MnO对Ca_2Mg_2Al_(28)O_(46)材料结构和性能的影响
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摘要
采用固相烧结法制备了含不同比例MnO的Ca_2Mg_2Al_(28)O_(46)材料,研究了材料的烧结性能、显微结构和热学性能。结果表明:1 650℃下Mn~(2+)取代Mg~(2+)固溶进入Mg Al_2O_4晶格形成Mg_(1–x)Mn_xAl_2O_4同构尖晶石固溶体,进而扩散进入Ca_2Mg_2Al_(28)O_(46),产生畸变的磁铅石结构,使晶粒形貌从六方片层状向等轴状发展,并加快了材料的致密化进程。含不同添加量MnO的Ca_2MgAl_(28)O_(46)材料1 750℃热处理后的体积密度为3.21～3.33 g/cm~3,闭口气孔率在0.4%～1.1%。随着MnO含量的增加,材料的热膨胀系数略有增大,但热导率明显提高,添加2%(质量分数)MnO试样的热膨胀系数由8.94×10~(–6)/K增加到9.41×10~(–6)/K,热导率由1.49 W/(m·K)增加到2.70 W/(m·K)。
Ca_2Mg_2Al_(28)O_(46) materials with different ratios of MnO were prepared via solid-state reaction sintering. The sintering properties, microstructure and thermal properties of the material were investigated. The results show that Mn~(2+) solid-dissolves into MgAl_2O_4 lattice by substitution of Mg~(2+) to form Mg_(1–x)Mn_xAl_2O_4 solid solution at 1 650 ℃, and then diffuses into Ca_2Mg_2Al_(28)O_(46),resulting in a distorted magnetoplumbite structure and drives the grain morphology from hexagonal to equiaxed. The addition of MnO accelerates the densification of the material, the bulk density of Ca_2Mg_2Al_(28)O_(46) materials with different additions of MnO is 3.21–3.33 g/cm~3, the closed porosity is 0.4%–1.1% after heat treatment at 1 750 ℃. The thermal expansion coefficient of the materials increases slightly and the thermal conductivity increases with the increase of MnO content. The thermal expansion coefficient of materials increases from 8.94×10~(–6)/K to 9.41×10~(–6)/K and the thermal conductivity increases from 1.49 W/(m·K) to 2.70 W/(m·K) at the addition of 2 %(in mass fraction) MnO.
Ca_2Mg_2Al_(28)O_(46) materials with different ratios of MnO were prepared via solid-state reaction sintering. The sintering properties, microstructure and thermal properties of the material were investigated. The results show that Mn~(2+) solid-dissolves into MgAl_2O_4 lattice by substitution of Mg~(2+) to form Mg_(1–x)Mn_xAl_2O_4 solid solution at 1 650 ℃, and then diffuses into Ca_2Mg_2Al_(28)O_(46),resulting in a distorted magnetoplumbite structure and drives the grain morphology from hexagonal to equiaxed. The addition of MnO accelerates the densification of the material, the bulk density of Ca_2Mg_2Al_(28)O_(46) materials with different additions of MnO is 3.21–3.33 g/cm~3, the closed porosity is 0.4%–1.1% after heat treatment at 1 750 ℃. The thermal expansion coefficient of the materials increases slightly and the thermal conductivity increases with the increase of MnO content. The thermal expansion coefficient of materials increases from 8.94×10~(–6)/K to 9.41×10~(–6)/K and the thermal conductivity increases from 1.49 W/(m·K) to 2.70 W/(m·K) at the addition of 2 %(in mass fraction) MnO.
引文
[1]GOBBELS M,WOERMANN E,JUNG J,The Al-rich part of the system Ca O-Al2O3-MgO.Part I.Phase relationships[J].J Solid State Chem,1995,120:358-363.
[2]IYI N,GOBBELS M,MATSUI Y.The Al-rich part of the system Ca O-Al2O3-MgO.Part II.Structure refinement of two new magnetoplumbite-related phases[J].J Solid State Chem,1995,120:364-371.
[3]SASAKI T,FUKUSHIMA J,HAYASHI Y,et al.Synthesis and photoluminescence properties of Mn4+-doped magnetoplumbite-related aluminate X-type Ca2Mg2Al28O46 and W-type CaMg2Al16O27 red phosphors[J].Ceram Int,2017,43(9):7147-7152.
[4]WANG B,LIN H,XU J,etal.Ca Mg2Al16O27:Mn4+-based Red Phosphor:A Potential Color Converter for High-Powered Warm W-LED[J].ACS Appl Mater Interfaces,2014(6):22905-22913.
[5]BANSAL N P,ZHU D M.Thermal properties of oxides with magnetoplumbite structure for advanced thermal barrier coatings[J].Surf Coat Technol,2008,202(12):2698-2703.
[6]杨文杰,贺柳青,李静,等.MnO添加对40(50Cu-Ni)-(NiFe2O4-10NiO)金属陶瓷惰性阳极的影响[J].人工晶体学报,2017,46(1):178-182.YANG W J,HE L Q,LI J,et al.J Synth Cryst(in Chinese),2017,46(1):178-182.
[7]YIN X L,CHEN M,WANG N,et al.Improvement of densification and mechanical properties of MgAl2O4-CaAl4O7-CaAl12O19 composite by addition of MnO[J].Ceram Int,2017,43:4706-4711.
[8]马丽景,王林宏,李殿卿,等.Mn、Fe取代六铝酸盐的结构和甲烷催化燃烧性能[J].化工学报,2006,57(11):2604-2609.MA Lijing,WANG Linhong,LI Dianqing,et al.J Chem Ind Eng(in Chinese),2006,57(11):2604-2609.
[9]彭森,吴孟强,黄同成,等.MnCO3掺杂对BMN陶瓷结构及介电性能的影响[J].硅酸盐学报,2017,45(3):339-345.PENG Sen,WU Mengqiang,HUANG Tongcheng,et al.J Chin Ceram Soc,2017,45(3):339-345.
[10]SAKO E Y,BRAULIO M A L,ZINNGREBE E,et al.In-depth microstructural evolution analyses of cement-bonded spinel refractory castables:novel insights regarding spinel and CA6 formation[J].J Am Ceram Soc,2012,95:1732-1740.
[11]夏忠锋,王周福,王玺堂,等.刚玉-尖晶石浇注料基质的物相及结构演变过程[J].耐火材料,2016,50(6):440-433.XIA Zhoufeng,WANG Zhoufu,WANG Xitang,et al.Refractories(in Chinese),2016,50(6):440-433.
[12]CHEN J H,CHEN H Y,MI W J.Synthesis of CaO·2MgO·8Al2O3 and its slag resistance mechanism[J].J Eur Ceram Soc,2017,37:1799-1804.
[13]FU L P,HUANG A,GU H Z,et al.Effect of nano-alumina sol on the sintering properties and microstructure of microporous corundum[J].Mater Design,2016,89:21-26.
[14]FU L P,GU H Z,HUANG A,et al.Effect of MgO micropowder on sintering properties and microstructures of microporous corundum aggregates[J].Ceram Int,2015,41:5857-5862.
[15]吴红丹,张锦化,周志辉,等.磁铅石结构NdMgAl11O19粉体的合成与晶格热膨胀[J].硅酸盐学报,2017,45(7):1-6.WU Hongdan,ZHANG Jinhua,ZHOU Zhihui,et al.J Chin Ceram Soc,2017,45(7):1-6.
[2]IYI N,GOBBELS M,MATSUI Y.The Al-rich part of the system Ca O-Al2O3-MgO.Part II.Structure refinement of two new magnetoplumbite-related phases[J].J Solid State Chem,1995,120:364-371.
[3]SASAKI T,FUKUSHIMA J,HAYASHI Y,et al.Synthesis and photoluminescence properties of Mn4+-doped magnetoplumbite-related aluminate X-type Ca2Mg2Al28O46 and W-type CaMg2Al16O27 red phosphors[J].Ceram Int,2017,43(9):7147-7152.
[4]WANG B,LIN H,XU J,etal.Ca Mg2Al16O27:Mn4+-based Red Phosphor:A Potential Color Converter for High-Powered Warm W-LED[J].ACS Appl Mater Interfaces,2014(6):22905-22913.
[5]BANSAL N P,ZHU D M.Thermal properties of oxides with magnetoplumbite structure for advanced thermal barrier coatings[J].Surf Coat Technol,2008,202(12):2698-2703.
[6]杨文杰,贺柳青,李静,等.MnO添加对40(50Cu-Ni)-(NiFe2O4-10NiO)金属陶瓷惰性阳极的影响[J].人工晶体学报,2017,46(1):178-182.YANG W J,HE L Q,LI J,et al.J Synth Cryst(in Chinese),2017,46(1):178-182.
[7]YIN X L,CHEN M,WANG N,et al.Improvement of densification and mechanical properties of MgAl2O4-CaAl4O7-CaAl12O19 composite by addition of MnO[J].Ceram Int,2017,43:4706-4711.
[8]马丽景,王林宏,李殿卿,等.Mn、Fe取代六铝酸盐的结构和甲烷催化燃烧性能[J].化工学报,2006,57(11):2604-2609.MA Lijing,WANG Linhong,LI Dianqing,et al.J Chem Ind Eng(in Chinese),2006,57(11):2604-2609.
[9]彭森,吴孟强,黄同成,等.MnCO3掺杂对BMN陶瓷结构及介电性能的影响[J].硅酸盐学报,2017,45(3):339-345.PENG Sen,WU Mengqiang,HUANG Tongcheng,et al.J Chin Ceram Soc,2017,45(3):339-345.
[10]SAKO E Y,BRAULIO M A L,ZINNGREBE E,et al.In-depth microstructural evolution analyses of cement-bonded spinel refractory castables:novel insights regarding spinel and CA6 formation[J].J Am Ceram Soc,2012,95:1732-1740.
[11]夏忠锋,王周福,王玺堂,等.刚玉-尖晶石浇注料基质的物相及结构演变过程[J].耐火材料,2016,50(6):440-433.XIA Zhoufeng,WANG Zhoufu,WANG Xitang,et al.Refractories(in Chinese),2016,50(6):440-433.
[12]CHEN J H,CHEN H Y,MI W J.Synthesis of CaO·2MgO·8Al2O3 and its slag resistance mechanism[J].J Eur Ceram Soc,2017,37:1799-1804.
[13]FU L P,HUANG A,GU H Z,et al.Effect of nano-alumina sol on the sintering properties and microstructure of microporous corundum[J].Mater Design,2016,89:21-26.
[14]FU L P,GU H Z,HUANG A,et al.Effect of MgO micropowder on sintering properties and microstructures of microporous corundum aggregates[J].Ceram Int,2015,41:5857-5862.
[15]吴红丹,张锦化,周志辉,等.磁铅石结构NdMgAl11O19粉体的合成与晶格热膨胀[J].硅酸盐学报,2017,45(7):1-6.WU Hongdan,ZHANG Jinhua,ZHOU Zhihui,et al.J Chin Ceram Soc,2017,45(7):1-6.