Purpose This paper aims to systematically demonstrate a methodology to determine the relative and absolute encapsulation efficiencies (αRe and αAb) for thermally- and chemically-robust inorganic pigments, typically like ZrSiO4-based pigments, thereby enhancing their coloring performance. Design/methodology/approach The authors designed a route, surplus alkali-decomposition and subsequently strong-acid dissolution (SAD2) to completely decompose three classic zircon pigments (Pr–ZrSiO4, Fe2O3@ZrSiO4 and CdS@ZrSiO4) into clear solutions and preferably used inductively coupled plasma-optical emission spectrometry (ICP-OES) to determine the concentrations of host elements and chromophores, thereby deriving the numeric data and interrelation of αRe and αAb. Findings Zircon pigments can be thoroughly decomposed into some dissoluble zirconate–silicate resultants by SAD2 at a ratio of the fluxing agent to pigment over 6. ICP-OES is proved more suitable than some other quantification techniques in deriving the compositional concentrations, thereby the values of αRe and αAb, and their transformation coefficient KRA, which maintains stably within 0.8–0.9 in Fe2O3@ZrSiO4 and CdS@ZrSiO4 and is slightly reduced to 0.67–0.85 in Pr–ZrSiO4. Practical implications The SAD2 method and encapsulation efficiencies are well applicable for both zircon pigments and the other pigmental or non-pigmental inhomogeneous systems in characterizing their accurate composition. Originality/value The authors herein first proposed strict definitions for the relative and absolute encapsulation efficiencies for inorganic pigments, developed a relatively stringent methodology to determine their accurate values and interrelation.

It is of particular significance to unveil the authentic coloration mechanism of the multivalent praseodymium colored ZrSiO4 yellow pigments for advanced decoration applications. We herein adopted a facile strategy to modulate the fluorine‐assisted zircon crystallization and thereby obtained ultrafine Pr‐ZrSiO4 yellow pigments, which have a remarkably narrow size distribution and average diameters within 250–400 nm. By virtue of some cogent combinative spectra of reflection, absorption, excitation, and emission from three types of elaborately‐designed H2‐, air‐, and O2‐based pigments, the coloration mechanism for the Pr‐colored zircon was systematically unveiled: both Pr4+ and Pr3+ coexist invariably in the pigments, while the former contributes primarily to the ligand‐to‐metal charge transfer from O2p to Pr(IV)4f for the blue–violet absorption to generate the yellow hue, and the latter is inclined to discolor the pigments. Therefore, an oxidizing atmosphere is preferable to produce brilliant Pr‐ZrSiO4 pigments with enhanced chromatic properties. The stark spectroscopic distinctions between the wide‐band absorption from the nonluminescent tetravalency and the narrow‐band absorption from the luminescent trivalency can expand our understanding to the rare‐earth‐based inorganic pigments.