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Precipitation of calcium phosphates from electrolyte solutions

I. A study of the precipitates in the physiological pH region

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Abstract

Precipitation of slightly soluble calcium phosphates from aqueous solutions of calcium chloride (3×10−4M to 1×10−1M) and sodium phosphate (Ptot. 1×10−3M to 6×10−2M, [NaOH]/[H3PO4]∼1.75, pH 7.4) was studied at 25° and 37°. Precipitates isolated 24 hours after mixing were identified by means of light and electron microscopy, X-ray and electron diffraction, chemical analyses and refractive indices. Over the widest range of reactant concentrations at 25°, octacalcium phosphate was predominantly formed, while at 37°, calcium deficient apatites were obtained. At the latter temperature OCP separated at very low concentration products only, i.e. at the precipitation boundary. At relatively high concentration products (Catot.×Ptot.>10−4) and at both temperatures, mixtures of dicalcium phosphate dihydrate (DCPD) and apatites were obtained, the concentration region decreasing with increasing temperature.

Résumé

La précipitation de phosphates de calcium, peu solubles, à partir de solutions de chlorure de calcium (3×10−4M à 1×10−1M) et de phosphate de sodium (Ptot. 1×10−3M à 6×10−2M, [NaOH]/[H3PO4]∼1.75, pH 7.4), est étudiée à 25° et à 37°. Les précipités, obtenus 24 heures après mélange, sont identifiés par microscopie optique et électronique, par diffraction électronique et aux rayons X, par analyses chimiques et par leurs indices de réfraction. Dans un large éventail de concentrations des réactifs à 25°, c'est surtout du phosphate octocalcique qui se forme, alors qu'à 37°, on obtient des apatites déficients en calcium. A cette dernière température, l'OCP se différencie seulement à des concentrations faibles, à la limite de précipitation. A des concentrations relativement élevées (Catot.×Ptot.>10−4)et aux deux températures, des mélanges de dihydrate de phosphate dicalcique (DCPD) et d'apatites sont obtenus, la zone de concentration diminuant avec l'augmentation de la température.

Zusammenfassung

Die Ausfällung von schwer löslichen Calciumphosphaten aus wäßrigen Calciumchloridlösungen (3×10−4M bis 1×10−1M) und Natriumphosphatlösungen (Ptot. 1×10−3M bis 6×10−2M, [NaOH]/H3PO4]∼1,75, pH 7,4) wurde bei 25° und bei 37° untersucht. Niederschläge, welche 24 Stunden nach dem Mischen isoliert wurden, konnten mittels Licht- und Elektronenmikroskopie, Röntgenstrahlen und Elektronendiffraktion, chemischen Analysen und Refraktions-Indices identifiziert werden. Über den weitesten Konzentrationsbereich der Versuchssubstanzen wurde bei 25° hauptsächlich Octocalciumphosphat gebildet, während bei 37° calciumarme Apatite entstanden. Bei der letztgenannten Temperatur fiel das OCP nur bei niedrigen Konzentrationsprodukten aus, d.h. an der Ausfällungsgrenze. Bei relativ hohen Konzentrationsprodukten (Catot.×Ptot.>10−4) und bei beiden Versuchstemperaturen wurden Gemische von Dicalciumphosphatdihydrat (DCPD) und Apatiten erhalten, indem der Konzentrationsbereich bei zunehmender Temperatur abnimmt.

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Authors and Affiliations

  1. Department of Physical Chemistry, Institute “Rudjer Bošković”, P. O. Box 1016, Zagreb, Croatia, Yugoslavia

    H. Füredi-Milhofer, B. Purgarić, Lj. Brečević & N. Pavković

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  1. H. Füredi-Milhofer
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  2. B. Purgarić
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  3. Lj. Brečević
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  4. N. Pavković
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Füredi-Milhofer, H., Purgarić, B., Brečević, L. et al. Precipitation of calcium phosphates from electrolyte solutions. Calc. Tis Res. 8, 142–153 (1971). https://doi.org/10.1007/BF02010131

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