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Calcium phosphate cements (CPCs) are commonly used as bone void fillers and to reinforce hardware in fracture repair. They are injectable, mouldable and self-setting in vivo, and in addition to being osteoconductive they can also be both bioactive and resorbable, which makes them interesting as bone regenerative biomaterials. The cement sets through a dissolution–precipitation process, and cement hardening occurs via the entanglement of the precipitated crystals. This type of setting reaction leads to an intricate microstructure, ranging from the nano- to the micrometre scale. Moreover, different types of porogens can be added to the cement paste, which changes the macrostructure of the hardened material. This chapter provides an overview of the structural organisation of CPCs at different length scales, which parameters influence it and also how this affects the characteristics of the cement. The structure and the porosity of the cement are dependent on the chemistry behind the setting reaction, as well as the size and size distribution of the starting powders, the choice of aqueous solution and the liquid-to-powder ratio. The structure of the cement, in turn, influences several important parameters of the cement. The microstructure can be correlated to the surface area, where a change in which affects both the resorbability and the bioactivity of the material. The mechanical properties of the cement can not only be strongly correlated to the structure and the porosity of the cement, but also to the efficacy of the crystal entanglement. Furthermore, CPCs can be used as drug delivery systems, where the structure of the cement influences both the amount of drug that can be loaded as well as the release rate.

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