Lee Hwanseok, Lee Hee-Seon, Kim Seonghoon, Jo Kanghee, Jo Ilguk, Lee Heesoo
School of Materials Science and Engineering, Pusan National University, Busan 46241, Republic of Korea.
Reliability Assessment Center, Korea Research Institute of Chemical Technology, Daejeon 34114, Republic of Korea.
Materials (Basel). 2023 Nov 20;16(22):7240. doi: 10.3390/ma16227240.
MnO and CeO were doped to improve the corrosion resistance of CSZ (calcia-stabilized zirconia), and we studied the phase formation, mechanical properties, and corrosion resistance by molten mold flux. The volume fraction of the monoclinic phase gradually decreased as the amount of MnO doping increased. The splitting phenomenon of the t(101) peak was observed in 2Mn_CSZ, and in 4Mn_CSZ, it was completely split, forming a cubic phase. The relative density increased and the monoclinic phase decreased as the doping amount increased, leading to an increase in Vickers hardness and flexural strength. However, in 3Mn_CSZ and 4Mn_CSZ, where cubic phase formation occurred, the tetragonal phase decreased, leading to a reduction in these properties. MnO-doped CSZ exhibited a larger fraction of the monoclinic phase compared to the original CSZ after the corrosion test, indicating worsened corrosion resistance. These results are attributed to the predominant presence of Mn and Mn forms, rather than the Mn form, which has a smaller basicity difference with SiO, and due to the low melting point. The monoclinic phase fraction decreased as the doping amount of CeO increased in CeO-doped CSZ, but the rate of decrease was lower compared to MnO-doped CSZ. The monoclinic phase decreased as the doping amount increased, but the Vickers hardness and flexural strength showed a decreasing trend due to the low relative density. The destabilization behavior of Ca in SEM-EDS images before and after corrosion was difficult to identify due to the presence of Ca in the slag, and the destabilization behavior of Ce due to slag after corrosion was not observed. In the XRD data of the specimen surface after the corrosion test, the fraction of the monoclinic phase increased compared to before the test but showed a lower monoclinic phase fraction compared to CSZ. It is believed that CeO has superior corrosion resistance compared to CaO because Ce predominantly exists in the form of Ce, which has a smaller difference in basicity within the zirconia lattice.
掺杂MnO和CeO以提高钙稳定氧化锆(CSZ)的耐腐蚀性,并且我们研究了通过熔渣的相形成、力学性能和耐腐蚀性。随着MnO掺杂量的增加,单斜相的体积分数逐渐降低。在2Mn_CSZ中观察到t(101)峰的分裂现象,而在4Mn_CSZ中,它完全分裂,形成立方相。随着掺杂量的增加,相对密度增加且单斜相减少,导致维氏硬度和抗弯强度增加。然而,在发生立方相形成的3Mn_CSZ和4Mn_CSZ中,四方相减少,导致这些性能降低。与原始CSZ相比,经腐蚀试验后,MnO掺杂的CSZ表现出更大比例的单斜相,表明耐腐蚀性变差。这些结果归因于Mn和Mn形态的大量存在,而不是与SiO碱度差异较小的Mn形态,并且由于熔点较低。在CeO掺杂的CSZ中,随着CeO掺杂量的增加,单斜相分数降低,但与MnO掺杂的CSZ相比,降低速率较低。随着掺杂量增加,单斜相减少,但由于相对密度较低,维氏硬度和抗弯强度呈下降趋势。由于炉渣中存在Ca,腐蚀前后SEM-EDS图像中Ca的失稳行为难以识别,并且未观察到腐蚀后由于炉渣导致的Ce的失稳行为。在腐蚀试验后试样表面的XRD数据中,与试验前相比,单斜相分数增加,但与CSZ相比,单斜相分数较低。据信,CeO与CaO相比具有优异的耐腐蚀性,因为Ce主要以Ce的形式存在,其在氧化锆晶格内的碱度差异较小。