Hydroxyapatite (HAP) was mineralized in poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAA) complex hydrogel immersed in a salt solution containing PAA. The transparent HAP/polymer composite swelled in water depending on the HAP content; high HAP content gave small swelling and vice versa. The HAP content reached about 80 wt % at most. Observation of the cross section of the composite by energy-dispersive analysis of X-ray (EDAX) revealed that the composite consisted of two phases, i.e., a hard HAP-rich phase and a soft polymer-rich phase. In the HAP-rich phase, the space inside the hydrogel was occupied by HAP, while HAP was not mineralized in the polymer-rich phase. The nucleation seemed to take place, at first, at the middle depth of the hydrogel where the HAP-rich phase was formed. The HAP-rich phase grew its size toward the surface of the hydrogel at the cost of the polymer-rich phase. The presence of phosphorus, P, in the polymer-rich phase indicated the adsorption of HPO(4)(2-) on the polymer chain of the hydrogel via hydrogen bonding, accompanied with Ca(2+) because of electrostatic constraints. This adsorption of ions in addition to Donnan distribution of ions leads to the formation of a hypercomplex that can be regarded as a precursor of the HAP-rich phase. The change of the hypercomplex into the HAP-rich phase is discontinuous and hence concluded as a phase transition. By comparison of our mineralization system with the biomineralization system of HAP and CaCO(3), the physicochemical mechanism of the mineralization process in the present system was found to be similar to that in biological systems. In this sense, we termed the present system an artificial biomineralization system.

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Several kinds of hydrogels were prepared as mimics for the collagen/acidic protein hydrogel employed as the polymer matrix for mineralization in natural bone formation. The hydrogels prepared as mineralization matrices were employed for synthesizing artificial bones. The artificial bone made from a network of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) prepared by heating (PVA/PAA-h-network) exhibited mechanical properties comparable with those of fish scales. To elucidate the formation mechanism of the artificial bone, we synthesized four further kinds of matrix. Artificial bones were obtained from both a PVA/PAA network prepared by repeated freezing and thawing (PVA/PAA-ft-network) and a chitosan/PAA network, in which hydrogen bonding exists between the two constituent polymers, similar to that observed in a natural collagen/acidic protein network. The artificial bone made from the chitosan/PAA network was confirmed to be formed by the phase transformation of a cartilaginous precursor by a process similar to the transformation of cartilaginous tissue to natural bone. In addition, skeletal phase material, i.e., a homogeneous solid phase of hydroxyapatite/polymers, was formed in the cartilaginous phase, i.e., the hypercomplex gel. The skeletal phase grew thicker at the expense of the cartilaginous phase until it formed the entirety of the composite. Artificial bones were also obtained from a gelatin/PAA network and a poly[N-(2-hydroxyethyl)acrylamide]-co-(acrylic acid) network. These experimental results suggested that the coexistence of proton donor and proton acceptor functions in the hydrogel is a key factor for bone formation. The hydroxyapatite content of our artificial bones was almost conterminous with those of natural bones.

CaCO 3 was mineralized from solutions supersaturated only by poly(acrylic acid) (PAA), without bubbling any CO 2 gas in the solution. For example, a layer of CaCO 3 was built up on the surface of a chitosan membrane from a supersaturated aqueous solution containing CaCl 2 , Na 2 CO 3 , and PAA. In this newly developed method, the PAA alone suppresses the precipitation of CaCO 3 from the bulk solution, and therefore, increases the supersaturated concentration. This concentration is estimated to be the same order as that attained in the method in which both CO 2 gas and PAA were used. At the same time, PAA supplies nucleation fields by forming a polymer complex with chitosan. The crystal system obtained was different from those obtained when using CO 2 gas. Self-organization of aragonite crystallites led to the formation of uniform, concentric, or branching patterns in the surface-domain structure. These patterns had morphologies similar to those discovered by other researchers, typically in the crystallization of ascorbic acid. Thicker layers of CaCO 3 could be formed on chitosan membranes, the surfaces of which had been converted to a polyelectrolyte complex (PEC) by exposure to PAA solution before the onset of mineralization. Under certain conditions, the CaCO 3 layer had a small spherical curvature, similar to a half-lens, and generated Newton's ring pattern from the interference fringes of visible light.

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