In_2O_3/SnO_2纳米粉制备表征与表面修饰研究
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摘要
本课题是总装备部新型无机-高分子纳米复合可视屏蔽材料项目的一个子课
题。大课题采取无机-高分子纳米复合技术路线，研制氧化铟、氧化锡等金属氧
化物纳米粒子／丙烯酸酯类聚合物纳米复合材料，要求高透光、高电磁屏蔽。有
机玻璃透明性好，但为绝缘体因而不具有屏蔽效能。在有机材料中掺加导电粒子，
由于其互相接触或处于极靠近的位置，通过空气或电解质之间的热释电子或隧道
效应而导电，但基体中导电粒子间必须有足够的透光间隙或粒子本身比可见光波
长小才具透明性。所以本研究的目的是利用液相法中较有前途的溶胶-凝胶法制
备氧化铟、氧化锡及其复合氧化物(In_2O_3／SnO_2)纳米粉料，并对其进行表面修
饰和综合表征，为大课题提供原材料并可望总结出普遍可行的纳米粒子制备、修
饰及表征方法。
本文第一部分对In_2O_3／SnO_2的导电机理及对In_2O_3／SnO_2纳米粉制备方法的
研究进展进行了综合评述。
本文第二部分详细地研究了溶胶-凝胶法制备In_2O_3／SnO_2纳米粉体的工艺条
件及参数，还对Sn-In_2O_3(锡掺杂氧化铟)纳米粉体的导电性能进行仔细研究；并
利用TG-DSC、FT-IR、XRD、SEM、EDS、TEM和BET等多种现代测试方法
对所制In_2O_3／SnO_2纳米粉体的结构、粒度、形貌、成分等进行了综合表征与分析。
在对溶胶-凝胶法制备In_2O_3／SnO_2纳米粉体的工艺研究中，研究了反应温度、
反应pH值、煅烧制度、反应物浓度、老化制度等对In_2O_3／SnO_2纳米粉体质量的
影响。总结出制备三种粉料的优化工艺条件为：NH_3·H_2O浓度为25-28％，反应
温度为50-70℃，老化制度为40℃／4h左右，超声分散30min，煅烧制度为800
℃／1h，其中合成氧化锡前驱料，SnCl_4·5H_2O的适宜浓度为20g／100mL左右，
反应pH值为8-11，合成氧化铟前驱料，InCl_3·4H_2O的适宜浓度为5-10g／100mL，
反应pH值为7或10.5以上，合成锡掺杂氧化铟前驱料，InCl_3·4H_2O的适宜浓度
为5-10g／100mL，并加入相应比例(Wt_(In2O3)／Wt_(SnO2)=9∶1)的SnCl_4·5H_2O，反应
pH值为7或10.5以上。
Sn-In_2O_3纳米粉体的电性能研究表明：Sn-In_2O_3前驱物在700-1000℃煅烧，
方块电阻较低，真空条件下煅烧试样的电阻比空气条件下煅烧试样的电阻低，
南京工业大学硕士学位论文
中文摘要
sno:掺杂10wt%左右时，试样方块电阻最低。
通过对InZO3/S nOZ纳米粉体表征，得出InZO3/S nOZ纳米粒子多呈球形、颗粒
均匀、分散性良好、组分均匀、纯度较高、平均粒径在4一50lun左右、比表面积
达67一156 mZ/g;snoZ纳米粉为正四面体金红石结构，InZo3和sn一InZo3纳米粉
为体心立方结构。
本文第三部分，结合丙烯酸酷类单体，对Sn一InZ仇纳米微粒进行表面修饰
研究，最后得出选用 KH一560和KH一570作表面修饰剂，添加量为0.5一lwt%左右，
pH值为5.4左右，采用球磨72小时，辅助超声分散工艺时，Sn一In20:纳米粉的
分散性较好，且与基体有较好的相容性。
本文最后部分，就整个研究工作进行了总结，并得出结论。
This program is from general assembly department about new nano complex of inorganic-macromolecule shielded material. Nano indium, tin oxide etc. particles/polymer composite was studied. High transparence and electromagnetic shielded efficiency are asked. The transparency of organic glass is good, but it is nonconductor and has no shielded efficiency. When conducting particles are added to organic materials, they are conductive. But the composite must have enough pervious light gap between conducting particles, or the particle size is less than the wavelength of visible light. So preparation of indium, tin oxide (In2O3/SnO2) nano powders by promising method of sol - gel in liquid and surface modification were studied. We hope to summarize general nano preparation, modification and characterization methods.
In the first part of the dissertation, the conducting mechanism and the current study on nano powders preparation methods of In2O3/SnO2 are reviewed.
In the second part, the processes were studied on preparing In2O3/SnO2 nano powders in details by sol - gel method, and the electrical property was carefully studied of tin doped indium oxide (Sn-In2O3) nano powder too. The structure, morphology, particle size, specific surface area, and composition of In2O3/SnO2 nano powder were characterized by means of TG-DSC, FT-IR, XRD, SEM, EDS , TEM and BET.
In the technology research of preparing In2O3/SnO2 nano powders, the influence factors were studied, such as reaction temperature, reaction pH value, dry technology, calcinating systems, reaction material concentration and ageing systems etc. The best technology conditions were reached finally.
Through study on the electrical performance of Sn-In2O3 nano powder, some conclusions were drawn. When Sn-In2O3 precursor was calcinated at 700-1000 , low square resistance was got. The resistance was lower when Sn-In2O3 precursor was calcinated in vacuum than air condition. When SnO2 wt % was controlled for 10 %, the square resistance of Sn-In2O3 was minimum.
Through the characterization of In2O3/SnO2 nano powders, some conclusions were drawn: SnO2 nano powder is rutile structure, and In2O3 and Sn-In2O3 nano powders are cubic structure. In2O3/SnO2 nano powders were well dispersing with
spherical uniform grain, and the mean grain was 4-50 nm. The purity and composition uniformity were very high, and the specific surface area was 67-156 nm.
In the third part, surface modification of Sn-In2O3 nano particle was studied and some conclusions were drawn finally. KH560 and KH570 were selected as surface modification agents, and the concentration of them was 0.5-1 wt %, and pH value was controlled for 5.4, and the best milled technology were 72 hours. Surface modified Sn-In2O3 nano powder was well dispersing in matrix.
In the last part, conclusions were summarized.
题。大课题采取无机-高分子纳米复合技术路线，研制氧化铟、氧化锡等金属氧
化物纳米粒子／丙烯酸酯类聚合物纳米复合材料，要求高透光、高电磁屏蔽。有
机玻璃透明性好，但为绝缘体因而不具有屏蔽效能。在有机材料中掺加导电粒子，
由于其互相接触或处于极靠近的位置，通过空气或电解质之间的热释电子或隧道
效应而导电，但基体中导电粒子间必须有足够的透光间隙或粒子本身比可见光波
长小才具透明性。所以本研究的目的是利用液相法中较有前途的溶胶-凝胶法制
备氧化铟、氧化锡及其复合氧化物(In_2O_3／SnO_2)纳米粉料，并对其进行表面修
饰和综合表征，为大课题提供原材料并可望总结出普遍可行的纳米粒子制备、修
饰及表征方法。
本文第一部分对In_2O_3／SnO_2的导电机理及对In_2O_3／SnO_2纳米粉制备方法的
研究进展进行了综合评述。
本文第二部分详细地研究了溶胶-凝胶法制备In_2O_3／SnO_2纳米粉体的工艺条
件及参数，还对Sn-In_2O_3(锡掺杂氧化铟)纳米粉体的导电性能进行仔细研究；并
利用TG-DSC、FT-IR、XRD、SEM、EDS、TEM和BET等多种现代测试方法
对所制In_2O_3／SnO_2纳米粉体的结构、粒度、形貌、成分等进行了综合表征与分析。
在对溶胶-凝胶法制备In_2O_3／SnO_2纳米粉体的工艺研究中，研究了反应温度、
反应pH值、煅烧制度、反应物浓度、老化制度等对In_2O_3／SnO_2纳米粉体质量的
影响。总结出制备三种粉料的优化工艺条件为：NH_3·H_2O浓度为25-28％，反应
温度为50-70℃，老化制度为40℃／4h左右，超声分散30min，煅烧制度为800
℃／1h，其中合成氧化锡前驱料，SnCl_4·5H_2O的适宜浓度为20g／100mL左右，
反应pH值为8-11，合成氧化铟前驱料，InCl_3·4H_2O的适宜浓度为5-10g／100mL，
反应pH值为7或10.5以上，合成锡掺杂氧化铟前驱料，InCl_3·4H_2O的适宜浓度
为5-10g／100mL，并加入相应比例(Wt_(In2O3)／Wt_(SnO2)=9∶1)的SnCl_4·5H_2O，反应
pH值为7或10.5以上。
Sn-In_2O_3纳米粉体的电性能研究表明：Sn-In_2O_3前驱物在700-1000℃煅烧，
方块电阻较低，真空条件下煅烧试样的电阻比空气条件下煅烧试样的电阻低，
南京工业大学硕士学位论文
中文摘要
sno:掺杂10wt%左右时，试样方块电阻最低。
通过对InZO3/S nOZ纳米粉体表征，得出InZO3/S nOZ纳米粒子多呈球形、颗粒
均匀、分散性良好、组分均匀、纯度较高、平均粒径在4一50lun左右、比表面积
达67一156 mZ/g;snoZ纳米粉为正四面体金红石结构，InZo3和sn一InZo3纳米粉
为体心立方结构。
本文第三部分，结合丙烯酸酷类单体，对Sn一InZ仇纳米微粒进行表面修饰
研究，最后得出选用 KH一560和KH一570作表面修饰剂，添加量为0.5一lwt%左右，
pH值为5.4左右，采用球磨72小时，辅助超声分散工艺时，Sn一In20:纳米粉的
分散性较好，且与基体有较好的相容性。
本文最后部分，就整个研究工作进行了总结，并得出结论。
This program is from general assembly department about new nano complex of inorganic-macromolecule shielded material. Nano indium, tin oxide etc. particles/polymer composite was studied. High transparence and electromagnetic shielded efficiency are asked. The transparency of organic glass is good, but it is nonconductor and has no shielded efficiency. When conducting particles are added to organic materials, they are conductive. But the composite must have enough pervious light gap between conducting particles, or the particle size is less than the wavelength of visible light. So preparation of indium, tin oxide (In2O3/SnO2) nano powders by promising method of sol - gel in liquid and surface modification were studied. We hope to summarize general nano preparation, modification and characterization methods.
In the first part of the dissertation, the conducting mechanism and the current study on nano powders preparation methods of In2O3/SnO2 are reviewed.
In the second part, the processes were studied on preparing In2O3/SnO2 nano powders in details by sol - gel method, and the electrical property was carefully studied of tin doped indium oxide (Sn-In2O3) nano powder too. The structure, morphology, particle size, specific surface area, and composition of In2O3/SnO2 nano powder were characterized by means of TG-DSC, FT-IR, XRD, SEM, EDS , TEM and BET.
In the technology research of preparing In2O3/SnO2 nano powders, the influence factors were studied, such as reaction temperature, reaction pH value, dry technology, calcinating systems, reaction material concentration and ageing systems etc. The best technology conditions were reached finally.
Through study on the electrical performance of Sn-In2O3 nano powder, some conclusions were drawn. When Sn-In2O3 precursor was calcinated at 700-1000 , low square resistance was got. The resistance was lower when Sn-In2O3 precursor was calcinated in vacuum than air condition. When SnO2 wt % was controlled for 10 %, the square resistance of Sn-In2O3 was minimum.
Through the characterization of In2O3/SnO2 nano powders, some conclusions were drawn: SnO2 nano powder is rutile structure, and In2O3 and Sn-In2O3 nano powders are cubic structure. In2O3/SnO2 nano powders were well dispersing with
spherical uniform grain, and the mean grain was 4-50 nm. The purity and composition uniformity were very high, and the specific surface area was 67-156 nm.
In the third part, surface modification of Sn-In2O3 nano particle was studied and some conclusions were drawn finally. KH560 and KH570 were selected as surface modification agents, and the concentration of them was 0.5-1 wt %, and pH value was controlled for 5.4, and the best milled technology were 72 hours. Surface modified Sn-In2O3 nano powder was well dispersing in matrix.
In the last part, conclusions were summarized.
引文
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[3] 竺培显，韩润生，方吕昌，合成二氧化锡超微粉末新方法及产品测试研究．矿物岩石地球化学通报，1997，16(增刊)：109-110
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