利用铬铁废渣制备黑色陶瓷釉
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摘要
利用铬铁废渣为Fe和Cr元素的致色前驱体制备了环境友好型黑色陶瓷釉。结果表明:黑釉中发色晶体为Fe–Cr–Co型混合尖晶石,黑釉中由于其尖晶石结构中Fe~(3+)的d–d跃迁、Co~(2+)的~4A_2(F)→~4T_1(P)跃迁以及Cr~(3+)的~4A_(2g)→~4T_(2g)跃迁,在可见光波长范围内吸收所有可见光,外观为黑色。随着烧成温度的增加,黑釉中主晶相及色度值无明显变化,表现出较好的高温稳定性。黑釉在酸和碱的浸蚀96 h下质量损失小于0.1%,表现出较好的耐化学性。黑釉中Cr元素以3价的形式存在,因此,利用铬铁废渣制备的黑釉中Cr的存在形式是无害的。
An environmental-friendly black glaze was prepared with a ferrochrome slag waste as chromium and iron precursors. The glaze with a black color could be obtained when a composite of Fe_2O_3 and Co_2O_3 was added. The color agent in black glaze is Fe-Cr-Co mixed spinel. Based on the result by ultraviolet-visible spectrophotometry(UV–Vis), the intensity of black color in glaze is related to the presence of d–d transitions of Fe~(3+), ~4A_2(F)→~4T_1(P) of Co~(2+), and ~4A_2 g→~4T_2 g of Cr~(3+) in spinel structures, practically absorbing in the whole visible region for the appearance of black color. The main crystal phases and color parameter of the prepared black glaze change slightly when the firing temperature increases, indicating a high-temperature stability. The black glaze has a chemical resistance against acid and alkaline attack after 96 h, showing a mass loss of less than 0.1% in mass. The results by X-ray photo electron spectroscopy show that Cr existing in the black glaze presents a trivalent state, indicating that the existence of Cr in the black glaze prepared by ferochromium slag waste could be harmless.
An environmental-friendly black glaze was prepared with a ferrochrome slag waste as chromium and iron precursors. The glaze with a black color could be obtained when a composite of Fe_2O_3 and Co_2O_3 was added. The color agent in black glaze is Fe-Cr-Co mixed spinel. Based on the result by ultraviolet-visible spectrophotometry(UV–Vis), the intensity of black color in glaze is related to the presence of d–d transitions of Fe~(3+), ~4A_2(F)→~4T_1(P) of Co~(2+), and ~4A_2 g→~4T_2 g of Cr~(3+) in spinel structures, practically absorbing in the whole visible region for the appearance of black color. The main crystal phases and color parameter of the prepared black glaze change slightly when the firing temperature increases, indicating a high-temperature stability. The black glaze has a chemical resistance against acid and alkaline attack after 96 h, showing a mass loss of less than 0.1% in mass. The results by X-ray photo electron spectroscopy show that Cr existing in the black glaze presents a trivalent state, indicating that the existence of Cr in the black glaze prepared by ferochromium slag waste could be harmless.
引文
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[11]TANG Yufei,WU Cong,SONG Yuan,et al.Effects of colouration mechanism and stability of CoAl2O4 ceramic pigments sintered on substrates[J].Ceram Int,2018,44,(1):1019-1025
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[13]JACAOBS J P,MALT A,REINTJES J G H,et al.The surface of catalytically active spinels[J].J Catal,1994,147(1):294-300.
[14]MURPHY V,Hughes H,MCLOUGHLIN P.Enhancement strategies for Cu(II),Cr(III)and Cr(VI)remediation by a variety of seaweed species[J].J Hazard Mater,2008,166(1):318-326.
[15]邱会东,杨治立,兰伟,等.高碳铬铁渣中铬的存在形态研究[J].铁合金,2008,39(6):29-31.QIU Huidong,YANG Zhili,LAN Wei,et al.Ferro-Alloys(in Chinese),2008,39(6):29-31.
[2]YURDAKUL H,TURAN S,OZEL E.The mechanism for the colour change of iron chromium black pigments in glazes through transmission electron microscopy techniques[J].Dyes Pigments,2011,91(2):126-133.
[3]SAHU N,BISWAS A,KAPURE G U.A short review on utilisation of ferrochromium slag[J].Min Proc Met Rev,2016,37(4):211-219
[4]LIU C,LIU L,TAN K,et al.Fabrication and characterization of porous cordierite ceramics prepared from ferrochromium slag[J].Ceram Int,2012,42(1):734-742.
[5]SILVA R D,PIANARO S A,TEBCHERANI S M.Preparation and characterization of glazes from combinations of different industrial wastes[J].Ceram Int,2012,38(4):2725-2731.
[6]张筱君,陈婷,江伟辉,等.复合包裹法制备C@SiO2@ZrSiO4黑色色料的研究[J].陶瓷学报,2016,37(1):17-22.ZHANG Youjun,CHEN Ting,JIANG Weihui,et al.J Ceram(in Chinese),2016,37(1):17-22.
[7]陈云霞,胡琪,曹春娥,等.Zn2+、Cr3+掺杂对水热合成纳米Co Al2O4尖晶石色料的影响[J].无机材料学报,2012,27(12):1317-1320.CHEN Yunxia,HU Qi,CAO Chune,et al.J Inorg Mater(in Chinese),2012,27(12):1317-1320.
[8]GILABERT J,M.D.PALACIOS,ORTS M J,et al.Solution of combustion synthesis of(Ni,Fe)Cr2O4 pigments:Effect of post-synthesis thermal treatments[J].Ceram Int,2017,43(15):10032-10040
[9]DUAN X,LIU J,YU F,et al.Co/Cr co-doped MgGa2O4,nanoparticles:Microstructure and optical properties[J].Mater Res Bull,2016,73:90-95.
[10]LI L,YAN Z F,LU G Q,et al.Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction[J].J Phys Chem B,2006,110(1):178.
[11]TANG Yufei,WU Cong,SONG Yuan,et al.Effects of colouration mechanism and stability of CoAl2O4 ceramic pigments sintered on substrates[J].Ceram Int,2018,44,(1):1019-1025
[12]MACADAM D L.Subtractive color mixture and color reproduction[J].JOSA,1938,28(12):466-479.
[13]JACAOBS J P,MALT A,REINTJES J G H,et al.The surface of catalytically active spinels[J].J Catal,1994,147(1):294-300.
[14]MURPHY V,Hughes H,MCLOUGHLIN P.Enhancement strategies for Cu(II),Cr(III)and Cr(VI)remediation by a variety of seaweed species[J].J Hazard Mater,2008,166(1):318-326.
[15]邱会东,杨治立,兰伟,等.高碳铬铁渣中铬的存在形态研究[J].铁合金,2008,39(6):29-31.QIU Huidong,YANG Zhili,LAN Wei,et al.Ferro-Alloys(in Chinese),2008,39(6):29-31.