CN115124074B - 一种高分散复合纳米二氧化锆的制备方法 - Google Patents
一种高分散复合纳米二氧化锆的制备方法 Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000006185 dispersion Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 150000003754 zirconium Chemical class 0.000 claims abstract description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 18
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 150000003746 yttrium Chemical class 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 claims description 5
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- IFJYVNTXUVQYOU-UHFFFAOYSA-J pentanoate zirconium(4+) Chemical compound [Zr+4].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O IFJYVNTXUVQYOU-UHFFFAOYSA-J 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012671 ceramic insulating material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01F17/00—Compounds of rare earth metals
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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Abstract
本发明公开了一种高分散复合纳米二氧化锆的制备方法,本发明将锆盐通过醇水解反应得到锆溶胶初液,将钇盐加入水中得到钇溶液,将锆溶胶初液、碱水溶液和钇溶液通过水热反应和高温高压水热细化得到纳米水合复合氧化锆浆料,陈化后进行固液分离再经过滤和洗涤得到提纯湿料。将提纯湿料、修饰剂、水及醇类通过高剪切修饰处理得到修饰料,将修饰料干燥后通过辊窑焙烧得到复合纳米二氧化锆干粉,再经粉碎、消磁、过筛得到高分散复合纳米二氧化锆成品。本发明制备的复合纳米二氧化锆具有晶粒均一且小、复合性好、韧度高、分散性好的特点。
Description
技术领域
本发明涉及一种高分散复合纳米二氧化锆的制备方法,属于纳米材料制备技术领域。
背景技术
二氧化锆具有高熔点、高电阻率、高折射率和低热膨胀系数的性质,使它成为重要的耐高温材料、陶瓷绝缘材料和陶瓷遮光剂,亦是人工钻的主要原料。
纯氧化锆在室温为单斜晶相,温度上升至约1173℃时会转变成四方晶相,上升至2370℃时,则转换成立方晶相,于2690℃变成液相。纯氧化锆从高温冷却至室温,经过相变态温度时正方晶转换成单斜晶,因其体积剧烈改变,造成烧结后的成品含有微裂缝,往往影响使用效果。二氧化锆室温下不以立方晶相(萤石晶体结构)存在,但借由添加其他的氧化物可大幅增加二氧化锆以立方晶相稳定存在的温度范围,复合相稳定剂的二氧化锆被称作稳定性氧化锆。
现有工艺制备的稳定性氧化锆复合性差,脆性大,分散性差,因此需要一种新的复合纳米二氧化锆的制备方法。
发明内容
针对上述不足,本发明提供一种高分散复合纳米二氧化锆的制备方法,本发明所采用的技术方案为:
一种高分散复合纳米二氧化锆的制备方法,其制备方法为:
将锆盐通过醇水解反应得到锆溶胶初液并在醇水解反应时加入表面活性剂,锆盐、水及醇的量为1∶(5~20)∶(0~20),将钇盐加入水中得到钇溶液,钇盐的量为锆盐的0.1~10%。
将锆溶胶初液、碱水溶液和钇溶液通过水热反应得到水合复合氧化锆浆料,再通过高温高压水热细化得到纳米水合复合氧化锆浆料,陈化后进行固液分离,再经过滤和洗涤得到提纯湿料。
将提纯湿料、修饰剂、水及醇类通过高剪切修饰处理得到修饰料,修饰剂、水及醇的加入量为锆盐∶修饰剂∶水∶醇=20∶(0.5~5)∶(1~10)∶(1~10)。
将修饰料干燥后通过辊窑焙烧得到复合纳米二氧化锆干粉,再经粉碎、消磁、过筛得到高分散复合纳米二氧化锆成品。
与现有技术相比,本发明的有益效果在于:本发明制备的复合纳米二氧化锆具有晶粒均一且小、复合性好、韧度高、分散性好的特点。
附图说明
图1为本发明的高分散复合纳米二氧化锆SEM图;
图2为本发明的高分散复合纳米二氧化锆XRD图。
具体实施方式
下面结合附图和实施例对本发明的技术方案做进一步的说明。
一种高分散复合纳米二氧化锆的制备方法,其制备方法具体包括如下步骤:
步骤1.在反应釜中将锆盐缓慢加入去离子水和醇中搅拌均匀并加入表面活性剂充分混合均匀得到锆溶胶初液,锆盐、去离子水及醇的量为1∶(5~20)∶(0~20);将锆盐重量0.1~10%的钇盐加入去离子水中得到钇溶液,钇溶液中钇盐与离子水的配比为1∶(2~15);将碱制备成一定比例的碱水溶液。
步骤2.将锆溶胶初液升温至50~110℃,缓慢加入碱水溶液调节PH=7~11,保温搅拌反应1~5h,再缓慢加入钇溶液并同时加入碱水溶液保持PH=7~11,保温搅拌反应1~60h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=7~11,再缓慢升温到150~220℃,釜内压力调节至0.7~1MPa,保温保压搅拌反应1~70h,得到纳米水合复合氧化锆浆料。
步骤3.将纳米水合复合氧化锆浆料降温至20~35℃,静置陈化10~70h,陈化后进行固液分离,将分离物料采用超滤、纳滤、高压反渗透膜过滤和洗涤得到提纯湿料。
步骤4.将提纯湿料、修饰剂、去离子水及醇类通过高剪切修饰处理1~20h得到修饰料,修饰剂、去离子水及醇的加入量为锆盐∶修饰剂∶去离子水∶醇=20∶(0.5~5)∶(1~10)∶(1~10)。
步骤5.采用超临界或冷冻或者喷雾干燥中的一种或者几种方式将修饰料干燥得到干燥粉,将干燥粉经过辊窑在400~1300℃进行焙烧,得到锆钇复合干粉;再经粉碎、消磁、过筛得到高分散复合纳米二氧化锆成品。
优选的,所述锆盐为醋酸锆、乙醇锆、硝酸锆、丙醇锆、氧氯化锆、异丙醇锆、己酸锆、戊酸锆、甲醇锆中的一种或者几种。
优选的,所述钇盐为硝酸钇、醋酸钇、氯化钇中的一种或者几种。
优选的,所述表面活性剂为聚氧乙烯脂肪胺、多元醇脂肪酸脂、月桂醇油醇中的一种或者几种,加入量为锆盐的0.1-8%。
优选的,所述修饰剂为脂肪醇聚氧乙烯醚硫酸酯、聚氧乙烯单月桂酸酯、含氟脂肪酸盐中的一种或者几种。
优选的,所述醇为甲醇、乙醇、丙醇、异丙醇、丁醇、二戊醇、己醇中的一种或者几种。
优选的,所述碱为氨水、乙醇胺、环己胺、丙醇胺、氢氧化钾中的一种或者几种,碱水溶液的浓度为5~20%。
优选的,焙烧过程中干燥粉的粉体厚度为0.5~5cm。
实施例1:
在反应釜中,按质量比1∶5∶3将醋酸锆加入去离子水和甲醇中搅拌均匀,再加入醋酸锆重量3%的表面活性剂聚氧乙烯脂肪胺,充分混合均匀得到锆溶胶初液;将醋酸锆重量5%的硝酸钇加入去离子水中得到钇溶液;将氨水调配成5~20%浓度的碱水溶液。将锆溶胶初液以0.5~5℃/min升温至80℃,以0.5-5L/min加入碱水溶液调节PH=8,保温搅拌反应1h,再以0.5-5L/min加入钇溶液并同时加入碱水溶液保持PH=8,保温搅拌反应40h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=8,再以0.5~5℃/min升温到180℃,釜内压力调节至0.7MPa,保温保压搅拌反应50h得到纳米水合复合氧化锆浆料。将纳米水合复合氧化锆浆料降温至20℃,密闭静置陈化20h。再进行固液分离,将分离物料加入去离子水采用超滤、纳滤、高压反渗透膜中的一种或几种并用方式过滤、再采用离心、抽滤、压滤中的一种或者几种并用方式洗涤,重复上述操作多次后得到提纯湿料。向提纯湿料中加入修饰剂脂肪醇聚氧乙烯醚硫酸酯、去离子水及甲醇,加入量为醋酸锆∶脂肪醇聚氧乙烯醚硫酸酯∶去离子水∶甲醇=20∶3∶3∶5,采用高速剪切分散设备高剪切修饰处理5h得到修饰料。采用超临界干燥将修饰料干燥得到干燥粉,将干燥粉以1cm的厚度经过辊窑在800℃焙烧,得到锆钇复合干粉,再经粉碎、消磁、过筛等工序得到高分散复合纳米二氧化锆成品。
实施例2:
在反应釜中,按质量比1∶5∶6将乙醇锆加入去离子水和乙醇中搅拌均匀,再加入乙醇锆重量4%的表面活性剂多元醇脂肪酸脂,充分混合均匀得到锆溶胶初液;将乙醇锆重量5%的醋酸钇加入去离子水中得到钇溶液;将环己胺调配成碱水溶液。将锆溶胶初液升温至90℃,加入碱水溶液调节PH=8.5,保温搅拌反应2h,再加入钇溶液并同时加入碱水溶液保持PH=8.5,保温搅拌反应30h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=8.5,再升温到190℃,釜内压力调节至0.8MPa,保温保压搅拌反应30h得到纳米水合复合氧化锆浆料。将纳米水合复合氧化锆浆料降温至30℃,密闭静置陈化30h。将陈化后的纳米水合复合氧化锆浆料采用与实施例1相同的处理方式得到提纯湿料。向提纯湿料中加入修饰剂聚氧乙烯单月桂酸酯、去离子水及乙醇,加入量为乙醇锆∶聚氧乙烯单月桂酸酯∶去离子水∶乙醇=20∶4∶5∶6,采用高速剪切分散设备高剪切修饰处理5h得到修饰料。采用冷冻干燥将修饰料干燥得到干燥粉,将干燥粉以2cm的厚度经过辊窑在900℃焙烧,得到锆钇复合干粉,再经粉碎、消磁、过筛等工序得到高分散复合纳米二氧化锆成品。
实施例3:
在反应釜中,按质量比1∶8∶3将硝酸锆加入去离子水和异丙醇中搅拌均匀,再加入硝酸锆重量5%的表面活性剂月桂醇油醇,充分混合均匀得到锆溶胶初液;将硝酸锆重量6%的氯化钇加入去离子水中得到钇溶液;将氢氧化钾调配成碱水溶液。将锆溶胶初液升温至95℃,加入碱水溶液调节PH=9,保温搅拌反应1.5h,再加入钇溶液并同时加入碱水溶液保持PH=9,保温搅拌反应50h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=9,再升温到200℃,釜内压力调节至0.9MPa,保温保压搅拌反应60h得到纳米水合复合氧化锆浆料。将纳米水合复合氧化锆浆料降温至20℃,密闭静置陈化40h。将陈化后的纳米水合复合氧化锆浆料采用与实施例1相同的处理方式得到提纯湿料。向提纯湿料中加入修饰剂含氟脂肪酸钾、去离子水及异丙醇,加入量为硝酸锆∶含氟脂肪酸钾∶去离子水∶异丙醇=20∶3∶5∶8,采用高速剪切分散设备高剪切修饰处理6h得到修饰料。采用冷冻干燥将修饰料干燥得到干燥粉,将干燥粉以1cm的厚度经过辊窑在1000℃焙烧,得到锆钇复合干粉,再经粉碎、消磁、过筛等工序得到高分散复合纳米二氧化锆成品。
附图1为本发明的高分散复合纳米二氧化锆SEM图,从图中可见本发明制备的高分散复合纳米二氧化锆成品粉末颗粒均一,稳定,外观圆润,颗粒小,整体颗粒成类球形,大小在5-10nm左右;
附图2为本发明的高分散复合纳米二氧化锆XRD图,从图中可见本发明制备的高分散复合纳米二氧化锆成品粉末峰型尖锐,结晶性好,峰型比较明显,无各种杂峰出现。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (4)
1.一种高分散复合纳米二氧化锆的制备方法,其特征在于,其制备方法为:
将锆盐缓慢加入去离子水和醇中搅拌均匀并加入表面活性剂充分混合均匀得到锆溶胶初液,锆盐、水及醇的量为1∶(5~20)∶(0~20),将钇盐加入水中得到钇溶液,钇盐的量为锆盐的0.1~6%;
将锆溶胶初液升温至50~110℃,缓慢加入碱水溶液调节PH=7~11,保温搅拌反应1~5h,再缓慢加入钇溶液并同时加入碱水溶液保持PH=7~11,保温搅拌反应1~60h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=7~11,再缓慢升温到150~220℃,釜内压力调节至0.7~1MPa,保温保压搅拌反应1~70h,得到纳米水合复合氧化锆浆料;陈化后进行固液分离,再经过滤和洗涤得到提纯湿料;
将提纯湿料、修饰剂、水及醇类通过高剪切修饰处理得到修饰料,修饰剂、水及醇的加入量为锆盐∶修饰剂∶水∶醇=20∶(0.5~5)∶(1~10)∶(1~10);
将修饰料干燥后通过辊窑焙烧得到复合纳米二氧化锆干粉,再经粉碎、消磁、过筛得到高分散复合纳米二氧化锆成品;
所述锆盐为醋酸锆、乙醇锆、硝酸锆、丙醇锆、氧氯化锆、己酸锆、戊酸锆、甲醇锆中的一种或者几种;
所述钇盐为硝酸钇、醋酸钇、氯化钇中的一种或者几种;
所述表面活性剂为聚氧乙烯脂肪胺、多元醇脂肪酸脂、月桂醇油醇中的一种或者几种,加入量为锆盐的0.1-8%;
所述修饰剂为脂肪醇聚氧乙烯醚硫酸酯、聚氧乙烯单月桂酸酯、含氟脂肪酸盐中的一种或者几种。
2.根据权利要求1所述的一种高分散复合纳米二氧化锆的制备方法,其特征在于,其制备方法具体包括如下步骤:
步骤1.在反应釜中将锆盐缓慢加入去离子水和醇中搅拌均匀并加入表面活性剂充分混合均匀得到锆溶胶初液,锆盐、去离子水及醇的量为1∶(5~20)∶(0~20);将锆盐重量0.1~6%的钇盐加入去离子水中得到钇溶液,钇溶液中钇盐与离子水的配比为1∶(2~15);将碱制备成一定比例的碱水溶液;
步骤2.将锆溶胶初液升温至50~110℃,缓慢加入碱水溶液调节PH=7~11,保温搅拌反应1~5h,再缓慢加入钇溶液并同时加入碱水溶液保持PH=7~11,保温搅拌反应1~60h,得到水合复合氧化锆浆料;再缓慢加入碱水溶液调节PH=7~11,再缓慢升温到150~220℃,釜内压力调节至0.7~1MPa,保温保压搅拌反应1~70h,得到纳米水合复合氧化锆浆料;
步骤3.将纳米水合复合氧化锆浆料降温至20~35℃,静置陈化10~70h,陈化后进行固液分离,将分离物料采用超滤、纳滤、高压反渗透膜过滤和洗涤得到提纯湿料;
步骤4.将提纯湿料、修饰剂、去离子水及醇类通过高剪切修饰处理1~20h得到修饰料,修饰剂、去离子水及醇的加入量为锆盐∶修饰剂∶去离子水∶醇=20∶(0.5~5)∶(1~10)∶(1~10);
步骤5.采用超临界或冷冻或者喷雾干燥中的一种或者几种方式将修饰料干燥得到干燥粉,将干燥粉经过辊窑在400~1300℃进行焙烧,得到锆钇复合干粉;再经粉碎、消磁、过筛得到高分散复合纳米二氧化锆成品。
3.根据权利要求1或2所述的一种高分散复合纳米二氧化锆的制备方法,其特征在于,所述醇为甲醇、乙醇、丙醇、丁醇、二戊醇、己醇中的一种或者几种。
4.根据权利要求1或2所述的一种高分散复合纳米二氧化锆的制备方法,其特征在于,所述碱为氨水、乙醇胺、环己胺、丙醇胺、氢氧化钾中的一种或者几种,碱水溶液的浓度为5~20%。
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