Effect of pigment micronization on microstructure, phase composition and colour evolution
MOLINARI C. 1, ARDIT M. 2, VERUCCHI D. 3, TINTORRI A. 3, MIGLIORI M. 3, TOSCHI T. 3, GUARINI G. 1, CONTE S. 1, CRUCIANI G. 2, DONDI M. 1, ZANELLI C. 1
1 CNR - ISSMC, Faenza, Italy; 2 Physics and Earth Sciences Department, University of Ferrara, Ferrara, Italy; 3 INCO Industria Colori S.p.A, Pavullo, Italy
Nowadays, ceramic decoration is being industrially carried out mainly by inkjet printing (IJP). The advent of digital decoration has changed the technological requirements of pigments and the way they are obtained. Ceramic pigments must be micronized (median particle diameter d50 ~300 nm) to fulfil IJP and shelf life requirements. Particle size distribution plays a crucial role for the ink compatibility and the final application. In this respect, pigment grindability is a key parameter, which has strong repercussions on tinctorial strength and resistance to amorphization of the pigment crystal structure. The reasons behind different pigment behavior during milling are still unknown. In order to deep investigate the relationship between crystal properties and milling effect, five pigments with distinct physical properties were selected (main constituting phase: zircon, spinel, malayaite, olivine, eskolaite). Model inks, characterized by different milling degree, were prepared and underwent lab-scale stirred media milling reproducing the industrial micronization conditions. Milling evolution was followed by determining particle size distribution (laser diffraction) and energy demand (mill electric consumption). The effect of the process on phase composition and crystal structure parameters was followed by XRPD-Rietveld analysis. Furthermore, to define the changes in color saturation, micronized pigments were characterized by optical spectroscopy (DRS) and colourimetry after application in glaze and fired at 1200°C. Finally, to point out the possible involvement of different mechanisms during the milling process, a detailed microstructural characterization was performed (SEM). Every pigment exhibits a distinct grindability with non-linear trends of comminution rate and specific energy consumption with particle size. Regardless the amount of energy involved, only a limited amorphization is observed, and a correlation between crystal size and cell strain is highlighted. Optical spectra suggest a specific effect of milling for each pigment, sometimes entailing a change in chromophores (in Cr-doped malayaite and Co-olivine). Microstructures hint at different mechanisms acting during comminution, with particle shapes proper of brittle fracture versus plastic deformation or fragments agglomeration. Overall, a complex dependence of grinding efficiency on the pigment bulk modulus arose, with a different relationship of particles size reduction, optical properties and tinctorial strength on milling cycles.