Liu Y, Sethuraman G, Wu W, Nancollas GH, Grynpas M
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York, 14260
J Colloid Interface Sci. 1997 Feb 1;186(1):102-9. doi: 10.1006/jcis.1996.4621.
The kinetics of growth of crystals induced by hydroxyapatite (HAP) seed crystals in supersaturated solutions of fluorapatite and of fluorapatite (FAP) seed crystals in supersaturated solutions of hydroxyapatite have been studied using the constant composition method. The reactions were investigated at relative supersaturations ranging from sigmaFAP = 0.99 to 12.0 at pH 6.5 and for HAP, sigmaHAP = 3.6 to 12.6 at pH 7.4. In FAP-supersaturated solutions, this phase was nucleated at the HAP surfaces and underwent growth at a rate more than three times greater than that on FAP seed crystals of equivalent surface area. Transmission electron microscopy (TEM) and electron diffraction imaging clearly demonstrated that the new needle-like HAP phase originated at the FAP surface with the 002 planes of HAP growing on FAP. In contrast, the mutual orientation of FAP crystallization on HAP seed crystals could not be established. Interfacial energies of FAP, HAP, and octacalcium phosphate (OCP) microcrystals against aqueous solutions were obtained by using a thin-layer wicking technique. The interfacial energy values measured in pure aqueous solutions were 18.5, 9.0, and 4.3 mJ m-2 for FAP, HAP, and OCP, respectively. The much smaller value for OCP as compared with the other phases may explain why this phase has been so frequently implicated as a possible precursor to the formation of apatite, especially in biological mineralization reactions.
采用恒组成法研究了羟基磷灰石(HAP)籽晶在氟磷灰石过饱和溶液中以及氟磷灰石(FAP)籽晶在羟基磷灰石过饱和溶液中诱导晶体生长的动力学。在pH 6.5时,研究了相对过饱和度范围为σFAP = 0.99至12.0时FAP的反应,对于HAP,在pH 7.4时研究了σHAP = 3.6至12.6时的反应。在FAP过饱和溶液中,该相在HAP表面成核,其生长速率比同等表面积的FAP籽晶上的生长速率快三倍以上。透射电子显微镜(TEM)和电子衍射成像清楚地表明,新的针状HAP相起源于FAP表面,HAP的002面在FAP上生长。相反,无法确定FAP在HAP籽晶上结晶的相互取向。通过使用薄层芯吸技术获得了FAP、HAP和磷酸八钙(OCP)微晶与水溶液的界面能。在纯水溶液中测得的界面能值,FAP、HAP和OCP分别为18.5、9.0和4.3 mJ m-2。与其他相相比,OCP的值要小得多,这可能解释了为什么该相经常被认为是磷灰石形成的可能前体,尤其是在生物矿化反应中。