牡蛎壳为原料制备医用CaCO3/HA复合生物材料

doi:10.15541/jim20190144

摘要/Abstract

摘要：

以牡蛎壳为原材料, 通过水热法制备了碳酸钙(CaCO₃)/羟基磷灰石(HA)复合材料, 拟达到降低HA生产成本并改善其降解性能的目的。通过物相分析和SEM、TEM观察发现制得的CaCO₃/HA复合材料呈现片层状, 其微观形貌呈现纳米颗粒状。实验通过控制钙、磷元素的投料比例制备了HA含量为20%、40%、60%的三种CaCO₃/HA复合材料(20%HA、40%HA、60%HA), 通过ICP测试计算得出HA的实际含量为17.52%、34.30%、43.24%。随着HA含量的增加, CaCO₃/HA复合材料的比表面积和热稳定性显著提升。体外降解实验结果表明, 三种不同HA含量的复合材料在PBS模拟体液中14 d的降解率分别为15.2%, 12.0%和10.8%, 降解率随HA比例的增高而降低。这些结果表明: 水热法合成CaCO₃/HA复合材料可通过钙、磷元素的投料比例来调控HA的转化率, 进而调控CaCO₃/HA复合材料的降解速率, 实现其在骨科领域的潜在应用。

关键词: 牡蛎壳, 羟基磷灰石, 碳酸钙, 降解性能, 骨科

Abstract:

To reduce the cost of HA and improve degradation performance of HA, oyster shells were used as raw materials to prepare CaCO₃/ hydroxyapatite (HA) composite materials by a hydrothermal method. Phase analysis and SEM/TEM observation revealed that as-prepared CaCO₃/HA composites had a morphology of HA nanoparticles growing on the lamellar CaCO₃. Three kinds of CaCO₃/HA composites (20%HA、40%HA、60%HA) with HA content of 20%, 40% and 60% were prepared by controlling the proportion of calcium and phosphorus. The actual content of HA in three obtained different composites, determined by ICP, were 17.52%, 34.30% and 43.24%, respectively. With the increase of HA content, the specific surface area and thermal stability of CaCO₃/HA composite are improved. Samples were immersed in PBS simulated body fluid for 14 d to evaluate their in vitro degradation ability. The results showed that degradation rates of three kinds of composites with different HA contents (20%HA, 40%HA and 60%HA) were 15.2%, 12.0% and 10.8%, respectively. The degradation rate decreased with the increase of HA proportion in the composite. All data indicates that the hydrothermal synthesis of CaCO₃/HA composite can control the conversion degree of HA and then adjust the degradation rate of CaCO₃/HA composite by designing the ratio of calcium and phosphorus elements, which have potential application in orthopedics.

Key words: oyster shell, hydroxyapatite, calcium carbonate, degradation rate, orthopedic application

中图分类号:

TQ342

刘子阳, 耿振, 李朝阳. 牡蛎壳为原料制备医用CaCO₃/HA复合生物材料[J]. 无机材料学报, 2020, 35(5): 601-607.

LIU Ziyang, GENG Zhen, LI Zhaoyang. Preparing Biomedical CaCO₃/HA Composite with Oyster Shell[J]. Journal of Inorganic Materials, 2020, 35(5): 601-607.

图/表 10

表1 牡蛎壳煅烧产物的重金属含量

Table 1 Heavy metal content of the calcined products of oyster shells

Element	Calcined product /(mg·kg^-1)	Limit/(mg·kg^-1)
Pb	<10	30
Cd	<1.5	5
Hg	<1	5
As	<1	3

图1 牡蛎壳经煅烧水洗后所得粉末的(a)XRD图谱、(b)EDS分析结果、(c)SEM照片和(d)TEM照片及SAED图谱

Fig. 1 (a) XRD pattern, (b) EDS analysis, (c) SEM micrograph and (d) TEM image and SAED pattern of the powders prepared by heating and washing the oyster shell

图2 水热产物的XRD图谱

Fig. 2 XRD patterns of of the synthesized samples

表2 样品中Ca、P离子含量及HA转化程度

Table 2 Ca and P concentrations and HA transition degree of samples

	20%HA	40%HA	60%HA
Concentration of Ca/(mg·L^-1)	(19.91±0.72)	(20.00±1.08)	(20.02±0.52)
Concentration of P/(mg·L^-1)	(1.62±0.17)	(3.19±0.22)	(4.02±0.19)
Degree of HA transition/%	(17.5±0.57)	(34.3±1.02)	(43.2±0.33)

图3 水热产物的SEM形貌照片

Fig. 3 SEM micrographs of the hydrothermally synthesized samples (a) 20%HA; (b) 40%HA; (c) 60%HA

图4 水热产物的TEM和HRTEM照片

Fig. 4 TEM and HRTEM images of the hydrothermally synthesized samples (a, b) 20%HA; (c, d) 40%HA; (e, f) 60%HA

图5 水热产物BET测试结果

Fig. 5 Specific surface area of the prepared samples

图6 样品热失重的曲线图

Fig. 6 TG curves of the prepared samples

表3 样品降解释放Ca2+浓度及降解率

Table 3 Ca2+ concentration and degradation rate of samples

	20%HA		40%HA		60%HA		CaCO₃
Degradation time/d	Concentration of Ca²⁺/(mg·L^-1)	Degradation rate/%	Concentration of Ca²⁺/(mg·L^-1)	Degradation rate/%	Concentration of Ca²⁺/(mg·L^-1)	Degradation rate/%	Concentration of Ca²⁺/(mg·L^-1)	Degradation rate/%
7	(16.13±0.40)	8.1	(13.39±0.23)	6.7	(11.61±0.92)	5.8	(18.93±0.17)	9.8
14	(30.26±1.12)	15.2	(24.02±0.83)	12.0	(21.62±1.36)	10.8	(42.70±0.19)	22.1
21	(43.20±1.47)	21.7	(33.40±1.38)	16.2	(28.11±1.07)	14.3	(56.41±0.32)	29.2

图7 样品降解试验后的SEM照片

Fig. 7 SEM micrographs of the samples after degradation

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牡蛎壳为原料制备医用CaCO₃/HA复合生物材料

Preparing Biomedical CaCO₃/HA Composite with Oyster Shell

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