纳米材料PbTiO_3，BaTiO_3及Ba_xSr_（1-x）TiO_3的制备研究
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摘要
PbTiO_3、Ba_xSr_(1-x)TiO_3及BaTiO_3是重要的压电陶瓷材料,具有优异的物理化学特性,它们的用途非常广泛。由于一维纳米材料和纳米粒子拥有不寻常的化学物理性质及在不同领域的广泛应用,引起了人们的普遍关注。随着现代科学技术的发展,许多合成方法用于制备一维纳米材料和纳米粒子。在这些制备方法中,反相微乳法、低温煅烧法和熔盐法等由于能有效控制颗粒的形貌及大小,而吸引了研究人员的关注。利用上述方法,我们合成项链状PbTiO_3纳米线、Ba_xSr_(1-x)TiO_3和BaTiO_3纳米粒子,同时研究了相关反应条件。
在环己烷/TritonX-100/正己醇/水相的微乳液体系中,以Ti(OC_4H_9)_4、H_2C_2O_4·2H_2O和Pb(NO_3)_2为原料,制备出混合草酸盐(PbC_2O_4+TiOC_2O_4·2H_2O)前驱体。然后在680℃煅烧4 h,得到具有不同形貌的PbTiO_3粒子,有球形纳米粒子,项链状纳米线以及由纳米粒子构成微米立方体和长方体。改变ω_0值(水与表面活性剂的物质的量的比)能有效控制产品的形貌和颗粒大小,并提出了其可能的形成机理。
以氢氧化钡、氢氧化锶和钛酸丁酯为原料,采用低温煅烧(300～500℃)法合成了钛酸锶钡纳米粒子。结果表明,所得钛酸锶钡纳米粒子大小分布均匀,粒径约为13～20 nm,粒子形状近似为球形,晶相结构为立方相。该粉体为完全互溶体的固溶体,随Sr含量的增加,晶胞参数a和晶胞体积V减小,a随组成呈线性关系,符合Vegard定律。
以氢氧化钡和钛酸丁酯为原料,采用固相研磨与低温(200～300℃)煅烧相结合的方法制得了钛酸钡纳米粉体。结果表明,所得钛酸钡纳米粉体的粒径约为15～20 nm,粒子形状近似为球形,晶体结构为立方相,钡钛物质的量之比约为1.0。该粉体在热处理温度为800～1000℃时,由立方相转变为四方相;而在热处理温度为668～892℃时,存在于晶格中的羟基被除去。
用TiO_2和Ba(OH)_2为钛源和钡源,以NaOH和KOH为熔剂,采用融盐法成功地合成了立方体状BaTiO_3纳米粒子。结果表明,在反应温度为200℃,反应8 h时所得粒子形貌不规则、颗粒大小分布不均匀;反应24 h时粒子形状为立方体,尺寸分布较均匀,粒径约为30～70 nm;而当反应时间延长至48 h和72 h时,样品形貌逐渐由立方体变为球形,且粒径增大。反应温度高于185℃时,能得到立方相、结晶良好、纯度高的BaTiO_3纳米粒子。另外,还初步探讨了融盐法制备BaTiO_3纳米粒子的形成机理。
PbTiO_3,Ba_xSr_(1-x)TiO_3 and BaTiO_3 are kinds of important piezo ceramic materials because of its excellent physics and chemical properties,which have been applicated in many fields.One-dimensional nanomaterial and nanoparticles have received considerable attention because of their unusual properties and potential applications in diverse fields. Owing to the need of nanotechnology and modern electronic industry,many methods have been utilized to synthesize one-dimensional nanomaterial and nanoparticles.Among of these methods,treverse microemulsion,low temperature calcination method and molten salt method can effectively control the morphology and size of product have attracted the investigator's attention.Using the above methods,we synthesized necklace-like PbTiO_3 nanowires,Ba_xSr_(1-x)TiO_3 nanoparticles and BaTiO_3 nanoparticles,and simultaneously studied the effect of the relevant reaction condition on the morphology and size of the products.
The mixed oxalate precursors(TiOC_2O_4·2H_2O+PbC_2O_4) were prepared by the chemical reaction of Ti(OC_4H_9)_4,H_2C_2O_4·2H_2O and Pb(NO_3)_2 in a reverse microemulsion system consisting of water,t-octylphenoxypolyethoxyethanol(Triton X-100),n-hexanol and cyclohexane.Calcination of the precursors at 680℃for 4 h yielded PbTiO_3 particles with varying size and morphology including spherical particles,necklace-like nanowires and rectangular parallelepiped-like microscale particles consisting of spherical nanoparticles.The morphologies and sizes of PbTiO_3 particls can be controlled by changing the molar ratio of water to surfactant Triton X-100(ω_0).The possible formation mechanism of PbTiO_3 particles is also proposed in the paper.
Ba_xSr_(1-x)TiO_3 nanoparticles were successfully prepared by the low temperature(300～500℃) calcination method,using barium hydroxide,strontium hydroxide,and tetrabutyl titanate as starting materials.It is confirmed that the barium strontium titanate nanoparticles with uniform size distribution and particle sizes of 13～20 nm,similar to spherical shape,are cubic perovskite structure.The powders are true solid solution,and as the increases of the doping proportion of Sr~(2+),both the cell parameter a and the cell volume V become smaller.The a values are linearly related with the compositions of the powders,which is in accord with Vegard's law.
BaTiO_3 nanopowders were synthesized by the combination of solid phase grinding and low temperature(200～300℃) calcination method,using barium hydroxide and tetrabutyl titanate as reactants.The results show that the prepared BaTiO_3 nanopowders with particle sizes of 15～20 nm and almost spherical particle shape are cubic phase,and their molar ratio of barium to titanate is about 1.0.The phase transition from cubic to tetragonal phase of barium titanate occurrs when the temperature of heat treatment is 800～1000℃,and the hydroxyl ions existing in the lattice of BaTiO_3 is removed when the temperature of heat treatment is 668～892℃.
BaTiO_3 nanoparticles with cubic morphology starting from Ba(OH)_2 and TiO_2 have been synthesized by molten salt method using NaOH and KOH as a flux.Results show that the products with irregular shape and uneven particle size distribution is prepared at 200℃and 8h;cubical BaTiO_3 nanoparticles with uniform size distribution which are 30～70 nm in sizes is obtained at 24 h;as the reaction time is prolonged to 48 h and 72 h,the morphology of the product is gradually changed into spherical shape from cubic shape and diameter of particles increased.When the reaction temperature is higher than 185℃,BaTiO_3 nanoparticles with cubic phase,high crystallinity and high purity is obtained.In addition,the formation mechanism of BaTiO_3 nanoparticles prepared by molten salt method is also discussed.
在环己烷/TritonX-100/正己醇/水相的微乳液体系中,以Ti(OC_4H_9)_4、H_2C_2O_4·2H_2O和Pb(NO_3)_2为原料,制备出混合草酸盐(PbC_2O_4+TiOC_2O_4·2H_2O)前驱体。然后在680℃煅烧4 h,得到具有不同形貌的PbTiO_3粒子,有球形纳米粒子,项链状纳米线以及由纳米粒子构成微米立方体和长方体。改变ω_0值(水与表面活性剂的物质的量的比)能有效控制产品的形貌和颗粒大小,并提出了其可能的形成机理。
以氢氧化钡、氢氧化锶和钛酸丁酯为原料,采用低温煅烧(300～500℃)法合成了钛酸锶钡纳米粒子。结果表明,所得钛酸锶钡纳米粒子大小分布均匀,粒径约为13～20 nm,粒子形状近似为球形,晶相结构为立方相。该粉体为完全互溶体的固溶体,随Sr含量的增加,晶胞参数a和晶胞体积V减小,a随组成呈线性关系,符合Vegard定律。
以氢氧化钡和钛酸丁酯为原料,采用固相研磨与低温(200～300℃)煅烧相结合的方法制得了钛酸钡纳米粉体。结果表明,所得钛酸钡纳米粉体的粒径约为15～20 nm,粒子形状近似为球形,晶体结构为立方相,钡钛物质的量之比约为1.0。该粉体在热处理温度为800～1000℃时,由立方相转变为四方相;而在热处理温度为668～892℃时,存在于晶格中的羟基被除去。
用TiO_2和Ba(OH)_2为钛源和钡源,以NaOH和KOH为熔剂,采用融盐法成功地合成了立方体状BaTiO_3纳米粒子。结果表明,在反应温度为200℃,反应8 h时所得粒子形貌不规则、颗粒大小分布不均匀;反应24 h时粒子形状为立方体,尺寸分布较均匀,粒径约为30～70 nm;而当反应时间延长至48 h和72 h时,样品形貌逐渐由立方体变为球形,且粒径增大。反应温度高于185℃时,能得到立方相、结晶良好、纯度高的BaTiO_3纳米粒子。另外,还初步探讨了融盐法制备BaTiO_3纳米粒子的形成机理。
PbTiO_3,Ba_xSr_(1-x)TiO_3 and BaTiO_3 are kinds of important piezo ceramic materials because of its excellent physics and chemical properties,which have been applicated in many fields.One-dimensional nanomaterial and nanoparticles have received considerable attention because of their unusual properties and potential applications in diverse fields. Owing to the need of nanotechnology and modern electronic industry,many methods have been utilized to synthesize one-dimensional nanomaterial and nanoparticles.Among of these methods,treverse microemulsion,low temperature calcination method and molten salt method can effectively control the morphology and size of product have attracted the investigator's attention.Using the above methods,we synthesized necklace-like PbTiO_3 nanowires,Ba_xSr_(1-x)TiO_3 nanoparticles and BaTiO_3 nanoparticles,and simultaneously studied the effect of the relevant reaction condition on the morphology and size of the products.
The mixed oxalate precursors(TiOC_2O_4·2H_2O+PbC_2O_4) were prepared by the chemical reaction of Ti(OC_4H_9)_4,H_2C_2O_4·2H_2O and Pb(NO_3)_2 in a reverse microemulsion system consisting of water,t-octylphenoxypolyethoxyethanol(Triton X-100),n-hexanol and cyclohexane.Calcination of the precursors at 680℃for 4 h yielded PbTiO_3 particles with varying size and morphology including spherical particles,necklace-like nanowires and rectangular parallelepiped-like microscale particles consisting of spherical nanoparticles.The morphologies and sizes of PbTiO_3 particls can be controlled by changing the molar ratio of water to surfactant Triton X-100(ω_0).The possible formation mechanism of PbTiO_3 particles is also proposed in the paper.
Ba_xSr_(1-x)TiO_3 nanoparticles were successfully prepared by the low temperature(300～500℃) calcination method,using barium hydroxide,strontium hydroxide,and tetrabutyl titanate as starting materials.It is confirmed that the barium strontium titanate nanoparticles with uniform size distribution and particle sizes of 13～20 nm,similar to spherical shape,are cubic perovskite structure.The powders are true solid solution,and as the increases of the doping proportion of Sr~(2+),both the cell parameter a and the cell volume V become smaller.The a values are linearly related with the compositions of the powders,which is in accord with Vegard's law.
BaTiO_3 nanopowders were synthesized by the combination of solid phase grinding and low temperature(200～300℃) calcination method,using barium hydroxide and tetrabutyl titanate as reactants.The results show that the prepared BaTiO_3 nanopowders with particle sizes of 15～20 nm and almost spherical particle shape are cubic phase,and their molar ratio of barium to titanate is about 1.0.The phase transition from cubic to tetragonal phase of barium titanate occurrs when the temperature of heat treatment is 800～1000℃,and the hydroxyl ions existing in the lattice of BaTiO_3 is removed when the temperature of heat treatment is 668～892℃.
BaTiO_3 nanoparticles with cubic morphology starting from Ba(OH)_2 and TiO_2 have been synthesized by molten salt method using NaOH and KOH as a flux.Results show that the products with irregular shape and uneven particle size distribution is prepared at 200℃and 8h;cubical BaTiO_3 nanoparticles with uniform size distribution which are 30～70 nm in sizes is obtained at 24 h;as the reaction time is prolonged to 48 h and 72 h,the morphology of the product is gradually changed into spherical shape from cubic shape and diameter of particles increased.When the reaction temperature is higher than 185℃,BaTiO_3 nanoparticles with cubic phase,high crystallinity and high purity is obtained.In addition,the formation mechanism of BaTiO_3 nanoparticles prepared by molten salt method is also discussed.
引文
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