Taking a fresh look at optical crowding of TiO2: the role of nanocarbonate as synergistic optical extender

Abstract

The light scattering potential of titanium dioxide (TiO2) is maximized when the TiO2 particles are correctly spaced in relation to the size of the particles, their spacing distance and the refractive index contrast with the surrounding medium. Nanoparticle extenders are claimed to improve TiO2 spacing due to the small particles acting to separate larger TiO2 particles (void size in respect to the separation of the surfaces ∼0.2 µm) and so preventing the TiO2 particles from reaching optical crowding. This concept has been challenged by previous work (Diebold 2011 J. Coat. Technol. Res. 8 541–52) using a combination of Monte Carlo simulations and image analysis techniques. Surprisingly in the light of traditional interpretations, the results showed that nanoparticles did not, in fact, space TiO2 particles under any conditions examined. Instead, TiO2 distributions and spacings were completely indifferent to the presence of smaller particles. This current paper undertakes to study why in certain cases extenders do in fact deliver significant synergy allowing TiO2 levels to be reduced in practice. The use of nano-calcium carbonate is demonstrated to provide a wide range of synergistic extension of TiO2 when in combination with synthetic latex binder, but, as found in the previous theoretical work, only a limited synergistic range in direct pigment packing studies using slurry pigment mixes only. A schematic model of the action of calcium carbonate containing a high nanoparticle fraction in the presence of binder is proposed, and is related to a combination of the potential reduction of contact between latex and TiO2 related to an increase in effective pigment volume fraction and surface area as well as the potential for differential flocculation. This model is supported by electron microscopy images and a measure of the ‘hardness’ of the skeletal elements making up the coating structure, determined via the bulk modulus using mercury intrusion porosimetry, enabling the effective incompressible pigment volume fraction in relation to compressible binder to be identified.