| The demand for aluminum and aluminum alloy was increased with their wide applications in automotive, aerospace, electronics and other industries. Nowadays, aluminum and aluminum alloy production and processing industries need simple, accurate method to measure hydrogen and environmentally friendly, efficient method to dehydrogenate. Proton conductor methods for measuring and removing hydrogen in aluminum liquid are not only convenient, reliable but also pollution-free. And they have been studied and applied in Europe and Japan. But China is still under study in this area. To fill the gap and provide theoretical basis and technical support for our production of low hydrogen, high-quality aluminum, perovskite-type conductors were used for making hydrogen sensor and hydrogen pump to measure and remove hydrogen in aluminum liquid in this study.BaZrO3and BaZr0.9Yb0.1O3-α were synthetized using the raw materials of BaCO3、ZrO2and Yb2O3by solid state reaction at1400℃for10hours. Then, the synthetized samples were sintered at1600℃for10hours. XRD results show that BaZrO3and BaZro.9Yb0.1O3-α were obtained after synthesis and their phases did not change after sintered.The conductivities of BaZrO3and BaZr0.9Yb0.103-α calculated by their AC impedance spectra indicate that the conductivities of BaZr0.9Yb0.1O3-α were substantially increased after Yb3+doped.740℃≤T≤900℃, the conductivities of BaZrO3are6.93×10-7S·cm-1～3.71×10-6S·cm-1. and the conductivities of BaZr0.9Yb0.1O3-α are3.05×10-4S·cm-1～1.37×10-3S·cm-1. Then the conductivity equations of BaZrO3and BaZr0.9Yb0.1O3-α can be obtained according to Arrhenius formula, BaZrO3, in the temperature rang of740℃～900℃, is σ=102.9/T exp(12093.8/T),BaZr0.9Yb0.1O3-α, in the temperature rang of480℃～900℃, is σ=5596.182/T exp(-9890.901/T)The IR spectra of BaZrO3and BaZr0.9Yb0.103-α show that the IR spectrum of BaZr0.9Yb0.1O3-α presented stronger O-H band absorption peak than BaZrO3. This demonstrates that BaZr0.9Yb0.1O3-α after Yb3+doped generated protons and the protons were existed in the form of O-H band.According to the SEM results of BaZrO3and BaZr0.9Yb0.1O3-α, it is discovered that BaZr0.9Yb0.1O3-α had smaller particles, more pores and looser structure than BaZrO3after sintered. Thus, BaZr0.9Yb0.1O3-α was still not suitable for making hydrogen sensor and hydrogen pump, although its conductivities were higher.Hydrogen sensor was made using CaZr0.9In0.1O3-α with Pt as the electrode and H2-Ar mixed gas (H2,1.14%) as the standard gas. The resistance of the hydrogen sensor, calculated by its AC impedance spectra, was2024Ω The measurement results of the hydrogen sensor display that the response time of the hydrogen sensor was three minutes and the relative error of the hydrogen sensor compared to LECO RH-404was14.7%. Therefore, the assembled hydrogen sensor can be used for monitoring hydrogen in the aluminum liquid rapidly and continuously.Hydrogen pump was made using CaZr0.9In0.1O3-α. The resistance of the hydrogen pump was4200Ω computed by its AC impedance spectra. Aluminum liquid dehydrogenation experiments were carried out at the voltage of1.0V,1.5V,2.0V,2.5V using the assembled hydrogen pump respectively. The results exhibit that the dehydrogenation speed was6.6×10-4ml/(100gAl·min) at the voltage of1.0V when the hydrogen solution in the aluminum liquid was not less than0.245ml/100gAl and the dehydrogenation limit was0.093ml/100gAl at the voltage of2.5V. So CaZr0.9In0.1O3-α proton conductor hydrogen pump can be used for rapid dehydrogenation of the aluminum with high hydrogen content or deep dehydrogenation of the aluminum with high quality requirements. |
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