CN107032775A - 一种纳米羟基磷灰石、硅酸二钙复合生物陶瓷及其制备方法和应用 - Google Patents

一种纳米羟基磷灰石、硅酸二钙复合生物陶瓷及其制备方法和应用 Download PDF

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CN107032775A
CN107032775A CN201611115394.0A CN201611115394A CN107032775A CN 107032775 A CN107032775 A CN 107032775A CN 201611115394 A CN201611115394 A CN 201611115394A CN 107032775 A CN107032775 A CN 107032775A
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nanometer hydroxyapatite
dicalcium silicate
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boilogical ceramic
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CN107032775B (zh
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廖建国
王佳
张春雷
张蕊
杨霏
郭俊
翟婷
胡鹏辉
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Henan Zhongsheng Technology Co ltd
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Abstract

本发明公开一种纳米羟基磷灰石、硅酸二钙复合生物陶瓷及其制备方法和应用。该复合生物陶瓷是由质量百分比为54~67%的四水合硝酸钙、13~33%的九水合硅酸钠、5~13%的碳酸钠和0~15%的磷酸氢二铵采用原位复合法制备得到纳米羟基磷灰石、硅酸钙、碳酸钙复合粉体,并通过干压预成型得到陶瓷素胚,常压烧结技术得到生物陶瓷。利用本发明的制备方法得到的生物陶瓷生物活性好、可降解性好、力学强度好,可作为骨修复材料,应用在生物医用材料领域;而且本发明的制备工艺简单,易推广应用。

Description

一种纳米羟基磷灰石、硅酸二钙复合生物陶瓷及其制备方法 和应用
技术领域
本发明属于生物医用材料技术领域,具体涉及原位复合法制备纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
背景技术
骨组织是人体中最坚硬的结缔组织,在维持基本功能时有着不可替代的作用。骨功能主要包括以下几个方面:保护体内器官;运动时为肌肉提供附着部位;产生红细胞和白细胞,白细胞为其他组织提供免疫保护,而红细胞与氧结合;是钙、磷酸根以及其他重要离子的存储器。
随着科学技术的发展和人口老龄化速度的加快,以及工业化、交通、体育等导致的创伤增加,对生物医用材料及其制品的需求越来越大。据资料显示,生物医用材料隶属于医疗器械范畴,所占医疗器械市场份额超过40%。作为高技术重要组成部分的生物医用材料已经进入一个快速发展的新阶段,其市场销售额正以每年16%的速度递增,预计在未来20年内,生物医用材料所占的份额将赶上药物市场,成为一个支柱产业。
长期以来,用于骨组织修复和重建的材料主要是自体骨移植和同种异体骨移植。但自体骨来源有限,容易引发供体组织并发症;异体骨移植则存在免疫排斥反应和从供体传染严重疾病的危险。因此,可用于骨组织修复的人工材料成为生物医用材料领域的研究重点。
生物医用材料的发展经历了从生物惰性无机骨修复材料到生物活性骨修复材料的历程。自1969年美国弗罗里达大学的Hench教授首次发现玻璃45S5能骨组织的键性结合,并提出“生物活性”的概念,生物材料的研究进入了一个新的阶段,即研究具有生物活性的医用生物材料。
近年来,国内外学者对人体骨组织和替代生物活性材料进行了大量研究,研究表明,不少含钙-硅组元的无机材料具有优良的生物活性和生物相容性,是修复骨缺损较为理想的候选材料。硅酸二钙(dicalcium silicate ,Ca2SiO4,,又称2CaO·SiO2,简写C2S)粉体在模拟体液中浸泡其表面可以快速诱导类骨碳酸羟基磷灰沉积,同时伴随着粉体降解,溶出钙、硅离子,且在一定浓度范围内能刺激成纤维细胞和成骨细胞显著增殖。但其难以烧结致密、力学性能不佳等缺点,大大限制了CaO-SiO2类陶瓷的临床应用。
人工合成纳米羟基磷灰石(Ca10(PO4)6(OH)2,nano-Hydroxyapatite,简称 n-HA)具有与人体硬组织中相近的无机成分,与自然骨的化学相似性,其良好的生物相容性和生物活性被大量研究所证实,使其在骨替代和骨重建材料方面吸引了广泛的研究,但HA陶瓷因其降解率差,在体内难以吸收,影响新骨的形成和改建等缺点限制了其适用范围。
发明内容
本发明的目的是基于硅酸二钙与羟基磷灰石的优良性能,采用原位复合法将二者的优良性能进行有机结合,得到综合性能良好的复合生物陶瓷,扩大其在生物材料领域的应用范围。
本发明的目的可通过下述技术措施来实现:
本发明的纳米羟基磷灰石、硅酸二钙复合生物陶瓷是由质量百分比为54~67%的四水合硝酸钙(Ca(NO3)2·4H2O)、13~33%的九水合硅酸钠(Na2SiO4·9H2O)、5~13%的碳酸钠(Na2CO3)和0~15%的磷酸氢二铵((NH4)2HPO4)采用原位复合法制备得到纳米羟基磷灰石、硅酸钙、碳酸钙复合粉体,并通过干压预成型得到陶瓷素胚,常压烧结技术得到生物陶瓷。
本发明的反应机理为:
Ca(NO3)2+Na2SiO3 →CaSiO3↓+2NaNO3
Ca(NO3)2+Na2CO3→CaCO3↓+2NaNO3
CaSiO3+CaCO3Ca2SiO4+CO2↑
5Ca2++3NH4++3小时PO42-→Ca5(PO4)3OH↓+3NH3↑+6H2O
本发明的制备方法是通过下述步骤来实现的:
a、按重量百分比称取四水合硝酸钙、九水合硅酸钠、碳酸钠和磷酸氢二铵,分别配置成半饱和溶液。
b、将四水合硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入分析纯试剂四水合硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸钙、碳酸钙复合粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体与聚乙烯醇溶液按质量比94:6混合,搅拌混匀3~6分钟,在压力为5Mpa的条件下采用干压预成型,制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,之后在炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
本发明的纳米羟基磷灰石、硅酸二钙复合生物陶瓷作为骨修复材料,应用在生物医用材料领域。
本发明的有益效果如下:
本发明将羟基磷灰石和硅酸二钙的优良性能进行有机结合,得出的复合生物陶瓷具有优良的生物活性、可降解性,并且其经烧结后的致密度更高,对有目的地设计生物材料组分,以达到与生物组织的有机连接具有重要意义。
附图说明
图1为本发明制备的纳米羟基磷灰石、硅酸二钙复合粉体样品850℃X射线衍射分析图谱。
图2为本发明制备的纳米羟基磷灰石、硅酸二钙复合粉体样品950℃X射线衍射分析图谱。
图3为本发明制备的纳米羟基磷灰石、硅酸二钙复合粉体样品1050℃X射线衍射分析图谱。
图4为本发明制备的纳米羟基磷灰石、硅酸二钙复合粉体样品1150℃X射线衍射分析图谱。
图5为本发明制备的纳米羟基磷灰石、硅酸二钙复合粉体样品1250℃X射线衍射分析图谱。
具体实施方式
本发明结合以下实施例作进一步详细说明。
实施例1
a、根据羟基磷灰石/硅酸二钙质量比为0:10时,按质量百分比计,称取下述原料:四水合硝酸钙(Ca(NO3)2·4H2O)54.76%、九水合硅酸钠(Ca(NO3)2·4H2O)32.94%、碳酸钠(Na2CO3)12.30%分别配置成半饱和溶液。
b、将硝酸钙溶液置于电动搅拌器下搅拌,然后将硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、步骤b制备出的沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到硅酸二钙粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体与聚乙烯醇溶液按质量比为94:6混合,搅拌混匀3~6分钟,采用干压预成型(压力约5MPa),制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,炉内随炉冷至室温,即得到不含纳米羟基磷灰石的硅酸二钙生物陶瓷。
实施例2
a、根据羟基磷灰石/硅酸二钙质量比为1:9时,按质量百分比计,称取下述原料:四水合硝酸钙(Ca(NO3)2·4H2O)56.03%、九水合硅酸钠(Ca(NO3)2·4H2O)30.85%、碳酸钠(Na2CO3)11.49%、磷酸氢二铵((NH4)2HPO4) 1.63%,分别配置成半饱和溶液。
b、将四水合硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、步骤b制备出的沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸二钙复合粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体按质量比与聚乙烯醇溶液质量比为94:6混合,搅拌混匀3~6分钟,采用干压预成型(压力约5MPa),制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
实施例3
a、根据羟基磷灰石/硅酸二钙质量比为2:8时,按质量百分比计,称取下述原料:四水合硝酸钙57.48%、九水合硅酸钠28.49%、碳酸钠10.63%和磷酸氢二铵3.40%分别配置成半饱和溶液。
b、将硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、步骤b制备出的沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸二钙复合粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体与聚乙烯醇溶液按质量比为94:6混合,搅拌混匀3~6分钟,采用干压预成型(压力约5MPa),制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
实施例4
a、根据羟基磷灰石/硅酸二钙质量比为5:5时,按质量百分比计,称取下述原料:四水合硝酸钙62.50%、九水合硅酸钠20.26%、碳酸钠7.56%和磷酸氢二铵9.68%分别配置成半饱和溶液。
b、将硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、步骤b制备出的沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸二钙复合粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体与聚乙烯醇溶液按质量比为94:6混合,搅拌混匀3~6分钟,采用干压预成型(压力约5MPa),制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
实施例5
a、根据羟基磷灰石/硅酸二钙质量比为7:3时,按质量百分比计,称取下述原料:四水合硝酸钙66.70%、九水合硅酸钠13.38%、碳酸钠5.00%和磷酸氢二铵14.92%分别配置成半饱和溶液。
b、将硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时。
c、步骤b制备出的沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸二钙复合粉体。
d、制备质量比6%的聚乙烯醇溶液作为粘结剂。
e、将步骤c制备的复合粉体按质量比与聚乙烯醇溶液质量比为94:6混合,搅拌混匀3~6分钟,采用干压预成型(压力约5MPa),制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚。
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。

Claims (3)

1.一种纳米羟基磷灰石、硅酸二钙复合生物陶瓷,其特征在于:它是由质量百分比为54~67%的四水合硝酸钙、13~33%的九水合硅酸钠、5~13%的碳酸钠和0~15%的磷酸氢二铵采用原位复合法制备得到纳米羟基磷灰石、硅酸钙、碳酸钙复合粉体,并通过干压预成型得到陶瓷素胚,常压烧结技术得到生物陶瓷。
2.一种用于制备权利要求1所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷
的方法,其特征在于:所述方法是通过下述步骤来实现的:
a、按重量百分比称取四水合硝酸钙、九水合硅酸钠、碳酸钠和磷酸氢二铵,分别配置成半饱和溶液;
b、将四水合硝酸钙溶液置于电动搅拌器下搅拌,然后将九水合硅酸钠溶液、碳酸钠溶液、磷酸氢二铵溶液依次滴入分析纯试剂四水合硝酸钙溶液中,调节溶液pH值大于12,搅拌3小时;
c、沉淀密封后在室温下陈化24小时,经抽滤,水洗5次,在80℃下干燥8小时,得到纳米羟基磷灰石、硅酸钙、碳酸钙复合粉体;
d、制备质量比6%的聚乙烯醇溶液作为粘结剂;
e、将步骤c制备的复合粉体与聚乙烯醇溶液按质量比94:6混合,搅拌混匀3~6分钟,在压力为5Mpa的条件下采用干压预成型,制备出纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚;
f、将步骤e制备得到的纳米羟基磷灰石、硅酸二钙复合生物陶瓷素胚在1300℃高温炉中常压烧结6小时,之后在炉内随炉冷至室温,即得到所述纳米羟基磷灰石、硅酸二钙复合生物陶瓷。
3.一种权利要求1所述的纳米羟基磷灰石、硅酸二钙复合生物陶瓷的应用,其特征在于:所述的纳米羟基磷灰石、硅酸二钙复合生物陶瓷作为骨修复材料,应用在生物医用材料领域。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107720796A (zh) * 2017-10-20 2018-02-23 西北工业大学 一种骨修复用C‑Ca‑P‑Si四组元生物复合材料的制备方法
CN108424139A (zh) * 2018-05-08 2018-08-21 西南交通大学 一种高致密度陶瓷材料及其制备方法
CN110272272A (zh) * 2018-03-15 2019-09-24 中国科学院上海硅酸盐研究所 一种氟掺杂羟基磷灰石生物陶瓷粉体材料及其制备方法和应用
CN110818403A (zh) * 2018-08-09 2020-02-21 苏州鼎安科技有限公司 一种气氛保护常压烧结制备透明磷酸钙生物陶瓷的方法
CN114133230A (zh) * 2021-11-24 2022-03-04 淄博金狮王科技陶瓷集团有限公司 生物活性陶瓷材料的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101700415A (zh) * 2009-11-13 2010-05-05 中国科学院上海硅酸盐研究所 硅酸钙/羟基磷灰石复合生物陶瓷材料及其制备方法和用途
EP2124867B1 (en) * 2007-02-09 2015-04-15 DENTSPLY International Inc. A method of treatment of the dental pulp and filling root canals using water-based materials
CN105272193A (zh) * 2015-11-13 2016-01-27 河南理工大学 一种纳米羟基磷灰石、硅酸三钙复合生物陶瓷及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2124867B1 (en) * 2007-02-09 2015-04-15 DENTSPLY International Inc. A method of treatment of the dental pulp and filling root canals using water-based materials
CN101700415A (zh) * 2009-11-13 2010-05-05 中国科学院上海硅酸盐研究所 硅酸钙/羟基磷灰石复合生物陶瓷材料及其制备方法和用途
CN105272193A (zh) * 2015-11-13 2016-01-27 河南理工大学 一种纳米羟基磷灰石、硅酸三钙复合生物陶瓷及其制备方法和应用

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107720796A (zh) * 2017-10-20 2018-02-23 西北工业大学 一种骨修复用C‑Ca‑P‑Si四组元生物复合材料的制备方法
CN110272272A (zh) * 2018-03-15 2019-09-24 中国科学院上海硅酸盐研究所 一种氟掺杂羟基磷灰石生物陶瓷粉体材料及其制备方法和应用
CN108424139A (zh) * 2018-05-08 2018-08-21 西南交通大学 一种高致密度陶瓷材料及其制备方法
CN110818403A (zh) * 2018-08-09 2020-02-21 苏州鼎安科技有限公司 一种气氛保护常压烧结制备透明磷酸钙生物陶瓷的方法
CN114133230A (zh) * 2021-11-24 2022-03-04 淄博金狮王科技陶瓷集团有限公司 生物活性陶瓷材料的制备方法
CN114133230B (zh) * 2021-11-24 2023-01-17 淄博金狮王科技陶瓷集团有限公司 生物活性陶瓷材料的制备方法

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