湿化学法合成羟基磷灰石晶体及其表征
巫剑波,秦草坪,袁秋华,郭志威,刘家裕,邓庆威,张培新

深圳大学化学与环境工程学院,深圳 518060

无机仿生材料; 羟基磷灰石; 湿化学法; 水浴合成; 常温合成; 高结晶度和纯度; 晶体表征

Synthesis and characterization of hydroxyapatite crystals using wet chemistry methods
Wu Jianbo, Qin Caoping, Yuan Qiuhua, Guo Zhiwei, Liu Jiayu, Deng Qingwei, and Zhang Peixin

College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, P.R.China

inorganic biomimetic materials; hydroxyapatite; wet chemistry method; water bath synthesis; room temperature synthesis; high crystallinity and purity; crystal characterization

DOI: 10.3724/SP.J.1249.2015.05465

备注

采用湿化学法通过两种方案合成羟基磷灰石(hydroxyapatite,HA)晶体,一种方案是以Ca(NO3)2·4H2O和Na2HPO4作为原料,加入NaOH溶液调节pH值在10.5～11.0之间,不添加分散剂,在40 ℃水浴条件下合成羟基磷灰石; 另一方案是在室温下(25 ℃)进行,在其他条件不变的情况下,以CaCl2·2H2O为钙源、乙醇胺作为分散剂合成羟基磷灰石.将两种方案合成的样品分别通过X射线衍射(X-ray diffraction, XRD)、傅里叶变换红外光谱(Fourier transform infrared spectroscopy, FTIR)、扫描电子显微镜(scanning electron microscopy, SEM)、X射线能量色散仪(energy-dispersive X-ray spectroscopy, EDX)、热重-差热分析和X射线光电子能谱(X-ray photoelectron spectroscopy, XPS)进行表征.XRD和FTIR结果显示,合成的两种HA粉末都具有较高结晶度和纯度.SEM分析表明,第1种方案可合成直径为30～50 nm,长50～150 nm的棒状晶体; 第2种方案则可制备粒径约100～150 nm的球状(或椭球状)晶体.热分析表明,所制备的HA在1 000 ℃范围内有显著的热稳定性.XPS和EDX分析则证实HA由Ca、P和O等元素组成,两种方案中钙和磷的摩尔比分别是1.60和1.63.

Hydroxyapatite(HA)crystals were synthesized by two new wet chemistry methods. The first method was carried out by using calcium nitrate tetrahydrate and disodium hydrogen phosphate as starting materials and adding sodium hydroxide to ensure the pH value ranging from 10.5 to 11.0 under 40 ℃ water bath with no dispersant. For the other method, hydroxyapatite was synthesized at room temperature(25 ℃)with calcium chloride dehydrate as calcium source and ethanolamine as dispersing agent, while other conditions remained the same as those in the first method. The obtained samples were characterized by X-ray diffraction(XRD), fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM)coupled with energy-dispersive X-ray spectroscopy(EDX), thermogravimetric analysis-differential thermal analysis(TG-DTA), and X-ray photoelectron spectroscopy(XPS), respectively. The XRD and FTIR results exhibit that the synthesized HA has a high crystallinity and purity. The SEM images reveal that rod-like HA crystals with a diameter of 30-50 nm and a length of 50-150 nm are formed by using the first method, while spherical or ellipsoidal HA crystals with a diameter of 100-150 nm around can be obtained through the second method. The thermal analysis shows that the synthesized HA has a remarkable heat stability up to 1 000 ℃,and the XPS and EDX studies indicate that HA samples are predominantly composed of elements including calcium(Ca), phosphorous(P), oxygen(O), etc. The ratios of Ca and P of HA samples in the first and the second methods are equal to 1.60 and 1.63, respectively.

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