二氧化钒及掺杂二氧化钒粉体的制备与形貌控制研究
摘要
VO_2(M)和VO_2(R)在68℃附近发生可逆相变,相变过程中光学透过率会发生突变,使其在控温薄膜领域有很好的应用前景。将VO_2粉体分散于有机高分子材料中制备复合薄膜,可以克服无机薄膜耐水性差,易开裂等缺点。但是要将粉体实现应用还需解决如下问题:1、降低VO_2的相变温度,实现在室温下的相转变。如何实现在VO_2粉体制备时进行掺杂实现相变温度的降低,是待解决的问题。2、VO_2相变时会产生体积变化,在复合薄膜中将产生微应力,需减小粉体的尺寸来减小此应力,同时可保证薄膜有良好的透明性。
NH_3气还原V_2O_5是一种简单易控的制备VO_2的方法,本论文在此基础上展开如下研究:
1.确定了NH_3还原法制备VO_2的反应条件,由试验分析了不同还原时间和热处理条件对产物晶体结构的影响。
2.在高温融熔水淬过程中加入掺杂剂进行掺杂,并结合还原反应制得掺杂VO_2。比较了钨酸、钨酸钠、钼酸铵作为掺杂剂对V_2O_5和VO_2晶体结构的影响。分析了掺杂元素对VO_2相变温度的降低效率。
3.利用水热反应对钒氧化物进行形貌控制,结合氨气还原制备了具有一定形貌的微纳米VO_2。考察了水、乙醇、草酸对V_2O_5粉体价态和形貌的影响,并对得到的钒氧化物进行还原和热处理,制备了具有一定形貌的VO_2粉体。
4.研究了水热条件下不同掺杂方式对VO_2粉体相变温度的影响。钨酸分别以溶胶凝胶法与直接加入法的方式进行反应,得到了不同的降温效率。
VO_2(M) undergoes a reversible semiconductor-metal phase transition with VO_2(R) at about 68℃.The optical transmittance will change drastically during the phase transition procedure.So VO_2 has attracted much attention for its potentiality in the temperature control film.The compound film VO_2 particles suspended in the polymer has many advantages for the application.But the phase transition temperature(Tt) is a little higher for the use in the atmosphere.So it is important to synthesize the doped VO_2 particles to decreased the Tt.Also size of the particles should be controled to lessen the stress caused by the phase transition and to make the film transparent.Up to now,reduction of V_2O_5 in ammonia gas is an easy way to synthesize VO_2 particles.Based on these results,research was developed as followes:
1.Reaction procedure was optimized to synthesize the VO_2 particles in the ammonia gas. Effect of the heat treatment on the crystal structureof the product was also analyzed.
2.The sol-gel method was used to prepare the doped V_2O_5.By reduction in ammonia, the W-doped VO_2(M) was synthesized.Tungsten acid,Na_2WO_4·2H_2O and ammonium molybdate were added as the dopant respectively.Effect of the dopants on the crystal structure of V_2O_5 and VO_2 was investigated.DSC was used to analyze the change of Tt for the doped VO_2.
3.Hydrothermal method was used to prepare the vanadium oxides with special morphologies.Reactions of water,ethanol and oxalic acid with V_2O_5 powders were conducted respectively under the hydrothermal condition.Reduction and the heat treatment turned the products to VO_2(M) with special size distrubution.
4.Different methods were used to prepare the doped VO_2 with tungsten acid and oxalic acid as the reactants under the hydrothermal condition.When tungsten acid was added directly and via the sol-gel method respectively,different deduction efficiency was got.
NH_3气还原V_2O_5是一种简单易控的制备VO_2的方法,本论文在此基础上展开如下研究:
1.确定了NH_3还原法制备VO_2的反应条件,由试验分析了不同还原时间和热处理条件对产物晶体结构的影响。
2.在高温融熔水淬过程中加入掺杂剂进行掺杂,并结合还原反应制得掺杂VO_2。比较了钨酸、钨酸钠、钼酸铵作为掺杂剂对V_2O_5和VO_2晶体结构的影响。分析了掺杂元素对VO_2相变温度的降低效率。
3.利用水热反应对钒氧化物进行形貌控制,结合氨气还原制备了具有一定形貌的微纳米VO_2。考察了水、乙醇、草酸对V_2O_5粉体价态和形貌的影响,并对得到的钒氧化物进行还原和热处理,制备了具有一定形貌的VO_2粉体。
4.研究了水热条件下不同掺杂方式对VO_2粉体相变温度的影响。钨酸分别以溶胶凝胶法与直接加入法的方式进行反应,得到了不同的降温效率。
VO_2(M) undergoes a reversible semiconductor-metal phase transition with VO_2(R) at about 68℃.The optical transmittance will change drastically during the phase transition procedure.So VO_2 has attracted much attention for its potentiality in the temperature control film.The compound film VO_2 particles suspended in the polymer has many advantages for the application.But the phase transition temperature(Tt) is a little higher for the use in the atmosphere.So it is important to synthesize the doped VO_2 particles to decreased the Tt.Also size of the particles should be controled to lessen the stress caused by the phase transition and to make the film transparent.Up to now,reduction of V_2O_5 in ammonia gas is an easy way to synthesize VO_2 particles.Based on these results,research was developed as followes:
1.Reaction procedure was optimized to synthesize the VO_2 particles in the ammonia gas. Effect of the heat treatment on the crystal structureof the product was also analyzed.
2.The sol-gel method was used to prepare the doped V_2O_5.By reduction in ammonia, the W-doped VO_2(M) was synthesized.Tungsten acid,Na_2WO_4·2H_2O and ammonium molybdate were added as the dopant respectively.Effect of the dopants on the crystal structure of V_2O_5 and VO_2 was investigated.DSC was used to analyze the change of Tt for the doped VO_2.
3.Hydrothermal method was used to prepare the vanadium oxides with special morphologies.Reactions of water,ethanol and oxalic acid with V_2O_5 powders were conducted respectively under the hydrothermal condition.Reduction and the heat treatment turned the products to VO_2(M) with special size distrubution.
4.Different methods were used to prepare the doped VO_2 with tungsten acid and oxalic acid as the reactants under the hydrothermal condition.When tungsten acid was added directly and via the sol-gel method respectively,different deduction efficiency was got.
引文
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