Interaction between Cr-bearing pigments and transparent glaze: A transmission electron microscopy study

Abstract Spinel ZnAl 2 O 4 and corundum Al 2 O 3 doped with chromium are used as pink pigments in porcelain glazes. However, alteration of the color can occur during firing, and the resulting glaze appears brown and green respectively, instead of the expected pink. To investigate the mechanism of color change, electron transparent sections were prepared by Focused Ion Beam (FIB) at the interface between pigment and glaze. Observations under a transmission electron microscope (TEM) reveal a common mechanism for both systems. Al migration from the pigment towards the silicate melt results in alteration of the grain of pigments, and formation of a Cr enriched phase, with the same crystalline structure than the initial pigment. Furthermore, the formation of anorthite is reported, due to the increase of the local concentration of Al in the melt. The different morphologies of altered grains of pigment encountered in the glaze are discussed base on the TEM observations.

[1]  P. Roeder,et al.  Crystallization of Chromite and Chromium Solubility in Basaltic Melts , 1991 .

[2]  D. Uhlmann,et al.  Crystallization behavior of anorthite , 1974 .

[3]  Arthur F. Miller.  Distribution of Cations in Spinels , 1959 .

[4]  M. Llusar,et al.  Influence of some mineralizers in the synthesis of sphene-pink pigments , 1998 .

[5]  Miss A.O. Penney.  (b) , 1974, The New Yale Book of Quotations.

[6]  M. F. Gazulla,et al.  Interaction of the chromium–iron black pigment with porcelanised stoneware , 2013 .

[7]  P. Richet,et al.  Glass formation in silicates: Insights from composition , 2006 .

[8]  R. Eppler,et al.  The Relative Stability of Ceramic Pigments , 2008 .

[9]  Olivier Dargaud,et al.  The stability of gahnite doped with chromium pigments in glazes from the French manufacture of Sèvres , 2017 .

[10]  C. Vollmer,et al.  Experimental determination of trace element partition coefficients between spinel and silicate melt: the influence of chemical composition and oxygen fugacity , 2015, Contributions to Mineralogy and Petrology.

[11]  Howard F. McMurdie,et al.  Phase diagrams for ceramists , 1964 .

[12]  Alexandre Brongniart,et al.  Traité des arts céramiques ou des poteries : considérées dans leur histoire, leur pratique et leur théorie , 2022 .

[13]  M. Cotte,et al.  Spectroscopic properties of Cr 3+ in the spinel solid solution , 2016 .

[14]  E. Cordoncillo,et al.  Towards more ecological ceramic pigments: Study of the influence of glass composition on the colour stability of a pink chromium-doped ceramic pigment , 2007 .

[15]  A. R. Cooper,et al.  Dissolution in Ceramic Systems: I, Molecular Diffusion, Natural Convection, and Forced Convection Studies of Sapphire Dissolution in Calcium Aluminum Silicate , 1964 .

[16]  Benjamin K. Wilson,et al.  Chromium phase behavior in a multi-component borosilicate glass melt , 2006 .

[17]  Louis R. Rossi,et al.  Elastic Properties of Oxide Solid Solutions: The System Al2O3−Cr2O3 , 1970 .

[18]  S. Turan,et al.  Production and characterisation of iron-chromium pigments and their interactions with transparent glazes , 2003 .

[19]  R. Eppler,et al.  The Interaction of Ceramic Pigments with Glazes , 2008 .

[20]  C. Leonelli,et al.  Crystallization of some anorthite-diopside glass precursors , 1991, Journal of Materials Science.

[21]  P. Roeder,et al.  The Range of Spinel Compositions in Terrestrial Mafic and Ultramafic Rocks , 2001 .

[22]  V. Kozhukharov,et al.  Influence of crystallinity on chromatic parameters of enamels coloured with malayaite pink pigments , 2003 .

[23]  A. Irving.  A review of experimental studies of crystal/liquid trace element partitioning , 1978 .

[24]  B. Chiou,et al.  Low temperature sintering and crystallisation behaviour of low loss anorthite-based glass-ceramics , 2003 .

[25]  M. Cotte,et al.  Spectroscopic properties of $$\hbox {Cr}^{3+}$$Cr3+ in the spinel solid solution $$\hbox {ZnAl}_{2-x}\hbox {Cr}_{x}\hbox {O}_4$$ZnAl2-xCrxO4 , 2016 .

[26]  Christine J. Byrne,et al.  How glaze composition affects chrome-tin pinks , 1994 .

[27]  A. Aghaei,et al.  Synthesis of Y(Al,Cr)O3 red pigments by co-precipitation method and their interactions with glazes , 2009 .

[28]  H. Yurdakul,et al.  The mechanism for the colour change of iron chromium black pigments in glazes through transmission electron microscopy techniques , 2011 .