Abstract
The principles of developing calcium phosphate cements (CPCs) for replacement and regeneration of bone tissue are considered. The basic classification of CPCs is given according to the phase composition of the reaction products in the setting systems. Processes of phase composition and development of microstructure and properties are discussed. Injectable CPC compositions are considered, and the factors affecting the injectability, as well as the ways to modify the cement pastes to improve their properties, are discussed. The results of research and development in the field of composite CPCs, including those reinforced by disperse phases, are described. In the final part of the review, some data on commercial CPCs and their biological behavior are presented.
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Hench, L.L. and Polak, J.M., Third-Generation Biomedical Materials, Science, 2002, vol. 295, pp. 1014–1017.
Barinov, S.M., Ceramic and Composite Materials Based on Calcium Phosphate for Medicine, Usp. Khim., 2010, vol. 79, no. 1, pp. 15–30.
Barinov, S.M. and Komlev, V.S., Calcium phosphate based bioceramics for bone tissue engineering, Zuerich: Trans. Tech., 2008.
Komath, M. and Varma, H.K., Development of a Fully Injectable Calcium Phosphate Cement for Orthopedic and Dental Applications, Bull. Mater. Sci., 2003, vol. 26, no. 3, pp. 415–422.
LeGeros, R.Z., Chahayeb, A., and Shulman, A., Apatite Calcium Phosphates: Possible Dental Restauration Materials, J. Dent. Res., 1982, vol. 61, pp. 343–347.
Brown, W.E. and Chow, L.C., A New Calcium Phosphate, Water Setting Cement, Cements Research Progress, Brown, W.E., Ed., Ohio: American Ceramics Society, 1987, pp. 352–379.
Chow, L.C. and Takagi, S., A Natural Bone Cement — A Laboratory Novelty Led To the Development of Revolutionary New Biomaterials, J. Res. Natl. Inst. Stand. Technol., 2001, vol. 106, pp. 1029–1033.
Albee, F. and Morrison, H., Studies in Bone Growth: Triple Calcium Phosphate as a Stimulus to Osteogenesis, Ann. Surg., 1920, vol. 71, pp. 32–38.
Brown, W.E., Environmental Phosphorus Handbook, New York: Willey and Sons, 1973, ch. 10, pp. 203–239.
Chow, L.C., Next Generation Calcium Phosphate-Based Biomaterials, J. Dent. Mater., 2009, vol. 28, no. 1, pp. 1–10.
Bohner, M., Design of Ceramic-Based Cements and Putties for Bone Graft Substitutions, Eur. Cells and Mater., 2010, vol. 20, pp. 1–12.
Dorozhkin, S.V., Calcium Orthophosphate Cements and Concretes, Materials, 2009, vol. 2, pp. 221–291.
Barinov, S.M. and Komlev, V.S., Biokeramika na osnove fosfatov kal’tsiya (Biokeramics Based on Calcium Phosphates), Moscow: Nauka, 2005.
Bohner, M., Reactivity of Calcium Phosphate Cements, J. Mater. Chem., 2007, vol. 17, pp. 3980–3986.
Am. Natl. Stand. Inst., Am. Dent. Assoc., Specification no. 6: Zinc Polycarboxylate Cement, J. Am. Dent. Assoc. 1980, vol. 101, pp. 669–671
Kopeikin, V.A., Petrova, A.P, and Rashkovan, I.L., Materialy na osnove metallofosfatov (Materials Based on Metallic Phosphates), Moscow: Khimiya, 1976.
Bigi, A., Panzavolta, S., and Rubini, K., Setting Mechanism of a Biomimetic Bone Cement, Chem. Mater., 2004, vol. 16, no. 19, pp. 3740–3745.
Rau, J.V., Fosca, Ì., Komlev, V.S., Fadeeva, I.V., Albertini, V.R., and Barinov, S.M., In Situ Time-Resolved Studies of Octacalcium Phosphate and Dicalcium Phosphate Dihydrate in Simulated Body Fluid: Co-Operative Interactions and Nanoapatite Crystal Growth, Cryst. Growth and Design, 2010, vol. 10, pp. 3824–3834.
Martin, R.I., TenHuissen, K.S., Leamy, P., and Brown, P.W., Enthalpies of Formation of Compounds in the P2O5-CaO-H2O System, J. Phys. Chem. B, 1997, vol. 101, pp. 9375–10379.
Lemaitre, J., Mirtchi, A.A., and Mortier, A., Calcium Phosphate Cements for Medical Use: State of the Art and Perspectives of Development, Silic. Ind, 1987, vol. 9–10.
Bohner, M., Lemaitre, J., and Ring, T.A., Effects of Sulfate, Pyrophosphate and Citrate Ions on the Physiochemical Properties of Cements Made of β-Tricalcium Phosphate — Phosphoric Acid — Water Mixtures, J. Am. Ceram. Soc., 1996, vol. 79, pp. 1427–1434.
Smirnov, V.V., Rau, J.V., Generosi, A., Rossi Albertini, V., Ferro, D., and Barinov, S.M., Elucidation of Real-Time Hardening Mechanism of Two Novel High-Strength Calcium Phosphate Bone Cements, J. Biomed. Mater. Res. B, 2009, vol. 93B, pp. 74–83.
Generosi, A., Smirnov, V.V., Rau, J.V., Rossi Albertini, V., Ferro, D., and Barinov S.M. Phasec Development in the Hardening Process of Two Calcium Phosphate Bone Cements: An Energy Dispersive X-Ray Diffraction Study, Mater. Res. Bull., 2008, vol. 43, pp. 561–571.
Smirnov, V.V., Barinov, S.M., Ievlev, V.M., Ferro, D., and Fedotov, A.Yu., Calcium Phosphate Bone Cement, Perspektivnye Materialy, 2008, no. 1, pp. 26–30.
Fadeeva, I.V., Barinov, S.M., Komlev, V.S., Fedotov, D.A., Durisin, J., and Medvecky, L., Apatite Formation in the Reaction-Setting Mixture of Ca(OH)2-KH2PO4 System, J. Biomed. Mater. Res, 2004, vol. 70A, no. 2, pp. 303–308.
Rodriguez-Lorenzo, L.M. and Vallet-Regi, M., Controlled Crystallization of Calcium Phosphate Apatites, Chem. Mater., 2000, vol. 12, pp. 2460–2465.
Fernandez, E., Planell, J.A., and Best, S.M., Precipitation of Carbonated Apatite in the Cement System Ca3(PO4)2-Ca(H2PO4)2-CaCO3, J. Biomed. Mater. Res, 1999, vol. 47, pp. 466–471.
Miyatomo, Y., Toh, T., Ishikawa, K., and Yuasa, T., Effect of Added NaHCO3 on the Basic Properties of Apatite Cement, J. Biomed. Mater. Res, 2001, vol. 54, pp. 311–319.
Bohner, M., Malsy, A.K., Camire, C.L., and Gbureck, U., Combining Particle Size Distribution and Isothermal Calorimetry Data to Determine the Reaction Kinetics of α-Tricalcium Phosphate — Water Mixtures, Acta Biomater., 2006, vol. 2, pp. 343–348.
Fernandez, E., Ginebra, M.P., Boltong, M.G., Driessens, F.C.M., Ginebra, J., de Maeyer, E.A.P., Verbeeck, R.M.H., and Planell, J.A., Kinetic Study of the Setting Reaction of a Calcium Phosphate Bone Cement, J. Biomed. Mater. Res, 1996, vol. 32 P, pp. 367–374.
Liu, Ch., Shen, W., Gu, Y., and Hu, L., Mechanism of the Hardening Process for a Hydroxyapatite Cement, J. Biomed. Mater. Res, 1997, vol. 35, pp. 75–80.
Kenny, S.M. and Burggy, M., Bone Cements and Fillers: a Review, J. Mater. Sci. Mater. Med., 2003, vol. 14, pp. 923–938.
TenHuisen, K.S., and Brown, P.W., Variations in Solution Chemistry during Calcium Deficient and Stoichiometric Hydroxyapatite Formation from CaHPO4 · 2H2O and Ca4(PO4)2O, J. Biomed. Mater. Res., 1997, vol. 36, pp. 233–241.
LeGeros, R.Z., Calcium Phosphate-Based Osteoinductive Materials, Chem. Rev., 2008, vol. 108, pp. 4742–4753.
Gurin, A.N., Komlev, V.S., Fadeeva, I.V., and Barinov, S.M., Oktacalcium Phosphate as a Precursor of Biological Mineralization, an Advanced Osteoplastic Material, Stomatologiya, 2010, no. 4, p.57.
Barinov, S.M. and Komlev, V.S., Osteoinductive Ceramic Materials for Repairing Bone Tissue: Octacalcium Phosphate, Materialovedenie, 2009, no. 10, pp. 34–41.
Kamakura, S., Sasano, Y., Homma, H., Suzuki, O., Kagayama, M., and Motegi, K., Implantation of Octacalcium Phosphate (OCP) in Rat Skull Defects Enhances Bone Repair, J. Dent. Res., 1999, vol. 78, pp. 1682–1687.
Dekker, R.J., de Bruijn, J.D., Stigter, M., Barrere, F., Layrolle, P., and van Blitterswijk, C.A., Bone Tissue Engineering on Amorphous Carbonated Apatite and Crystalline Octacalcium Phosphate Coated Titanium Discs, Biomaterials, 2005, vol. 26, pp. 5231–5239.
Bermudez, O., Boltong, M.G., Driessens, F.C.M., and Planell J.A., Development of an Octacalcium Phosphate Cement, J. Mater. Sci. Mater. Med., 1994, vol. 5, pp. 144–150.
Komlev, V.S., Fadeeva, I.V., Gurin, A.N., Shvorneva, L.I., Bakunova, N.V., and Barinov, S.M., New Calcium Phosphate Cements based on Tricalcium Phosphates, Dokl. Chem, 2011, vol. 437, no. 1, pp. 75–78.
Komlev, V.S., Fadeeva, I.V., Barinov, S.M., Rau, J.V., Fosca, M., Gurin, A.N., and Gurin, N.A., J. Biomater. Appl., (in press).
Komlev, V.S., Fadeeva, I.V., Fomin, A.S., Shvorneva, L.I., Barinov, S.M., and Ferro, D., Synthesis of Octacalcium Phosphate by Precipitation from Solution, Dokl. Chem., 2010, vol. 432, no. 2, pp. 178–182.
Sena, M., Yamashita, Y., Nakano, Y., Ohgaki, M., Nakamura, S., Yamashita, K., and Takagi, Y., Octacalcium Phosphate-Based Cement as a Pulp-Capping Agent in Rats, Oral. Serg. Oral Med. Oral Pathol. Oral Radiol. Endod., 2004, vol. 97, pp. 749–755.
Generosi, A., Rau, J.V., Komlev, V.S., Albertini, V.R., Fedotov, A.Yu., and Barinov, S.M., Anomalous Hardening Behavior of a Calcium Phosphate Bone Cement, J. Phys. Chem. B, 2010, vol. 114, pp. 973–979.
Rau, J.V., Generosi, A., Komlev, V.S., Fosca, M., Barinov, S.M., and Albertini, V.R., Real-Time Monitoring of the Mechanism of Poorly Crystalline Apatite Cement Conversion in the Presence of Chitosan, Simulated Body Fluid and Human Blood, Dalton Transactions, 2010, vol. 39, pp. 11412–11423.
Lewis, G., Injectable Bone Cements for Use in Vertebroplasty and Kyphoplasty: State-of Art Review, J. Biomed. Mater. Res. B, 2006, vol. 76B, pp. 456–468.
Bigi, A., Bracci, B., and Panzavolta, S., Effect of Added Gelatin on the Properties of Calcium Phosphate Cement, Biomaterials, 2004, vol. 25, pp. 2893–2899.
Carey, L.E., Xu, H.H.K., Simon, Jr.C.G., Takagi, S., and Chow, L.C., Premixed Rapid-Setting Calcium Phosphate Composites for Bone Repair, Biomaterials, 2005, vol. 26, pp. 5002–5014.
Skryabin, K.G., Vikhoreva, G.A., and Varlamov, V.P., Khitin i khitozan: Poluchenie, svoistva i primenenie (Chitin and Chitosan: Formation, Properties and Application), Moscow: Nauka, 2002.
Rau, J.V., Generosi, A., Smirnov, V.V., Ferro, D., Rossi Albertini, V., and Barinov, S.M., Energy Dispersive X-Ray Diffraction Study of Phase Development During Hardening of Calcium Phosphate Bone Cements with Addition of Chitosan, Acta Biomater., 2008, vol. 4, pp. 1089–1094.
Bohner, M., Calcium Orthophosphates in Medicine, from Ceramics to Calcium Phosphate Cements, Injury, 2000, vol. 3.
Takagi, S. and Chow, L., Formation of Macropores in Calcium-Phosphate Cement Implants, J. Dent. Res. SI., 1995, vol. 74, p.559.
Barralet, J.E., Grover, L., Gaunt, T., Wright, A.J., and Gibson, I.R., Preparation of Macroporous Calcium Phosphate Cement Tissue Engineering Scaffolds, Biomaterials, 2002, vol. 23, pp. 3063–3072.
Tas, A.C., Preparation of Porous Apatite Granules from Calcium Phosphate Cement, J. Mater. Sci. Mater. Med., 2008, vol. 19, pp. 2231–2239.
Habraken, W.J.E.M., de Jonge, L.T., Wolke, J.G.C., Yubao, L., Mikos, A.G., and Jansen, J.A., Introduction of Gelatin Microspheres Into An Injectable Calcium Phosphate Cement, J. Biomed. Mater. Res. A, 2008, vol. 87, pp. 643–655.
Markovic, M., Takagi, S., and Chow, L.C., Formation of Macropores in Calcium Phosphate Cements through the Use of Mannitol Crystals, Key Eng. Mater., 2001, vols. 192–195, pp. 773–776.
Takagi, S. and Chow, L.C., Formation of Macropores in Calcium Phosphate Cement Implants, J. Mater. Sci. Mater. Med., 2001, vol. 12, pp. 135–139.
Smirnov, V.V., Porous Cements to Fill Defects in Bone Tissue, Materialovedenie, 2009, no. 8, pp. 16–19.
Khairoun, I., Boltong, M.G., Driessens, F.C.M., and Planell, J.A., Some Factors Controlling the Injectability of Calcium Phosphate Bone Cements, J. Mater. Sci. Mater. Med., 1998, vol. 9, pp. 425–428.
Bohner, M. and Baroud, G., Injectability of Calcium Phosphate Pastes, Biomaterials, 2005, vol. 26, pp. 1553–1563.
Leroux, L., Hatim, Z., Freche, M., and Lacout, J.L., Effects of Various Adjuvants (Lactic Acid, Glycerol and Chitosan) on the Injectability of a Calcium Phosphate Cement, Bone, 1999, vol. 25, no. 2, pp. 31–34.
Gbureck, U., Barralet, J.E., Spatz, K., and Grover, L.M., Ionic Modification of Calcium Phosphate Cement Viscosity. Part I: Hypodermic Injection and Strength Improvement of Apatite Cement, Biomaterials, 2004, vol. 25, pp. 2187–2195.
Gbureck, U., Dembski, S., Thull, R., and Barralet, J.E., Factors Influencing Calcium Phosphate Cement Shelf-Life, Biomaterials, 2005, vol. 26, pp. 3691–3697.
Xu, H.H.R., Carey, L.E., Simon, Jr. C.G., Takagi, S., and Chow, L.C., Premixed Calcium Phosphate Cements: Synthesis, Physical Properties, and Cell Cytotoxicity, Dental Mater., 2007, vol. 23, no. 4, pp. 433–441.
Smirnov, V.V., Egorov, A.A., Barinov, S.M., and Shvorneva, L.I., Composite Calcium Phosphate Bone Cements Reinforced by Particulate Titanium, Dokl. Chem., 2007, vol. 413, no. 2, pp. 82–85.
Barinov, S.M. and Shevchenko, V.Ya., Prochnost’ tekhnicheskoi keramiki (Strength of Engineering Ceramics), Moscow: Nauka, 1996.
Neira, I.S., Kolen’ko, Yu.V., Kommareddy, K.P., Manjubala, I., Yoshimura, M., and Guitian, F., Reinforcing of a Calcium Phosphate Cement with Hydroxyapatite Crystals of Various Morphologies, ASM Appl. Mater. Interfaces, 2010, vol. 2, no. 11, pp. 3276–3284.
Xu, H.H.K. and Quinn, J.B., Calcium Phosphate Cement Containing Resorbable Fibers for Short-Term Reinforcement and Macroporosity, Biomaterials, 2002, vol. 23, pp. 193–202.
Egorov, A.A., Smirnov, V.V, and Barinov, S.M., Effect of Titanium Particle Sizes on Mechanical Properties of Bone Calcium Phosphate Cements, Materialovedenie, 2011, no. 1, pp. 11–14.
Egorov, A.A., Reinforcing of Calcium Phosphate Cements for Medical Use, Perspektivnye Materialy, 2008, no. 5, pp. 297–300.
Duracan, C. and Brown, P.W., Calcium-Deficient Hydroxyapatite-PGLA Composites: Mechanical and Microstructural Investigation, J. Biomed. Mater. Res., 2000, vol. 51, no. 4, pp. 726–734.
Majekodunmi, A.O., Deb, S., and Nicholson, J.W., Effect of Molecular Weight and Concentration of Poly (Acrylic Acid) on the Formatiom of a Polymeric Calcium Phosphate Cement, J. Mater. Sci. Mater. Med., 2003, vol. 14, pp. 747–752.
Xu, H.H.R., Takagi, S., Sun, L., Hussain, L., Chow, L.C., Guthrie, W.F., and Yen, J.H., Development of Nonrigid, Durable Calcium Phosphate Cement for Use in Periodontal Bone Repair, J. Am. Dent. Assoc., 2006, vol. 137, pp. 1131–1138.
Miyazaki, K., Horibe, T., Antonucci, J.M., Takagi, S., and Chow, L.C., Polymeric Calcium Phosphate Cements: Analysis of Reaction Products and Properties, Dental Mater., 1993, vol. 9, no. 1, pp. 46–50.
Khashaba, R.M., Moussa, M.M., Mettenburg, D.J., Rueggeberg, F.A., Chutkan, N.B., and Borke, J.L., Polymeric-Calcium Phosphate Cement Composites — Material Properties: in Vitro and in Vivo Investigation, Int. J. Biomater., 2010. doi 10.1155/2010/691452
Ikenaga, M., Hardouin, P., Lemaitre, J., Andrianjavoto, H., et al., Biomechanical Characterization of a Biodegradable Calcium Phosphate Hydraulic Cement: A Comparison with Porous Biphasic Calcium Phosphate Ceramics, J. Biomed. Mater. Res., 1998, vol. 40, pp. 139–144.
Ooms, E.M., Wolke, J.G.C., Ven Der Waerden, J.P.C.M., and Jansen, J.A., Trabecular Bone Response to Injectable Calcium Phosphate (Ca-P) Cement, J. Biomed. Mater. Res., 2002, vol. 61, pp. 9–18.
Yuan, H., Li, Y., de Bruijn, J.D., de Groot, K., et al., Tissue Responses of Calcium Phosphate Cement: a Study in Dogs, Biomaterials, 2000, vol. 21, pp. 1283–1290.
Hidaka, N., Yamano, Y., Kadoya, Y., and Nishimura, N., Calcium Phosphate Bone Cement for Treatment of Distal Radius Fractures: a Preliminary Report, J. Orthop. Sci., 2002, vol. 7, pp. 182–187.
Chaung, H.M., Hong, C.H., Chiang, C.P., et al., Comparison of Calcium Phosphate Cement Mixture and Pure Calcium Hydroxide as Direct Pulp-Capping Agents, J. Formos. Med. Assoc., 1996, vol. 95, pp. 545–550.
Gehrke, S.A., Junior, B.K., and Martins, N.M.B., Use of Bone Regeneration Cement for Bone Grafting in Atrophic Areasnclinical, Radiographic and Histological Analysis, Implants: Int. J. Oral Implantology, 2009, vol. 10, pp. 24–30.
Friedman, C.D., Costantino, P.D., Takagi, S., et al., Bone Source Hydroxyapatite Cement: a Novel Biomaterial for Craniofacial Skeletal Tissue Engineering and Reconstruction, J. Biomed. Mater. Res., 1998, vol. 43, pp. 428–432.
Baker, S., Weinzweig, J., Kirschner, R., et al., Applications of a New Carbonated Calcium Phosphate Bone Cement: Early Experience in Pediatric and Adult Craniofacial Reconstruction, Plast. Reconstr. Surg., 2002, vol. 109, pp. 1789–1796.
Stanton, D.C., Chou, J.C., and Carrasco, L.R., Injectable Calcium-Phosphate Bone Cement (Norian) for Reconstruction of a Large Mandibular Defect: a Case Report, J. Oral Maxillofac. Surg., 2004, vol. 62, pp. 235–240.
Lye, K., Tideman, H., Merkx, M., and Jansen, J., Bone Cements and Their Potential Use in a Mandibular Endoprosthesis, Tissue Eng., 2009, vol. 15, pp. 485–496.
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Barinov, S.M., Komlev, V.S. Calcium phosphate bone cements. Inorg Mater 47, 1470–1485 (2011). https://doi.org/10.1134/S0020168511130024
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DOI: https://doi.org/10.1134/S0020168511130024