First-principles modeling combined with experimental methods were used to study hydroxyapatite in which Sr2+ is substituted for Ca2+. Detailed analyses of cation-oxygen bond distributions, cation-cation distances, and site 1-oxygen polyhedron twist angles were made in order to provide an atomic-scale interpretation of the observed structural modifications. Density functional theory periodic band-structure calculations indicate that the Ca2+ to Sr2+ substitution induces strong local distortion on the hydroxyapatite lattice: the nearest neighbor Sr-O bond structures in both cationic sites are comparable to pure SrHA, while Sr induces more distortion at site 2 than site 1. Infrared vibrational spectroscopy (FTIR) and extended X-ray absorption fine structure (EXAFS) analysis suggest increasing lattice disorder and loss of OH with increasing Sr content. Rietveld refinement of synchrotron X-ray diffraction patterns shows a preference for the Ca1 site at Sr concentrations below 1 at.%. The ideal statistical occupancy ratio Sr2/Sr1=1.5 is achieved for approximately 5 at.%; for higher Sr concentrations occupation of the Ca2 site is progressively preferred.

SummaryAtomic Force Microscopy was employed in order to relate the features observed on the surface of a 50/70 asphalt binder according to its local stiffness and elastic recovery. Indentations were performed in different points of the surface and a significant variation of elasticity was observed between the points on the so-called bee structure and the matrix. Also, indentations varying the maximum force were performed on similar white spots in the bee structure and the recovery was followed up to 1 h after indentation. It was observed that the elastic recovery is very much dependent on the colloidal structure of the bee. The final surface state of the binder, close to the bee for usual bees is not the same as the initial one indicating severe plastic deformation. Also, permanent phase change could be observed for bright spots presented in not well-structured bee arrangements. A surface hardening was observed in the bee region.

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SummarySamples of unmodified and modified asphalt binders containing 1% polyphosphoric acid were studied. Fourier-transform infrared spectroscopy was used to evaluate the structural indices of the functional groups present in the samples and the results indicated there was a strong interaction between the polyphosphoric acid and oxygenated species. Contact angle measurements indicated that adhesion of the binder to the aggregate depended on the polyphosphoric acid content. Atomic force microscopy was used to relate features observed on the surface of the asphalt binder 50/70, with their local mechanical properties such as stiffness and elasticity. It was observed that the surface of the sample containing 1% polyphosphoric acid provides stiffness values lower than the unmodified asphalt binder.