Environmentally benign rare earth pigments: effect of calcium dopant and tuning of bandgaps for different color hues
Authors: V. Divya , Jayan Divya , Kumar Asoka 
Published: November 2021

Purpose

As there is a strong inducement to develop new colored inorganic materials to substitute the current industrial pigments that are based on toxic metals hazardous to health and the environment, the purpose of this paper is to invent environmentally benign rare earth-based colorants as viable alternatives to the traditional toxic pigment formulations. Herein, the authors developed a series of rare earth pigments having the general formula Ca0.1 Ln0.9 PO4 ( Ln = Y , Pr , mixed rare earth oxides, RE and Di). After studying all the optical properties, the authors have gone for some coloring application in plastic like PMMA.

Design/methodology/approach

The designed pigments were synthesized by traditional solid-state method. Stoichiometric amounts of each reagent were mixed in an agate mortar and the mixtures were calcined at optimized temperature 1000 °C for 4 h in electric furnace followed by auto–cooling. The samples were characterized by X-ray diffraction diffraction, UV–vis spectroscopy, scanning electron microscope (SEM), particle size distribution, color coordinates determination, acid/alkali test, thermo gravimetric (TG) analysis and CIE–1976 L*a*b* color scales. Among the various lanthanide ions and calcium ion as dopant, the pigment composition shows various hues ranges from green to yellow. The designed pigments consist of non–toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates like PMMA.

Findings

The present investigations establish that various color hues can be achieved by the incorporation of suitable chromophore metal ions like calcium in various rare earth host lattice by tuning of the band gaps. The coloring mechanism is based on the strong absorption of the pigments in the blue and red regions due to electronic transitions of the micro states of rare earth ion. The pigment composition shows various hues ranges from green to yellow. The coloring mechanism is based on the tuning of band gap by the dopant like calcium in various rare earth host lattice. In addition, this pigment was chemically and thermally stable. Finally, it has applied in plastics like PMMA.

Research limitations/implications

Mechanism of the color appearance using band calculations and on possible applications of rare earth phosphate powders as pigments in plastics and paints have not been explored much. However, the properties of the Ca-doped rare earth phosphate implies that this material has a potential to be applied as a satisfactory pigment for coating or coloring except for glaze, which may cause a side reaction at high temperatures, especially taking into consideration the economics and ecologies. The possibility of Ca2+ incorporation in CePO4 with monazite structure-type has been established.

Practical implications

The designed pigments consist of non-toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates. Thus, the present environmental friendly pigment powders may find potential alternative to the classical toxic inorganic pigments for various applications.

Social implications

There is a strong incentive to design new colorants based on inorganic materials to substitute for industrial pigments that are based on heavy elements hazardous to health and the environment. However, several industrial yellow pigments such as cadmium yellow (CdS), chrome yellow (PbCrO4) and nickel titanium yellow (TiO2-NiO-Sb2O3) contain the harmful elements (e.g. Cd, Pb, Cr and Sb) for the human body as well as the environment. The designed pigments consist of non-toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates. Thus, the present environmental friendly pigment powders may find potential alternative to the classical toxic inorganic pigments for various applications.

Originality/value

There is a strong incentive to design new colorants based on inorganic materials to substitute for industrial pigments that are based on heavy elements hazardous to health and the environment. However, several industrial yellow pigments such as cadmium yellow (CdS), chrome yellow (PbCrO4) and nickel titanium yellow (TiO2-NiO-Sb2O3) contain the harmful elements (e.g. Cd, Pb, Cr and Sb) for the human body as well as the environment. So, the authors have developed new class of inorganic pigments that are both non-toxic and environmentally unimpeachable, while preserving or even exceeding the optical, thermal and chemical characteristics of the existing commercial pigments. The developed colorants find practical applications in polymer matrix like PMMA.