Investigation of the impact of mechanical activation on synthesis of the MgO-TiO2 system

N. Djordjevic, M. Vlahović, Sanja Martinović, Slavica Mihajlović, Nenad Vušović, M. Sokić
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Abstract

In this study, a mixture of magnesium oxide and titanium dioxide was mechanically activated in order to investigate the possibility of mechanochemical synthesis of magnesium titanate. Mechanical activation was performed for 1000 min in a high-energy vibro mill (type MH954/3, KHD Humboldt Wedag AG, Germany). The mill is equipped with housing having a horizontally placed shutter. The cylindrical stainless steel working vessel, with inner dimensions of 40 mm in height and 170 mm in diameter, has working elements consisting of two free concentric stainless steel rings with a total weight of 3 kg. The engine power is 0.8 kW. Respecting the optimal amount of powder to be activated of 50-150 g and the stoichiometric ratio of the reactants in the equation presenting the chemical reaction of magnesium titanate synthesis, the starting amounts were 20.2 g (0.5 mol) of MgO and 39.9 g (0.5 mol) TiO2. During the experiments, X-ray diffraction analysis of the samples taken from the reaction system after 60, 180, 330, and 1000 min of mechanical activation was performed. Atomic absorption spectrophotometry was used for chemical composition analysis of samples taken at different activation times. Based on the X-ray diffraction analysis results, it can be concluded that the greatest changes in the system took place at the very beginning of the mechanical activation due to the disturbance of the crystal structure of the initial components. X-ray diffraction analysis of the sample after 1000 min of activation showed complete amorphization of the mixture, but diffraction maxima characteristic for magnesium titanate were not identified. Therefore, the mechanical activation experiments were stopped. Evidently, the energy input was not sufficient to overcome the energy barrier to form a new chemical compound - magnesium titanate. The failure to synthesize magnesium titanate is explained by the low negative Gibbs energy value of -25.8 kJ/mol (despite the theoretical possibility that the reaction will happen), as well as by the amount of mechanical energy entered into the system during activation which was insufficient to obtain the reaction product. Although the synthesis of MgTiO3 was not achieved, significant results were obtained which identify models for further investigations of the possibility of mechanochemical reactions of alkaline earth metals and titanium dioxide.
机械活化对MgO-TiO2体系合成影响的研究
在本研究中,为了探讨机械化学合成钛酸镁的可能性,机械活化氧化镁和二氧化钛的混合物。机械活化在高能振动磨机(MH954/3型,KHD Humboldt Wedag AG,德国)中进行了1000分钟。磨机配备有一个水平放置的百叶窗的外壳。圆柱形不锈钢工作容器,内部尺寸为40毫米高,直径170毫米,工作元件由两个自由同心不锈钢环组成,总重量为3公斤。发动机功率为0.8 kW。根据钛酸镁合成化学反应方程中反应物的化学计量比和最佳活化粉量50 ~ 150 g,起始量为MgO 20.2 g (0.5 mol), TiO2 39.9 g (0.5 mol)。实验中,对机械活化60、180、330和1000 min后的反应体系样品进行x射线衍射分析。采用原子吸收分光光度法对不同活化时间的样品进行化学成分分析。根据x射线衍射分析结果可以得出,由于初始组分的晶体结构受到干扰,在机械活化的一开始,体系发生了最大的变化。活化1000 min后样品的x射线衍射分析显示混合物完全非晶化,但没有确定钛酸镁的衍射最大值特征。因此,机械活化实验停止。显然,能量输入不足以克服能量势垒形成新的化合物-钛酸镁。钛酸镁合成失败的原因是-25.8 kJ/mol的负吉布斯能值很低(尽管理论上有可能发生反应),以及在活化过程中进入系统的机械能不足以获得反应产物。虽然没有实现MgTiO3的合成,但获得了重要的结果,为进一步研究碱土金属与二氧化钛机械化学反应的可能性确定了模型。
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