Bioinspired Mineralization of Inorganics from Aqueous Media Controlled by Synthetic Polymers

Abstract

The formation of inorganic structures in nature is commonly controlled by biogenic macromolecules. The understanding of mineralization phenomena and the nucleation and growth mechanisms involved is still a challenge in science but also of great industrial interest. This article focuses on the formation and mineralization of two archetypical inorganic materials: zinc oxide and amorphous calcium carbonate (ACC). Zinc oxide is selected as a model compound to investigate the role that polymers play in mineralization. Most of the effort has been devoted to the investigation of the effects of double-hydrophilic block and graft copolymers. Recent work has demonstrated that latex particles synthesized by miniemulsion polymerization, properly functionalized by various chemical groups, have similar effects to conventional block copolymers and are excellently suited for morphology control of ZnO crystals. Latex particles might serve as analogues of natural proteins in biomineralization. The second example presented, ACC, addresses the issue of whether this amorphous phase is an intermediate in the biomineralization of calcite, vaterite, or aragonite. Conditions under which amorphous calcium carbonate can be obtained as nanometer-sized spheres as a consequence of a liquid-liquid phase segregation are presented. Addition of specific block copolymers allows control of the particle size from the micrometer to the submicrometer length scale. The physical properties of novel materials synthesized from concentrated solution and their potential applications as a filler of polymers are also discussed.

Effect of Molecular Weights of Poly(acrylic acid) on Crystallization of Calcium Carbonate by the Delayed Addition Method

“…Small fraction of rhombohedral calcite was observed in the product of run 20 ( Figure 1d). It was found that the vaterite particles had a spherical shape with smooth surfaces for the early addition time (1 min), whereas the vaterite particles showed a spherical shape with rough surfaces and some irregularly shaped particles for the late addition time (3,20, and 60 min) in all the cases. In the previous report, we suggested that irregularly shaped particles and rough surfaces in the later addition might be caused by dissolution and recrystallization of the resulting vaterite particles before adding PAA-Na.…”

“…34 A 0.1 M CaCl 2 aqueous solution (adjusted to pH 8.5 with dilute aqueous NH 3 ) and a 0.1 M (NH 4 ) 2 CO 3 aqueous solution (adjusted to pH 10.0 with aqueous NH 3 ) were simultaneously injected via syringes into distilled water (adjusted to pH 8.5 with dilute aqueous NH 3 ). An aqueous solution of PAA-Na was then added into the reaction mixture after incubation at 30 C for several minutes (0, 1, 3, 20, or 60 min).…”

“…[1][2][3][4][5][6][7] Calcium carbonate (CaCO 3 ), one of the most abundant inorganic biominerals, exists as three anhydrous crystalline polymorphs (calcite, aragonite, vaterite), two hydrated metastable forms (monohydrocalcite and calcium carbonate hexahydrate), and an unstable amorphous phase. [8][9][10][11] In biomineralization process, a final crystalline phase might result from a multistage crystallization process, initiated by the formation of an amorphous precursor and crystalline intermediates that undergo subsequent phase transformations.…”

Early Age Hydration, Microstructure and Micromechanical Properties of Cement Paste Modified with Polymeric Vesicles

“…Therefore, amphiphilic copolymers are widely used in many industrial applications, e.g. templates for the preparation of inorganic nano-particles (Gorna et al 2007;Sun and Gutmann 2004), crystal growth modifiers (Rudloff et al 2002), electrolyte components for rechargeable batteries (Singh et al 2007), "vehicles" of active substances release (Khanal and Nakashima 2005;Kojima et al 2008), etc.…”

Biomimetic Polymers for Chiral Resolution and Antifreeze Applications

“…Therefore, the use of synthetic soluble hydrophilic polymers and polyelectrolytes is advantageous for achieving control over crystallization reactions. [26][27][28][29][30][31][32][33] The synthesis of bio-inspired soluble polymers for use as a soft template opens up the possibility to design polymeric model systems for the image. These molecules are non-superimposable and therefore are chiral.…”