水热制备锌、硅、镁、铁等元素掺杂羟基磷灰石及其表征

doi:10.15541/jim20200664

无机材料学报 ›› 2021, Vol. 36 ›› Issue (10): 1091-1096.DOI: 10.15541/jim20200664

水热制备锌、硅、镁、铁等元素掺杂羟基磷灰石及其表征

宋可可¹(), 黄浩², 鲁梦婕³, 杨安春², 翁杰¹^,²(), 段可⁴()

1.西南交通大学医学院, 成都610031
2.西南交通大学材料科学与工程学院, 材料先进技术重点实验室, 成都610031
3.西南医科大学附属医院病理科, 泸州 646000
4.西南医科大学附属医院骨与关节外科, 四川省骨科置入器械研发及应用技术工程实验室, 泸州 646000

收稿日期:2020-11-20 修回日期:2020-12-28 出版日期:2021-10-20 网络出版日期:2021-01-25
通讯作者: 翁杰, 教授. E-mail: jweng@swjtu.cn; 段可, 副教授. E-mail: keduan9@126.com
作者简介:宋可可(1996-), 女, 硕士研究生. E-mail: 793952151@qq.com
基金资助:
国家重点研发计划(2016YFB0700803);广东省重点领域研发计划项目(2019B010941002);国家自然科学基金(51572228);西南医科大学附属医院创业计划(19038)

Hydrothermal Preparation and Characterization of Zn, Si, Mg, Fe Doped Hydroxyapatite

SONG Keke¹(), HUANG Hao², LU Mengjie³, YANG Anchun², WENG Jie¹^,²(), DUAN Ke⁴()

1. College of Medicine, Southwest Jiaotong University, Chengdu 610031, China
2. Key Lab on Advanced Technologies of Materials (MOE), School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China
3. Pathology department, Affiliated Hospital of Southwest Medical University, Luzhou 646000, China
4. Sichuan Provincial Lab of Orthopaedic Engineering, Department of Orthopaedics, Affiliated Hospital of Southwest Medical University, Luzhou 646000, China

Received:2020-11-20 Revised:2020-12-28 Published:2021-10-20 Online:2021-01-25
Contact: WENG Jie, professor. E-mail: jweng@swjtu.cn; DUAN Ke, associate professor. E-mail: keduan9@126.com
About author:SONG Keke(1996-), female, Master candidate. E-mail: 793952151@qq.com
Supported by:
National Key Research and Development Program(2016YFB0700803);Research and Development Plan Projects in Key Fields of Guangdong Province(2019B010941002);National Natural Science Foundation of China(51572228);Entrepreneurship Plan of Affiliated Hospital of Southwest Medical University(19038)

摘要/Abstract

摘要：

微量元素掺杂是赋予羟基磷灰石材料更多生物学功能的一条有效途径, 但不同元素的掺杂行为尚待进一步揭示。本研究使用并行水热合成方式, 制备分别含有锌、硅、镁、铁、锰、铜、锶、硒、钴的9种羟基磷灰石粒子, 并对其物理化学特性进行研究。结果表明, 元素掺杂显著改变了羟基磷灰石粒子的形貌和晶体生长方向, 但不改变其物相组成和官能团。晶体的(211)和(112)晶面衍射峰的强度均降低, 结晶度下降。元素实际掺杂效率分析结果显示锰>锌>镁>铁(三价)>锶>钴>铜>硒>硅, 与元素的离子半径大小相关。锰、锌、镁三种元素掺杂量较高, 因其离子半径与其替代的钙离子接近。铜元素掺杂效率较低是由于其在合成溶液中与氨产生络合作用, 硅元素和硒元素则因几何结构和电荷(SiO₃^2-、SeO₃^2-/PO₄^3-)差异导致掺杂率低。本研究揭示了掺杂行为与离子特性之间的联系, 为功能化羟基磷灰石的设计和开发提供有益的参考基础。

关键词: 羟基磷灰石, 元素掺杂, 水热合成, 掺杂行为

Abstract:

Doping of trace elements is an effective way to endow hydroxyapatite with more biological functions. But the behaviors of different element doping remained to be further revealed. Here, nine kinds of hydroxyapatite particles containing zinc, silicon, magnesium, iron, manganese, copper, strontium, selenium, and cobalt, respectively, were prepared by parallel hydrothermal synthesis, and their physicochemical properties were studied. The results show that the morphology and crystal growth direction of hydroxyapatite particles are significantly changed, while the phase composition is maintained. The peak intensity of (211) and (112) plane diffraction peaks decreased, accompanied by decreased crystallinity. Analysis results show that the actual doping efficiency obeys the tendency of manganese > zinc > magnesium > iron (trivalent) > strontium > cobalt > copper > selenium > silicon. Among these elements, doping amounts of Mn, Zn and Mg are higher, because their ion radii are closed to that of Ca ²⁺. The low doping efficiency of copper is caused by its complexation with ammonia in synthetic solution, while silicon and selenium are caused by different geometry and charge of SiO₃^2-, SeO₃^2- from that of PO₄^3-. This study reveals the reasonable relationship between doping behavior and ion characteristics, providing a useful reference for design and development of functionalized hydroxyapatite.

Key words: hydroxyapatite, element doping, hydrothermal synthesis, doping behavior

中图分类号:

R318

宋可可, 黄浩, 鲁梦婕, 杨安春, 翁杰, 段可. 水热制备锌、硅、镁、铁等元素掺杂羟基磷灰石及其表征[J]. 无机材料学报, 2021, 36(10): 1091-1096.

SONG Keke, HUANG Hao, LU Mengjie, YANG Anchun, WENG Jie, DUAN Ke. Hydrothermal Preparation and Characterization of Zn, Si, Mg, Fe Doped Hydroxyapatite[J]. Journal of Inorganic Materials, 2021, 36(10): 1091-1096.

图/表 7

图1 1%、3%和5%不同元素掺杂HA样品的SEM照片

Fig. 1 SEM images of hydroxyapatite samples doped by different elements at 1%, 3% and 5% doping amount (a1-a3) Zn-HA; (b1-b3) Si-HA; (c1-c3) Mg-HA; (d1-d3) Fe-HA; (e1- e3) Mn-HA; (f1-f3) Sr-HA; (g1-g3) Se-HA; (h1-h3) Co-HA; (i1-i3) Cu-HA; (j1) HA

图2 5%元素掺杂的样品在2θ=20°~70°范围内的XRD图谱

Fig. 2 XRD patterns from 2θ=20° to 70° of hydroxyapatite samples with 5% doping amount

表1 5%元素掺杂样品的结晶度及晶格参数

Table 1 Crystallinity and lattice parameters of 5% element doped samples (1 Å =0.1 nm)

Sample	Crystallinity/%	a/Å	b/Å	c/Å
HA	97.24	9.44	9.44	6.89
5%Zn-HA	82.60	9.45	9.45	6.88
5%Si-HA	95.19	9.43	9.43	6.88
5%Mg-HA	85.75	9.45	9.45	6.88
5%Fe-HA	95.40	9.44	9.44	6.89
5%Mn-HA	94.01	9.42	9.42	6.87
5%Sr-HA	85.37	9.44	9.44	6.90
5%Se-HA	92.85	9.43	9.43	6.88
5%Co-HA	92.31	9.43	9.43	6.88
5%Cu-HA	91.15	9.45	9.45	6.88

图3 5%不同元素掺杂HA样品官能团的FT-IR光谱图

Fig. 3 FT-IR spectra of functional groups of hydroxyapatites doped by different elements at 5% doping amount

图4 5%元素掺杂样品的实际掺杂效率

Fig. 4 Actual doping efficiency of hydroxyapatite doped by different element at 5% doping amount

表2 Ca2+和所掺杂阳离子的离子(原子)半径尺寸

Table 2 Ion (atom) radius size of doped elements

Ion	Radius dimension/nm
Ca²⁺	0.099
Sr²⁺	0.113
Mn²⁺	0.080
Co²⁺	0.074
Zn²⁺	0.074
Cu²⁺	0.072
Mg²⁺	0.065
Fe³⁺	0.064

图5 磷酸根离子和正硅酸根离子的空间构型

Fig. 5 Spatial configurations of phosphate ion and n-silicate ion

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水热制备锌、硅、镁、铁等元素掺杂羟基磷灰石及其表征

Hydrothermal Preparation and Characterization of Zn, Si, Mg, Fe Doped Hydroxyapatite

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