提高热电材料β-FeSi_2转化率的工艺研究
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摘要
随着全球环境污染和能源危机的日益严重,开发新型环保能源替代材料已越来越受到世界各国的重视。β-FeSi_2是一种半导体热电材料,可在高温环境中工作,具有在500~900℃温度范围内的高温热电转换功能;β-FeSi_2具有抗氧化性强、原料来源丰富、性能稳定、价格低廉等优点,选用低纯度的工业原料进行制备对其热电性能无明显影响;另外,在β-FeSi_2制备过程中掺杂微量的Cu、Co、B、Al等元素可以形成p型或者n型半导体,明显提高了β-FeSi_2的热电性能,避免由于半导体两只脚材料的热膨胀系数不同而引起的热电元器件制作上的困难。正是由于以上优点,β-FeSi_2已成为一种很有发展前途的热电材料。
本文采用燃烧合成-热处理工艺合成热电材料β-FeSi_2,用简单的方法来快速制备高纯度的β-FeSi_2。使用该工艺可以提高β-FeSi_2的实际应用价值,为该材料的广泛推广应用、直接投入工业生产降低了成本。本文以Fe粉、Si粉、KNO_3为原料,通过球磨混料增加反应物的机械能,经过球磨工艺后的试样有利于燃烧合成反应的进行。本文从以下几个方面进行了研究:1.对比分析掺杂Cu和不掺杂Cu对最终合成产物β-FeSi_2的影响,总结掺杂形成p型或者n型半导体的机理;2.在配料阶段通过改变铁硅原子配比,研究不同的硅含量对合成产物β-FeSi_2转化率的影响;3.对于燃烧合成的中间产物α-Fe_2Si_5选用箱式电阻炉分别选取不同的保温温度、保温时间进行退火处理,之后进行XRD分析,总结相转变α-Fe_2Si_5→β-FeSi_2合理的热处理工艺。
研究表明:1.掺杂0.5 at%的Cu在热处理过程中能显著提高共析反应(α→β+Si)的反应进程,完全地将α-Fe_2Si_5转变为β-FeSi_2,形成P型半导体,而未掺杂Cu的燃烧合成产物经过热处理工艺,XRD衍射图谱显示始终存在相转变不完全的α-Fe_2Si_5相;2.以不同的铁硅原子比例配制的原料经过燃烧合成-热处理工艺制备热电材料β-FeSi_2,对其转化率有较大的影响,在混料阶段按Fe:Si=1:3的原子比例制备β-FeSi_2,XRD分析表明,过量的Si单质提高了Si+ε→β的相转变过程,很大程度上能够消除ε相,增加β-FeSi_2的含量;3.当热处理条件为800℃、2h时完全消除了α-Fe_2Si_5相,β-FeSi_2峰值最强,产物颗粒尺寸明显减小,大尺寸颗粒消失,内部组织比较均匀。
As global environmental pollution and the growing energy crisis,the development of new environmentally friendly energy alternative materials have attracted more and more concern all over the world.β-FeSi_2 is a semiconductor thermoelectric materials that can work in high temperature environments,has high temperature thermoelectric conversion function in the temperatures range of 500~900℃.β-FeSi_2 have many advantages such as oxidation resistance, rich sources of raw materials, stable performance and prices, more over, there are not significantly affect on the preparaed thermoelectric performance when choose low purity of industrial raw material.In addition,doped with trace elements of Cu、Co、B、Al etc during the preparation ofβ-FeSi_2 formed p-type semiconductor or n-type semiconductor can improve the thermoelectric performance ofβ-FeSi_2 obviously and avoid the difficulty of making thermoelectricity components due to the different thermal expansion coefficient of the semiconductor two feet materials.Because of the above advantages,β-FeSi_2 has become a promising thermoelectric materials.
In this paper,we synthesis the thermoelectric materialsβ-FeSi_2 by the way of combustion synthesis-heat treatment process, with simple way to prepare high purity ofβ-FeSi_2. This technology can improve the practical application value ofβ-FeSi_2 and reduce the cost of application of this materials widely and investment in industrial production directly. We take the powders of Fe、Si and KNO_3 as raw material,increase the mechanical energy through the ball mill mixing that be helpful for reactants the synthesis reaction. This paper study the following aspects:1.Comparative analysis the effects of doped copper and no-doped copper on final synthesis productsβ-FeSi_2, summarized the doped mechanism of formation p-type or n-type semiconductor. 2.Effect of different silicon content on the productivity of synthesis materialβ-FeSi_2 by change the atomic ratio of Fe to Si in the mixing stage. 3.For combustion synthesis intermediate productsα-Fe_2Si_5, we selected different insulation temperature and holding time to annealing treatment by box resistance furnace, then analyzed by means of X-ray diffraction(XRD), and summarized reasonable treatment parameters of phase transformation ofα-Fe_2Si_5→β-FeSi_2.
The results show that 0.5 at% copper doped in heat-treatment process could accelerate eutectoid reaction precess (α→β+Si),the transformation fromα-Fe_2Si_5 phase toβ-FeSi_2 phase is completely and finally formed P-type semiconductor. In xrd spectrum of combustion products not doped Cu after heat-treatment,α-Fe_2Si_5 phase always be found.Thermoelectric materialβ-FeSi_2 was prepared by the method of combustion synthesis-heat treatment process, Samples ofβ-FeSi_2 were prepared in the mixing stage and the atomic ratio of Fe to Si was 1:3,the XRD analysis shows that the excessive content of silicon accelerated the phase transformation of Si+ε→β,andεphase was eliminated in a large extent,the content ofβ-FeSi_2 increased.When the heat treatment temperature was 800℃,α-Fe_2Si_5 phase eliminated absolutely in 2h,when the diffraction peak ofβ-FeSi_2 displayed the maximum value.Further more,the particle size of products reduced significantly,large-size particles disappeared,and the internal structure of products became more uniform.
本文采用燃烧合成-热处理工艺合成热电材料β-FeSi_2,用简单的方法来快速制备高纯度的β-FeSi_2。使用该工艺可以提高β-FeSi_2的实际应用价值,为该材料的广泛推广应用、直接投入工业生产降低了成本。本文以Fe粉、Si粉、KNO_3为原料,通过球磨混料增加反应物的机械能,经过球磨工艺后的试样有利于燃烧合成反应的进行。本文从以下几个方面进行了研究:1.对比分析掺杂Cu和不掺杂Cu对最终合成产物β-FeSi_2的影响,总结掺杂形成p型或者n型半导体的机理;2.在配料阶段通过改变铁硅原子配比,研究不同的硅含量对合成产物β-FeSi_2转化率的影响;3.对于燃烧合成的中间产物α-Fe_2Si_5选用箱式电阻炉分别选取不同的保温温度、保温时间进行退火处理,之后进行XRD分析,总结相转变α-Fe_2Si_5→β-FeSi_2合理的热处理工艺。
研究表明:1.掺杂0.5 at%的Cu在热处理过程中能显著提高共析反应(α→β+Si)的反应进程,完全地将α-Fe_2Si_5转变为β-FeSi_2,形成P型半导体,而未掺杂Cu的燃烧合成产物经过热处理工艺,XRD衍射图谱显示始终存在相转变不完全的α-Fe_2Si_5相;2.以不同的铁硅原子比例配制的原料经过燃烧合成-热处理工艺制备热电材料β-FeSi_2,对其转化率有较大的影响,在混料阶段按Fe:Si=1:3的原子比例制备β-FeSi_2,XRD分析表明,过量的Si单质提高了Si+ε→β的相转变过程,很大程度上能够消除ε相,增加β-FeSi_2的含量;3.当热处理条件为800℃、2h时完全消除了α-Fe_2Si_5相,β-FeSi_2峰值最强,产物颗粒尺寸明显减小,大尺寸颗粒消失,内部组织比较均匀。
As global environmental pollution and the growing energy crisis,the development of new environmentally friendly energy alternative materials have attracted more and more concern all over the world.β-FeSi_2 is a semiconductor thermoelectric materials that can work in high temperature environments,has high temperature thermoelectric conversion function in the temperatures range of 500~900℃.β-FeSi_2 have many advantages such as oxidation resistance, rich sources of raw materials, stable performance and prices, more over, there are not significantly affect on the preparaed thermoelectric performance when choose low purity of industrial raw material.In addition,doped with trace elements of Cu、Co、B、Al etc during the preparation ofβ-FeSi_2 formed p-type semiconductor or n-type semiconductor can improve the thermoelectric performance ofβ-FeSi_2 obviously and avoid the difficulty of making thermoelectricity components due to the different thermal expansion coefficient of the semiconductor two feet materials.Because of the above advantages,β-FeSi_2 has become a promising thermoelectric materials.
In this paper,we synthesis the thermoelectric materialsβ-FeSi_2 by the way of combustion synthesis-heat treatment process, with simple way to prepare high purity ofβ-FeSi_2. This technology can improve the practical application value ofβ-FeSi_2 and reduce the cost of application of this materials widely and investment in industrial production directly. We take the powders of Fe、Si and KNO_3 as raw material,increase the mechanical energy through the ball mill mixing that be helpful for reactants the synthesis reaction. This paper study the following aspects:1.Comparative analysis the effects of doped copper and no-doped copper on final synthesis productsβ-FeSi_2, summarized the doped mechanism of formation p-type or n-type semiconductor. 2.Effect of different silicon content on the productivity of synthesis materialβ-FeSi_2 by change the atomic ratio of Fe to Si in the mixing stage. 3.For combustion synthesis intermediate productsα-Fe_2Si_5, we selected different insulation temperature and holding time to annealing treatment by box resistance furnace, then analyzed by means of X-ray diffraction(XRD), and summarized reasonable treatment parameters of phase transformation ofα-Fe_2Si_5→β-FeSi_2.
The results show that 0.5 at% copper doped in heat-treatment process could accelerate eutectoid reaction precess (α→β+Si),the transformation fromα-Fe_2Si_5 phase toβ-FeSi_2 phase is completely and finally formed P-type semiconductor. In xrd spectrum of combustion products not doped Cu after heat-treatment,α-Fe_2Si_5 phase always be found.Thermoelectric materialβ-FeSi_2 was prepared by the method of combustion synthesis-heat treatment process, Samples ofβ-FeSi_2 were prepared in the mixing stage and the atomic ratio of Fe to Si was 1:3,the XRD analysis shows that the excessive content of silicon accelerated the phase transformation of Si+ε→β,andεphase was eliminated in a large extent,the content ofβ-FeSi_2 increased.When the heat treatment temperature was 800℃,α-Fe_2Si_5 phase eliminated absolutely in 2h,when the diffraction peak ofβ-FeSi_2 displayed the maximum value.Further more,the particle size of products reduced significantly,large-size particles disappeared,and the internal structure of products became more uniform.
引文
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