Synthesis and Coloring Mechanism of Metallic Glaze in R₂O-RO-Al₂O₃-SiO₂-P₂O₅ System

Abstract

A copper-red and silver-white metallic glaze of R₂O-RO-Al₂O₃-SiO₂-P₂O₅ system was synthesized by adjusting the firing temperature and glaze components. The coloration mechanism of the metallic glaze was revealed via investigation of the microstructure of the glaze. Our research reveals that the metallic glaze with different colors is mainly due to the amount of Fe₂O₃. The metallic glaze shows a silver-white luster due to a structural color of α-Fe₂O₃ crystals with a good orientation when the sample contains 0.093 9 mol of Fe₂O₃, maintaining temperatures at 1 150 °C for 0.5 h. The metallic glaze is copper-red which is dominated by the coupling of chemical and structural color of α-Fe₂O₃ crystals when the sample contains 0.078 3 mol of Fe₂O₃. After testing the amount of SiO₂, we find that 4.049 9 mol is the optimal amount to form the ceramic network, and 0.27 mol AlPO₄ is the best amount to promote phase separation.

Keywords

metallic glaze / phase separation / coloring mechanism / chemical color / structural color

References

[1] Cao Z, Luo T, Fang Y, et al. Effect of Glaze Phase Separation on Lead-free CuO-MnO₂ System Metallic Luster Glaze[J]. Bulletin Of The Chinese Ceramic Society, 2020, 39(12): 3 964-3 970 (in Chinese)

[2] Xu Y, Cheng Z, Wu K, et al. Effects of Fe₂O₃ on Structure and Coloring of Grey-blue Glaze of Yixing Jun Pottery[J]. Journal of Ceramics, 2022, 43(02): 323-329 (in Chinese)

[3] Zhu JF, Shi P, Wang F, et al. Preparation of Separative-phase Fancy Glaze Derived from Iron Ore Slag[J]. Ceramics International, 2016, 42(4): 5 250-5 257

[4] Li WD, Luo HJ, Li JA, et al. Studies on the Microstructure of the Black-glazed Bowl Sherds Excavated from the Jian Kiln Site of Ancient China[J]. Ceramics International, 2008, 34: 1 473-1 480

[5] Shi J, Sun G, Xiao Z, et al. The Coloration of Phase-separative Glaze Based on R₂O-RO-Fe₂O₃-Al₂O₃-SiO₂[J]. Journal of Ceramics, 2020, 41(05): 671-677 (in Chinese)

[6] Yang S, Chen Jiaying. Structural Color of Butterfly Wings Living in Temperate Zone[J]. Optical Technique., 2021, 47(3): 339-34 (in Chinese)

[7] Zhu C, Zhang H, Fa W, et al. Nano-silver-induced Ceramic Coloring via Control of Glaze Interface and Phase Separation[J]. Rare Metals, 2021, 40(08): 2 292-2 300

[8] Shi XT, Zhang T. The Preparation Process and Mechanism of the Iron-red Fancy Glaze under High Temperature Reducing Atmosphere[J]. Applied Mechanics and Materials, 2014, 670: 318-322

[9] Li M, Li W, Lu X, et al. Controllable Preparation and Decorative Effect of Iron-based Crystalline Glazes[J]. J. Chin. Ceram. Soc., 2020, 48: 1 134-1 144

[10] Huang X, Zhan H, Liu Q, et al. Correlation Between Glaze Color and Crystallization Process of Fe₂O₃ in Glaze Melt[J]. J. Chin. Ceram. Soc., 2022, 50(09): 2 448-2 454

[11] Li W, Luo H, Li J, et al. Studies on the Microstructure of the Black-glazed Bowl Sherds Excavated from the Jian Kiln Site of Ancient China[J]. Ceramics International, 2008, 34(6): 1 473-1 480

[12] Qiu B, Gu X, Liu K, et al. Effect of Chemical Composition on Phase Separation Iron-red glaze[J]. Bulletin of The Chinese Ceramic Society, 2019, 38(05): 1 568-1 572 (in Chinese)

[13] Mirdali NK, Daday M, Daday MT. Development and Characterization of Low-temperature Metallic Glazes in Na₂O-B₂O₃-SiO₂ (NBS) System[J]. Ceramics International, 2019, 45(17): 21 661-21 667

[14] Yang Changan. Research on Separative-phase Glaze and Its Structural Color, 2016, Xi’an: Shaanxi University of Science and Technology [D]

[15] Subhashini, Shashikala HD, Udayashankar NK. Influence of Fe³⁺ions on Optical, Structural, Thermal and Mechanical Properties of Li₂O-Na₂O-K₂O-ZnO-B₂O₃ Based Glass System[J]. Ceramics International, 2020, 46(4): 5 213-5 222

[16] Park JH, Yu H, Chung YJ. A Study on the Changing Properties of Iron Oxides in Black Glazes using Raman Microscope[J]. Journal of Conservation Science, 2019, 35(2): 117-129

[17] Gong X, You J, Wang J, et al. Microstructures of Several Iron Oxide Compounds and Their Raman Spectroscopic Studies[J]. Spectroscopy and Spectral Analysis, 2018, 38(S1): 241-242 (in Chinese)

[18] Guo C, Hu Y, Qian H, et al. Magnetite (Fe₃O₄) Tetrakaidecahedral microcrystals: Synthesis, Characterization, and Micro-Raman Study[J]. Materials Characterization, 2011, 62(1): 148-151

[19] Shi J, Sun G, Xiao Z, et al. Effect of Sintering Process on Color Appearance and Microstructure of Colorful Glaze Based on Fe₂O₃-Al₂O₃-SiO₂ System[J]. Journal of Ceramics, 2021, 42(05): 849-854 (in Chinese)

[20] Kang J, Chen Z, Zhu X, et al. Effect of Replacement of Na₂O by Fe₂O₃ on the Crystallization Behavior and Acid Resistance of MgO-Al₂O₃-SiO₂ Glass-ceramics[J]. Journal of Non-Crystalline Solids, 2019, 503–504: 1-6

[21] Shi Y, Han X, Li B, et al. Modification of Glass Network and Crystallization of CaO-Al₂O₃-MgO-SiO₂-based Glass Ceramics with the Addition of Iron Oxide[J]. Ceramics International, 2020, 46(7): 9 207-9 217

[22] Yu Q, Yan C, Deng Y, et al. Effect of Fe₂O₃ on Non-isothermal Crystallization of CaO-MgO-Al₂O₃-SiO₂ Glass[J]. Transactions of Nonferrous Metals Society of China, 2015, 25(7): 2 279-2 284

[23] Fang Wenbing. Preparation and Application of Photonic-crystals Pigments, 2020, Suzhou: Soochow University [D]