓宽了氧化锗材料的发展和应用。
具体实施方式
下面将结合本发明实施例进一步的对技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅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所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
1)无机纤维材料的处理:200℃下,干燥无机纤维6小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:4:0.008:0.02的比例配制的表面处理剂溶液后,于220℃下烘干1小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为1:0.5:10:10:0.05:10-4的比例配制混合液,搅拌20min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于80℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;50℃老化20h后,经超临界干燥后;在惰性气体氮气保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行600℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
实施例2
1)无机纤维材料的处理:150℃下,干燥无机纤维6小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:2:0.004:0.012的比例配制的表面处理剂溶液后,于160℃下烘干3小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为0.5:2:50:40:0.5:10-2的比例配制混合液,搅拌15min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于50℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;20℃老化50h后,经乙醇或二氧化碳超临界干燥后;在惰性气体氖保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行1200℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
实施例3
1)无机纤维材料的处理:180℃下,干燥无机纤维5小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:3:0.006:0.016的比例配制的表面处理剂溶液后,于200℃下烘干2小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为1::30:20:0.1:10-3的比例配制混合液,搅拌20min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于70℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;40℃老化35h后,经乙醇或二氧化碳超临界干燥后;在惰性气体氦气保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行800℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
实施例4
1)无机纤维材料的处理:180℃下,干燥无机纤维4小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:3:0.007:0.014的比例配制的表面处理剂溶液后,于180℃下烘干3小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为0.5:1:40:30:0.2:10-4的比例配制混合液,搅拌15min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于65℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;45℃老化30h后,经乙醇或二氧化碳超临界干燥后;在惰性气体氮气保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行900℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
实施例5
1)无机纤维材料的处理:175℃下,干燥无机纤维4小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:4:0.007:0.018的比例配制的表面处理剂溶液后,于220℃下烘干2小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为1:2:35:25:0.4:10-2的比例配制混合液,搅拌18min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于75℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;40℃老化45h后,经乙醇或二氧化碳超临界干燥后;在惰性气体氖保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行1000℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
实施例6
1)无机纤维材料的处理:200℃下,干燥无机纤维5小时;将无机纤维浸入按无机纤维、蒸馏水、表面活性剂及偶联剂重量比为1:3:0.006:0.016的比例配制的表面处理剂溶液后,于200℃下烘干3小时,冷却得表面处理后的无机纤维;
其中,无机纤维为玻璃纤维;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为1:2:35:40:0.5:10-3的比例配制混合液,搅拌14min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于65℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;25℃老化35h后,经乙醇或二氧化碳超临界干燥后;在惰性气体氦气保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行1100℃高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
上述各实施例所用原料种类及其比例,如表1和表2所示。
表1
表2
实施例中所得样品性能列于下表3。
表3
以上实施例仅用以说明本发明的技术方案而非对其限制,所属领域的普通技术人员应当理解,参照上述实施例可以对本发明的具体实施方式进行修改或者等同替换,这些未脱离本发明精神和范围的任何修改或者等同替换均在申请待批的权利要求保护范围之内。
Claims (9)
1.一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述复合材料包括氧化锗和氧化钡杂化气凝胶、无机纤维材料,所述制备方法包括如下步骤:
1)无机纤维材料的处理:150~200℃下,干燥无机纤维4~6小时;将无机纤维浸入按重量比为1:2~4:0.004~0.008:0.012~0.02的比例的无机纤维、蒸馏水、表面活性剂及偶联剂配制的表面处理剂溶液处理后,于160~220℃下烘干1~3小时,冷却;
其中,所述无机纤维为玻璃纤维,所述玻璃纤维包括按质量百分比计的下述组份:50~60%,SiO2;12~18%,Al2O3;21~27%,B2O3;0~2%,CaO;0.5~3%,MgO;0.5~4%,ZnO;0.5~4%,TiO2;0.5%~3%,CaF2;
2)氧化锗和氧化钡杂化溶胶的制备:将氯化锗、氯化钡、醇类物质、去离子水、环氧丙烷和催化剂按照摩尔比为0.5~1:0.5~2:10~50:10~40:0.05~0.5:10-4~10-2的比例配制混合液,搅拌10~20min静置后,得氧化锗和氧化钡杂化溶胶;
3)浸渗:用步骤2)的氧化锗和氧化钡杂化溶胶浸渗经步骤1)处理后的无机纤维材料;
4)制备氧化锗和氧化钡杂化气凝胶复合材料:于50~80℃下,使步骤3)所得浸渗物中的氧化锗和氧化钡杂化溶胶发生胶凝,得氧化锗和氧化钡杂化凝胶;20~50℃下老化20~50h后,经乙醇或二氧化碳超临界干燥后;在惰性气体保护下,将氧化锗和氧化钡杂化气凝胶复合材料进行高温煅烧,得氧化锗和氧化钡杂化气凝胶复合材料。
2.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述步骤4)中惰性气体为氮气、氦气或氖。
3.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述步骤4)中高温煅烧温度为600~1200℃。
4.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述醇类物质为甲醇、乙醇、丙醇或丁醇。
5.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述催化剂为盐酸、硫酸、磷酸、甲酸、乙酸、乙二酸或氢氟酸。
6.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述偶联剂为γ-氨丙基三乙氧基硅烷、N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷、甲基三甲氧基硅烷或乙烯基三甲氧基硅烷。
7.如权利要求1所述的一种氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述表面活性剂为十二烷基二甲基苄基氯化铵、十二烷基苯磺酸钠、十二烷基二甲基氧化胺、十二烷基二甲基胺乙内酯或甘油聚氧乙烯醚。
8.如权利要求1~7任意一种所述的氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述方法制备的氧化锗和氧化钡杂化凝胶比表面积300~400m2/g,孔隙率80~90%。
9.如权利要求1~7任意一种所述的氧化锗和氧化钡杂化气凝胶复合材料的制备方法,其特征在于,所述方法制备出的氧化锗和氧化钡杂化气凝胶复合材料在1000℃下的热导率小于0.035w/m·k,收缩率小于3.4%。
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