非晶前体介导的无镁白钨矿的形成

Toshiisa Konishi, Sadayuki Watanabe
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摘要

磷酸钙(CPs)作为人工骨移植替代物被广泛应用。然而,尽管这些因素会影响CP材料的物理化学性质,但对CP材料的粒度和形态的控制尚未得到实质性的实现。最近的研究表明,在N,N-二甲基甲酰胺(DMF)和乙二醇(EG)的有机溶剂中,采用沉淀法合成了一种结构类似于β-磷酸三钙高温多晶的纳米结构均匀的无mg whitlockite (WH)。因此,本研究旨在通过溶剂热反应在DMF-EG二元溶剂中合成WH颗粒,研究WH颗粒的形成机理。非晶态前驱体在3 h发生成核,主要受有机磷酸盐的缓慢水解影响,延迟了达到临界过饱和度,阻碍了快速成核。对反应时间对氢质酸生成影响的研究表明,在反应时间4 ~ 9 h之间,非晶前驱体通过固-固相变介导氢质酸生成。(2021年3月19日收稿;2021年4月13日录用)
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AMORPHOUS-PRECURSOR MEDIATED FORMATION OF MAGNESIUM-FREE WHITLOCKITE
Calcium phosphates (CPs) were widely used as synthetic bone graft substitutes. However, the control of particle size and morphology of CP materials have not been achieved substantially, even though these factors would influence the physicochemical properties. Recent studies revealed that a uniform nanostructured Mg-free whitlockite (WH), which was structurally similar to a high temperature polymorph of β-tricalcium phosphate, was synthesized by precipitation in organic solvents of N,N-dimethylformamide (DMF) and ethylene glycol (EG). The present study therefore aims to synthesize WH particles in the DMF-EG binary solvents by a solvothermal reaction to investigate the formation mechanism of the WH particles. The nucleation of the amorphous precursor, which occurred at 3 h, was dominated by the slow hydrolysis of organophosphate, which retarded reaching critical supersaturation and hindered the fast nucleation. The investigation on the effect of reaction time on WH formation revealed that the amorphous-precursor mediated WH formation via a solid-solid phase transformation occurred between 4 and 9 h of reaction time. (Received Mar 19, 2021; Accepted Apr 13, 2021)
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