自蔓延镁热还原法制备六硼化钙粉末研究
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摘要
作为一种重要的金属硼化物,CaB_6具有高熔点、高强度、高的化学稳定性、低的电子功函数、较强的中子吸收能力等优异性能,被广泛用作耐火材料、金属脱氧剂、中子吸收剂、耐磨剂及功能陶瓷材料等。一般来说,用来制备CaB_6的硼源为B_4C或B_2O_3,但这两种原料都需在高温下获得,生产成本很高。本研究以价格低廉的六硼酸钙为原料,以金属镁粉为还原剂,采用燃烧合成法成功制备了CaB_6粉末。
为了获得较好的硼酸钙原料,对水热合成的五水合六硼酸钙进行了热分析和高温研究。热分析结果表明CaB_6O_(10)·5H_2O分四步脱水,在800℃处有一个相变放热峰,900℃附近出现一个吸热峰;化学分析、XRD分析等表明CaO_(10)·5H_2O在600℃保温2 h结晶水全部脱去,并转化为无定形的无水六硼酸盐CaB_6O_(10),800℃非晶态CaB_6O_(10)向晶态转变并放出热量,900℃晶态CaB_6O_(10)分解为四硼酸钙CaB_4O_7和玻璃态的B_2O_3。
基于热力学理论对CaB_6O_(10)-Mg体系绝热温度和反应吉布斯自由能进行了理论计算和分析。结果表明体系绝热温度高达2406.69 K,高温下CaB_6O_(10)分解为B_2O_3和CaO,体系中B_2O_3-MgO、B_2O_3-CaO、Ca_3(BO_3)_2-B_2O_3-Mg、B_2O_3-CaO-Mg等反应吉布斯自由能均小于0,都有可能发生。XRD分析表明燃烧产物中除CaB_6和MgO外,还存在副产物Mg_3B_2O_6和Ca_3(BO_3)_2,采用1+1盐酸煮沸30 min除去副产物可获得较纯净的CaB_6粉末。在热力学分析、差热分析、燃烧产物XRD分析等基础上建立了CaB_6O_(10)-Mg体系反应模型,探析了燃烧反应机理。
工艺规律研究表明,增大原料粒径和制样压力有助于氧化还原反应的发生;Mg粉过量5-15wt.%,原料转化率有所提高,但过量超过15wt.%转化率急剧降低,最佳镁粉使用量为过量5wt.%;添加稀释剂会大大降低原料转化率,当添加量为40wt.%时燃烧反应不再发生;热爆温度高于600℃原料坯体才能被点燃,温度越高越利于燃烧反应的进行;制样时添加粘结剂会带走燃烧体系的热量,降低B_2O_3转化率。
酸洗产物电镜分析表明CaB_6颗粒分散均匀,单体呈正方形,颗粒大小不均,一部分颗粒较大,一部分较小,小颗粒因表面能较大,吸附在一起聚集成絮状。
As one of important metal-borides,calcium hexaboride(CaB_6) has been attracting much attention for its high melting point,high strength and high Chemical stability,as well as other outstanding properties such as low electronic work function,strong neutron-absorbing.CaB_6 is applied in refractory materials,metal deoxidant,neutron absorbent,wear-resisting agent and functional ceramic materials.Generally,CaB_6 is produced from B_4C or B_2O_3 which is obtained at high temperature and high cost.In this study,the CaB_6 powder was prepared through combustion synthesis by using calcium hexaborate and magnesium as starting materials.
In order to gain calcium hexaborate with high quality,thermal analysis and the phase transition of CaB_6O_(10)·5H_2O at high temperature was investigated.It is indicated that CaB_(6)O_(10)·5H_2O was dehydrated by 4 steps from thermal analysis and there existed one exothermic peak near 800℃and one endothermic peak near 900℃,respectively.Chemical analysis,XRD,TG-DTA analyses showed that CaB_6O_(10)·5H_2O was dehydrated and inverted into amorphous CaB_6O_(10) at 600℃,amorphous CaB_6O_(10) transformed into a new anhydrous crystalline hexaborate CaB_6O_(10) at 800℃,and crystalline CaB_6O_(10) decomposed and formed CaB_4O_7 and vitreous B_2O_3 at 900℃.
Based on thermal dynamic theory,the adiabatic temperature and Gibbs free energies of CaB_6O_(10)-Mg system were calculated and analysized.The calculated adiabatic temperature of CaB_6O_(10)-Mg system reached 2406.69 K and CaB_6O_(10) was decomposed into B_2O_3 and CaO at high temperature.Gibbs energies of B_2O_3-MgO,B_2O_3-CaO,Ca_3(BO_3)_2-B_2O_3-Mg and B_2O_3-CaO-Mg are negative,so the reactions among them are all possible.The XRD analyses of combustion products showed that there existed a small amount of Mg_3B_2O_6 and Ca_3(BO_3)_2 besides CaB_6 and MgO.The XRD patterns of products leached by 1+1 HCl indicated that the major part of the leached sample is comprised by CAB_6,showing that MgO and by-products were efficiently leached out.The reaction model of CaB_6O_(10)-Mg system was proposed depending on thermal dynamic analysis,DTA,X-ray analysis of combustion products and so on.The mechanism of combustion reaction was discussed simply.
The study on technological conditions was also investigated.Large particle size of CaB_6O_(10) and high compacting pressure is beneficial to the production of CAB_6.The conversion of B_2O_3 increased with the excess quantities of Mg between 5-15 wt.%.However, the conversion of B_2O_3 in materials descends dramatically when the excess of Mg preponderates over 15 wt.%.The optimal raw material ratio is the excess quantity of Mg by 5 wt.%.The add-on of diluent would decrease the conversion of materials.When the adding quantity of MgO reached 40 wt.%,the combustion reaction could not occurred.Only when the explosive temperature is higher than 600℃the material could be iginited,and higher explosive temperature is helpful to combustion reaction.The add-on of binder would carry off the heat of CaB_6O_(10)-Mg system and decreased the conversion of B_2O_3.
SEM photos of leached products showed that CaB_6 particles were uniformly distributed, and the single grain appeared square.However,the sizes of CaB_6 particles were not equality, some were lager,and others were too small.Many small CaB_6 grains agglomerated together like spong because of the large surface energy.
为了获得较好的硼酸钙原料,对水热合成的五水合六硼酸钙进行了热分析和高温研究。热分析结果表明CaB_6O_(10)·5H_2O分四步脱水,在800℃处有一个相变放热峰,900℃附近出现一个吸热峰;化学分析、XRD分析等表明CaO_(10)·5H_2O在600℃保温2 h结晶水全部脱去,并转化为无定形的无水六硼酸盐CaB_6O_(10),800℃非晶态CaB_6O_(10)向晶态转变并放出热量,900℃晶态CaB_6O_(10)分解为四硼酸钙CaB_4O_7和玻璃态的B_2O_3。
基于热力学理论对CaB_6O_(10)-Mg体系绝热温度和反应吉布斯自由能进行了理论计算和分析。结果表明体系绝热温度高达2406.69 K,高温下CaB_6O_(10)分解为B_2O_3和CaO,体系中B_2O_3-MgO、B_2O_3-CaO、Ca_3(BO_3)_2-B_2O_3-Mg、B_2O_3-CaO-Mg等反应吉布斯自由能均小于0,都有可能发生。XRD分析表明燃烧产物中除CaB_6和MgO外,还存在副产物Mg_3B_2O_6和Ca_3(BO_3)_2,采用1+1盐酸煮沸30 min除去副产物可获得较纯净的CaB_6粉末。在热力学分析、差热分析、燃烧产物XRD分析等基础上建立了CaB_6O_(10)-Mg体系反应模型,探析了燃烧反应机理。
工艺规律研究表明,增大原料粒径和制样压力有助于氧化还原反应的发生;Mg粉过量5-15wt.%,原料转化率有所提高,但过量超过15wt.%转化率急剧降低,最佳镁粉使用量为过量5wt.%;添加稀释剂会大大降低原料转化率,当添加量为40wt.%时燃烧反应不再发生;热爆温度高于600℃原料坯体才能被点燃,温度越高越利于燃烧反应的进行;制样时添加粘结剂会带走燃烧体系的热量,降低B_2O_3转化率。
酸洗产物电镜分析表明CaB_6颗粒分散均匀,单体呈正方形,颗粒大小不均,一部分颗粒较大,一部分较小,小颗粒因表面能较大,吸附在一起聚集成絮状。
As one of important metal-borides,calcium hexaboride(CaB_6) has been attracting much attention for its high melting point,high strength and high Chemical stability,as well as other outstanding properties such as low electronic work function,strong neutron-absorbing.CaB_6 is applied in refractory materials,metal deoxidant,neutron absorbent,wear-resisting agent and functional ceramic materials.Generally,CaB_6 is produced from B_4C or B_2O_3 which is obtained at high temperature and high cost.In this study,the CaB_6 powder was prepared through combustion synthesis by using calcium hexaborate and magnesium as starting materials.
In order to gain calcium hexaborate with high quality,thermal analysis and the phase transition of CaB_6O_(10)·5H_2O at high temperature was investigated.It is indicated that CaB_(6)O_(10)·5H_2O was dehydrated by 4 steps from thermal analysis and there existed one exothermic peak near 800℃and one endothermic peak near 900℃,respectively.Chemical analysis,XRD,TG-DTA analyses showed that CaB_6O_(10)·5H_2O was dehydrated and inverted into amorphous CaB_6O_(10) at 600℃,amorphous CaB_6O_(10) transformed into a new anhydrous crystalline hexaborate CaB_6O_(10) at 800℃,and crystalline CaB_6O_(10) decomposed and formed CaB_4O_7 and vitreous B_2O_3 at 900℃.
Based on thermal dynamic theory,the adiabatic temperature and Gibbs free energies of CaB_6O_(10)-Mg system were calculated and analysized.The calculated adiabatic temperature of CaB_6O_(10)-Mg system reached 2406.69 K and CaB_6O_(10) was decomposed into B_2O_3 and CaO at high temperature.Gibbs energies of B_2O_3-MgO,B_2O_3-CaO,Ca_3(BO_3)_2-B_2O_3-Mg and B_2O_3-CaO-Mg are negative,so the reactions among them are all possible.The XRD analyses of combustion products showed that there existed a small amount of Mg_3B_2O_6 and Ca_3(BO_3)_2 besides CaB_6 and MgO.The XRD patterns of products leached by 1+1 HCl indicated that the major part of the leached sample is comprised by CAB_6,showing that MgO and by-products were efficiently leached out.The reaction model of CaB_6O_(10)-Mg system was proposed depending on thermal dynamic analysis,DTA,X-ray analysis of combustion products and so on.The mechanism of combustion reaction was discussed simply.
The study on technological conditions was also investigated.Large particle size of CaB_6O_(10) and high compacting pressure is beneficial to the production of CAB_6.The conversion of B_2O_3 increased with the excess quantities of Mg between 5-15 wt.%.However, the conversion of B_2O_3 in materials descends dramatically when the excess of Mg preponderates over 15 wt.%.The optimal raw material ratio is the excess quantity of Mg by 5 wt.%.The add-on of diluent would decrease the conversion of materials.When the adding quantity of MgO reached 40 wt.%,the combustion reaction could not occurred.Only when the explosive temperature is higher than 600℃the material could be iginited,and higher explosive temperature is helpful to combustion reaction.The add-on of binder would carry off the heat of CaB_6O_(10)-Mg system and decreased the conversion of B_2O_3.
SEM photos of leached products showed that CaB_6 particles were uniformly distributed, and the single grain appeared square.However,the sizes of CaB_6 particles were not equality, some were lager,and others were too small.Many small CaB_6 grains agglomerated together like spong because of the large surface energy.
引文
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