CN1939542A - 一种CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷及其制备方法 - Google Patents
一种CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷及其制备方法,玻璃陶瓷中,CaO和P2O5总含量在80~90mol%,Na2O的含量在4~7mol%,其余为TiO2和ZrO2。其制备过程如下:将原料混合均匀,经干燥后加热熔融,然后取出倒在不锈钢钢板上冲压制备玻璃;将冲压所得玻璃球磨成粉后,冷压成块并烧结获得玻璃陶瓷。该玻璃陶瓷不含SiO2,无有毒元素,具有良好的生物活性,在模拟人体体液中浸泡4天有一层致密均匀的羟基磷灰石生成;具有较高强度(大于90MPa),可以进行切削,便于加工;具有较高的Ca/P比以及和人体硬组织相似的成分,可以作为人体硬组织替代和修复材料。该生物玻璃陶瓷具有生物玻璃陶瓷的共性,和金属植入物相比可望获得更快的成骨能力和更高的骨键合强度。
Description
技术领域:
本发明涉及玻璃陶瓷领域,特别是涉及临床医学应用的具有高强度和高生物活性的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷及其制备方法。
背景技术:
人体硬组织修复与重建材料是生物医学材料中发展最早、最成熟的领域。迄今为止,用于硬组织修复与替换的材料有金属与合金、生物玻璃陶瓷、聚合物、复合材料及人和动物的骨骼衍生物等,见参考文献[1]:俞耀庭.生物医用材料.天津:天津大学出版社,2000:116。生物活性玻璃陶瓷是一类能与生物软组织或骨组织键合的生物材料,具有金属、高分子及生物惰性材料不可比拟的优势。因此,人们对这类新型材料产生了浓厚的兴趣,并研制出多种生物活性玻璃陶瓷,例如:45S5Bioglass生物玻璃(Na2O-CaO-SiO2-P2O5系)、Ceravital微晶玻璃(Na2O-K2O-MgO-CaO-P2O5-SiO2系)、A-W生物玻璃陶瓷(MgO-CaO-SiO2-P2O5系)、羟基磷灰石生物活性陶瓷(HA,组成为:Ca10(PO4)6(OH)2)等等,见参考文献[2]和[3],参考文献[2]:Larry L.Hench.Bioceramics.J.Am.Ceram.Soc.1998,81[7]:1705-1728;参考文献[3]:杨为中,周大利,尹光福和郑昌琼.生物医学工程学杂志.2003,20(3):541-545。和其它生物惰性材料相比,生物玻璃陶瓷具有更好的生物相容性、更高的骨键合强度和更快的成骨能力,见参考文献[4]:李玉宝.生物医学材料.北京:化学工业出版社,2003:82。但是大多数生物活性玻璃都含有大量的SiO2,而Nagase et al.发现在实验老鼠腹腔注射含二氧化硅钙磷玻璃的当量盐水时老鼠死亡,而不含二氧化硅时则不显示毒性,见参考文献[5]:Nagase M,Abe Y,Chigira M and Udagawa E.Toxicity of silica-containing calciumposphate glasses demonstrated in mice.Biomaterials.1992,13:172-175。
生物玻璃陶瓷在临床上作为骨替代材料是通过骨传导途径完成的。由于其良好的生物相容性,植入机体后不引起明显反应,植入物周围宿主骨痂可通过爬行面汇合,并将植入物包裹,使之起到充填和连接骨缺损的作用。但是其较低的韧性限制了它的推广应用。氧化锆陶瓷是新近发展起来的仅次于氧化铝的一种很重要的结构陶瓷。由于它的良好性能,如高硬度、高强度和较高的断裂韧性,因而越来越受到人们的重视,见参考文献[6]:刘维良.先进陶瓷工艺学.武汉:武汉理工大学出版社.2004:176-180。氧化锆很早就作为晶核剂而加入到玻璃陶瓷中。在玻璃成分中加入氧化锆微粒,可使玻璃断裂强度从2MPa提高到3MPa,见参考文献[7]:汤继文、张玉德和刘春梅.生物活性玻璃陶瓷人工骨材料的研究进展.山东医药.1997,37[5]:45-50。CaO-P2O5系玻璃陶瓷是新近发展起来的一种新型生物玻璃陶瓷,该系陶瓷的成分与人体骨组织接近,具有良好的生物活性并且无毒,见参考文献[8]:Kasuga T and Abe Y.Calcium phosphate invert glasses with soda andtitania.J.Non-cryst.Solids.1999,243:70-74。本发明在CaO-P2O5系玻璃陶瓷基础上,引入ZrO2,形成CaO-P2O5-Na2O-TiO2-ZrO2系玻璃陶瓷。它是一种不含SiO2的生物玻璃,具有较高的Ca/P比以及和人体硬组织相似的成分,具有较高的断裂强度和生物活性,更适合做人体植入材料。
发明内容
本发明的目的是提供一种新型CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷及其制备方法。该玻璃陶瓷具有良好的生物活性、较高硬度、强度和可切削性,具有和人体硬组织相似的成分,可以作为人体硬组织替代和修复材料。
本发明的技术方案是:
本发明提供一种CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,CaO和P2O5总含量在80~90mol%,Na2O的含量在4~7mol%,其余为TiO2和ZrO2。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,所述玻璃陶瓷中,Ca与P摩尔比为0.5~1.5。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,所述玻璃陶瓷中,ZrO2的含量在0.5~10mol%。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,所述玻璃陶瓷制备包括玻璃的制备和陶瓷的制备。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其制备过程如下:将原料用电动搅拌机搅拌混合均匀,经鼓风干燥箱干燥后加热熔融,然后快速取出倒在不锈钢钢板上冲压。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,所述玻璃所用原料为化学试剂:CaCO3,Na2CO3,TiO2,ZrO2和H3PO4(液体,重量百分比为85%),均为分析纯。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,混合均匀的原料经干燥后捣碎,捣碎的原料粒度为5~10μm;再在1300~1400℃下加热熔融、保温0.5~1小时后,立即取出倒在不锈钢钢板上冲压得玻璃。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,在模拟人体体液中浸泡4-7天表面有均匀致密的羟基磷灰石生成,表面活性高。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,所述陶瓷制备过程如下:将冲压所得玻璃球磨成粉后冷压成块并烧结。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,冷压压力为80~150MPa,玻璃粉烧结温度为800~850℃,时间为1~2小时。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,所制得的陶瓷抗弯强度大于90MPa,优于45S5Bioglass生物玻璃。
本发明提供的CaO-P2O5-Na2O-TiO2-ZrO2系玻璃陶瓷具有良好的生物活性,在模拟人体体液(SBF)中浸泡4-7天后表面有羟基磷灰石生成。其良好的生物活性和力学性质不仅可以作为牙齿、颌面骨及中耳骨亦可作为人工椎体、椎间盘和髂嵴等医用材料。
本发明的有益效果是:
本发明玻璃陶瓷不含SiO2,无有毒元素,具有良好的生物活性,在模拟人体体液中浸泡4天有一层致密均匀的羟基磷灰石生成;具有较高强度(大于90MPa),可以进行切削,便于加工;具有较高的Ca/P比以及和人体硬组织相似的成分,可以作为人体硬组织替代和修复材料。该生物玻璃陶瓷具有生物玻璃陶瓷的共性,和金属植入物相比可望获得更快的成骨能力和更高的骨键合强度。
附图说明:
图1快速冲压所得CaO-P2O5-Na2O-TiO2-ZrO2玻璃;
图2快速冲压所得60CaO30P2O54Na2O3TiO23ZrO2玻璃经1000#砂纸打磨后形貌图;
图3 60CaO30P2O54Na2O3TiO23ZrO2玻璃在模拟人体体液中浸泡4天后的形貌图;
图4 60CaO30P2O54Na2O3TiO23ZrO2玻璃在模拟人体体液中浸泡4天后的形貌图的放大照片;
图5 60CaO30P2O55Na2O3TiO22ZrO2玻璃在模拟人体体液中浸泡7天后的形貌图;
图6 60CaO30P2O55Na2O3TiO22ZrO2玻璃模拟人体体液中浸泡7天后的X-射线衍射图谱;
图7 CaO-P2O5-Na2O-TiO2-ZrO2玻璃粉碎冷压烧结后所得玻璃陶瓷;
图8 60CaO30P2O55Na2O3TiO22ZrO2玻璃陶瓷的成份衍射图谱;
图9 60CaO30P2O54Na2O3TiO23ZrO2玻璃陶瓷在模拟人体体液中浸泡7天后的形貌图。
具体实施方式:
实施例1
用分析纯CaCO3,Na2CO3,TiO2,ZrO2和H3PO4(85%)为原料配制按表1所述成分玻璃浆液,用电动搅拌机将原料混合均匀,然后置于50℃干燥箱内干燥24h。将干燥后原料捣成粉末(粒度为5-10μm)置于铂金坩埚内在1350℃保温0.5h,立即取出倒在不锈钢钢板上并快速冲压即得玻璃。所得玻璃宏观形貌见图1。
表1CaO-P2O5-Na2O-TiO2-ZrO2玻璃成份
编号 | 成分mol% | ||||
12345678910 | 60CaO60CaO60CaO60CaO60CaO60CaO60CaO60CaO60CaO60CaO | 30P2O530P2O530P2O530P2O530P2O530P2O530P2O530P2O530P2O530P2O5 | 7Na2O6Na2O5Na2O4Na2O6.5Na2O5.5Na2O7Na2O7Na2O7Na2O7Na2O | 3TiO23TiO23TiO23TiO23TiO23TiO22TiO21TiO22.5TiO21.5TiO2 | 1ZrO22ZrO23ZrO20.5ZrO21.5ZrO21ZrO22ZrO20.5ZrO21.5ZrO2 |
实施例2
将冲压所得60CaO30P2O54Na2O3TiO23ZrO2玻璃在模拟人体体液(表2)中37℃浸泡4天后,表面有一层致密均匀的羟基磷灰石生成。其浸泡前微观形貌如图2所示,浸泡后微观形貌如图3、图4所示。
表2人体中的血浆和模拟人体体液(SBF)中的离子浓度(mM)
离子 | Na+ | K+ | Mg2+ | Ca2+ | Cl- | HPO4 2- | SO4 2- | HCO3 - |
血浆SBF | 142.0142.0 | 5.05.0 | 1.51.5 | 2.52.5 | 103.0148.8 | 1.01.0 | 0.50.5 | 27.04.2 |
实施例3
将冲压所得60CaO30P2O55Na2O3TiO22ZrO2玻璃在37℃模拟人体体液(表2)中浸泡7天后,表面有一层致密均匀的羟基磷灰石生成。浸泡后微观形貌如图5所示,其X-射线衍射图谱如图6所示。
实施例4
将冲压所得玻璃经球磨机粉碎后冷压成40×9×6mm试样,冷压压力为100MPa,以10℃/min速率随炉升温,在850℃保温1h,随炉冷却。所得陶瓷宏观形貌如图7所示,其成份主要为β-Ca3(PO4)2和β-Ca2P2O7(如图8)。
实施例5
将冲压所得60CaO30P2O55Na2O3TiO22ZrO2玻璃陶瓷在模拟人体体液(表2)中37℃浸泡7天后,表面有一层致密均匀的羟基磷灰石生成。浸泡后微观形貌如图9所示。
实施例6
对冲压所得玻璃经球磨机粉碎后冷压并烧结所得陶瓷进行三点弯曲实验,测试结果显示CaO-P2O5-Na2O-TiO2-ZrO2系玻璃陶瓷的抗弯强度大于90MPa,其性能优于45S5Bioglass生物玻璃。
实施例7
用分析纯CaCO3,Na2CO3,TiO2,ZrO2和H3PO4(液体,重量百分比为85%)为原料配制按表1所述成分玻璃浆液,用电动搅拌机将原料混合均匀,然后置于50℃干燥箱内干燥24h。将干燥后原料捣成粉末(粒度为5-10μm)置于铂金坩埚内在1300℃保温1h,立即取出倒在不锈钢钢板上并快速冲压即得玻璃。
表3CaO-P2O5-Na2O-TiO2-ZrO2玻璃成份
编号 | 成分mol% | ||||
12345 | 60CaO60CaO60CaO60CaO60CaO | 20P2O520P2O520P2O520P2O520P2O5 | 7Na2O6Na2O5Na2O4Na2O6.5Na2O | 3TiO26TiO29TiO212TiO213TiO2 | 10ZrO28ZrO26ZrO24ZrO20.5ZrO2 |
将冲压所得玻璃在37℃模拟人体体液(表2)中浸泡7天后,表面有一层致密均匀的羟基磷灰石生成,表面活性高。
将冲压所得玻璃经球磨机粉碎后用150MPa压力冷压成40×9×6mm试样,然后以10℃/min速率随炉升温,在800℃保温2h,随炉冷却。所得陶瓷宏观形貌,其成份主要为β-Ca3(PO4)2和β-Ca2P2O7。
将冲压所得玻璃陶瓷在模拟人体体液(表2)中37℃浸泡7天后,表面有一层致密均匀的羟基磷灰石生成,其良好的生物活性和力学性质不仅可以作为牙齿、颌面骨及中耳骨亦可作为人工椎体、椎间盘和髂嵴等医用材料。
实施例8
用分析纯CaCO3,Na2CO3,TiO2,ZrO2和H3PO4(液体,重量百分比为85%)为原料配制按表1所述成分玻璃浆液,用电动搅拌机将原料混合均匀,然后置于50℃干燥箱内干燥24h。将干燥后原料捣成粉末(粒度为5-10μm)置于铂金坩埚内在1400℃保温0.8h,立即取出倒在不锈钢钢板上并快速冲压即得玻璃。
表4CaO-P2O5-Na2O-TiO2-ZrO2玻璃成份
编号 | 成分mol% | ||||
12345 | 42CaO42CaO42CaO42CaO42CaO | 42P2O542P2O542P2O542P2O542P2O5 | 7Na2O6Na2O5Na2O4Na2O6.5Na2O | 3TiO23TiO23TiO23TiO23TiO2 | 6ZrO27ZrO28ZrO29ZrO26.5ZrO2 |
将冲压所得玻璃在37℃模拟人体体液(表2)中浸泡7天后,表面有一层致密均匀的羟基磷灰石生成,表面活性高。
将冲压所得玻璃经球磨机粉碎后用80MPa压力冷压成40×9×6mm试样,然后以10℃/min速率随炉升温,在800℃保温2h,随炉冷却。所得陶瓷宏观形貌,其成份主要为β-Ca3(PO4)2和β-Ca2P2O7。
将冲压所得玻璃陶瓷在模拟人体体液(表2)中37℃浸泡7天后,表面有一层致密均匀的羟基磷灰石生成,其良好的生物活性和力学性质不仅可以作为牙齿、颌面骨及中耳骨亦可作为人工椎体、椎间盘和髂嵴等医用材料。
Claims (8)
1、一种CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,其特征在于:CaO和P2O5总含量在80~90mol%,Na2O的含量在4~7mol%,其余为TiO2和ZrO2。
2、按照权利要求1所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,其特征在于:所述玻璃陶瓷中,Ca与P摩尔比为0.5~1.5。
3、按照权利要求1所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷,其特征在于:所述玻璃陶瓷中,ZrO2的含量在0.5~10mol%。
4、按照权利要求1所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其特征在于包括玻璃的制备和陶瓷的制备,具体步骤如下:
(1)玻璃的制备
以CaCO3,Na2CO3,TiO2,ZrO2和H3PO4为原料,按所述成分将原料混合均匀,配制玻璃浆液,经干燥后捣碎加热熔融,然后取出倒在不锈钢钢板上冲压;
(2)陶瓷的制备
将冲压所得玻璃球磨成粉后,冷压成块并烧结。
5、按照权利要求4所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其特征在于:所述步骤1中,玻璃浆液经干燥后捣碎,捣碎后粉的粒度为5~10μm。
6、按照权利要求4所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其特征在于:所述步骤1中,在1300~1400℃下加热熔融、保温时间0.5~1小时后,立即取出倒在不锈钢钢板上冲压得玻璃。
7、按照权利要求4所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其特征在于:所述步骤2中,将冲压所得的玻璃球磨成粉,粉的粒度为1~10μm。
8、按照权利要求4所述的CaO-P2O5-Na2O-TiO2-ZrO2生物玻璃陶瓷的制备方法,其特征在于:所述步骤2中,冷压压力为80~150MPa,玻璃粉烧结温度为800~850℃,时间为1~2小时。
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US5196381A (en) * | 1990-01-16 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Metaphosphate glass composition |
DE4428839C2 (de) * | 1994-08-01 | 1997-01-23 | Ivoclar Ag | Alkali-Zink-Silicat-Glaskeramiken und -Gläser und Verfahren zur Herstellung der Glaskeramiken |
US6130178A (en) * | 1998-04-16 | 2000-10-10 | Corning Incorporated | Strong miserite glass-ceramics |
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