CN106904954B - 一种具有生物活性的陶瓷材料、制备方法及其应用 - Google Patents
一种具有生物活性的陶瓷材料、制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 74
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 57
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 23
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 19
- 239000003462 bioceramic Substances 0.000 claims abstract description 18
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 12
- 230000003628 erosive effect Effects 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 23
- 239000012890 simulated body fluid Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- -1 silicon ion Chemical class 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 13
- 229910052586 apatite Inorganic materials 0.000 description 10
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 10
- 238000012876 topography Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 229910003641 H2SiO3 Inorganic materials 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010031264 Osteonecrosis Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种具有生物活性的陶瓷材料、制备方法及其应用。具有生物活性的陶瓷材料化学式为Ca10Si3O15F2，本发明制备的氟硅酸钙生物陶瓷材料可以提高陶瓷材料的韧性，同时氟的引入可以加速矿化过程中羟基磷灰石在生物陶瓷表面的沉积，随着矿化时间的延长而增加羟基磷灰石的厚度，不会降解，还可以抵御外来酸侵蚀；本发明制备方法简单，次品率极低，产物性能稳定，可重复性好，且无废气排出，环境友好；制备得到的陶瓷材料具有良好的生物活性，韧性足够好、强度高，可以用来作为骨修复、骨缺损和牙齿修复填充材料。
Description
技术领域
本发明涉及一种具有生物活性的陶瓷材料、制备方法及其应用，属于生物医学材料。
背景技术
骨缺损修复材料是临床需求量最大的材料之一，目前随着人口老龄化、交通事故造成的骨折、骨组织坏死等引起的骨缺损患者人口数日益增多。骨修复材料市场巨大，寻找更好的骨组织再生修复材料是医学生物材料研究的热点，获得新型仿生人工骨修复材料已成为生物材料发张的主要趋势之一。
生物陶瓷是组织工程的一个重要研究方向，是新型的仿生人工骨修复材料，由于其潜在的市场价值，受到多方面的研究；同时具有较好的生物活性及生物相容性，在医疗方面得到广泛的应用。将生物陶瓷植入体内后，在其表面先形成一层羟基磷灰石[Ca10(PO4)6(OH)2]，羟基磷灰石一旦与有机成分结合，就会具有很强的硬度，在生物体内起到支持功能，促进骨修复。但是目前可以诱导羟基磷灰石形成的材料大多韧性较差，且降解速度过快、稳定性不好，阻止了其在生物医学方面的应用。另外，目前生物材料的制备方法条件要求苛刻、生产良品率不高，直接导致生产成本的提高，不利于推广应用。
发明内容
针对上述现有技术存在的问题，本发明的目的是提供一种具有良好生物活性、稳定性好且不易降解的陶瓷材料，本发明的目的之二是提供一种制备条件要求低、可重复性好、制备成本低的陶瓷材料的制备方法及陶瓷材料的应用。
为达到以上目的，本发明采用的技术方案是：一种具有生物活性的陶瓷材料，化学式为Ca10Si3O15F2。
本发明还公开了一种具有生物活性的陶瓷材料的制备方法，具体步骤如下：
(1)将含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物为原料，按照化学计量比称取各原料，研磨混合均匀，得到两者混合物；
(2)将步骤(1)得到的含钙离子Ca2+和硅离子Si4+的混合物在空气气氛下进行烧结，烧结温度为：750～950℃，烧结时间为：3～10小时；自然冷却，研磨混合均匀；
(3)将步骤(2)得到的粉体混合物与含有氟离子F-的化合物研磨均匀，压制成陶瓷片，压制压力为10MPa～15MPa，压制好后进行煅烧，煅烧温度为：900～1200℃，烧结时间为：3～15小时，自然冷却，研磨混合均匀，得到生物陶瓷材料。
上述制备方法中，所述的含有钙离子Ca2+的化合物为碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙的一种；所述含有硅离子Si4+的化合物为二氧化硅或硅酸中的一种；所述的含有氟离子F-的化合物为氟化钙。
作为制备方法的一个优选方案，上述含有钙离子Ca2+的化合物有两种，其中一种是氟化钙，氟化钙提供的钙占总钙量的10vol％～40vol％，另一种来源于碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙中的一种。
作为制备方法参数的优选方案，步骤(2)的烧结温度为800～950℃，烧结时间为4～10小时；步骤(3)的煅烧温度为950～1200℃，煅烧时间为5～10小时。
进一步，作为上述制备方法最优的方案，步骤(2)的烧结温度为830℃，烧结时间为9小时；步骤(3)中，压制压力为13MPa，煅烧温度为1100℃，煅烧时间为6小时。
最后，本发明公开了一种具有生物活性的陶瓷材料的应用，具体是：将陶瓷材料Ca10Si3O15F2置于模拟体液中进行矿化后，在其表面得到稳定的类骨羟基磷灰石，可以用于骨修复、骨缺损填充和牙齿修复填充。
与现有技术方案相比，本发明技术方案优点在于：
(1)本发明制备的生物陶瓷材料不含有对人体有害的元素，矿化前陶瓷表面平整光滑，模拟体液矿化1天之后，表面已变得粗糙、不平整；在模拟体液中矿化3天后，陶瓷表面已经完全被纳米级的磷灰石均匀地所覆盖，肉眼已经不能观察到陶瓷基体，表面具有磷灰石沉积；矿化7天后，磷灰石层厚度进一步增大且更加致密，说明随着时间的延长稳定性越好，且不会出现降解的状况；经长时间观测，生成的羟基磷灰石形态稳定、不易降解，氟元素具有良好的诱导磷灰石沉积的能力并可以抵制外来酸侵蚀，使得材料本身不但可以在表面沉积类骨磷灰石，还具有优异的抗腐蚀性能，更加保证了其稳定性，从而有效的解决了传统硅酸钙在生物医学方面存在的缺陷，具有较强的实用意义。
(2)本发明提供的氟硅酸钙生物陶瓷的制备方法，首先合成硅酸钙混合粉体，再将硅酸钙混合粉体与氟化钙混合利用高温烧结制备得到氟硅酸钙生物陶瓷，其方法简单，次品率极低，产物性能稳定，可重复性好，且无废气排出，环境友好。
(3)本发明制备的氟硅酸钙生物陶瓷抗弯强度为60-100MPa，弹性模量为20-80GPa，韧性足够好、强度高，适合用作骨修复、骨缺损填充材料以及齿科填充修复材料。
附图说明
图1为实施例1制得的氟硅酸钙未矿化的X射线物相衍射图谱；
图2为实施例1制得的氟硅酸钙陶瓷与矿化3天后的红外光谱对比图；
图3为实施例1制得的氟硅酸钙陶瓷矿化前(A)与矿化3天后(B)的表面形貌照片；
图4为实施例1制得的氟硅酸钙矿化3天后的X射线物相衍射图谱；
图5为实施例2制得的氟硅酸钙未矿化的X射线物相衍射图谱；
图6为实施例2制得的氟硅酸钙陶瓷与矿化7天后的红外光谱对比图；
图7为实施例2制得的氟硅酸钙陶瓷矿化前(A)与矿化7天后(B)的表面形貌照片；
图8为实施例2制得的氟硅酸钙陶瓷矿化7天后的X射线物相衍射图谱。
具体实施方式
下面结合附图和实施例对本发明作进一步描述。
实施例1：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取碳酸钙CaCO3：9克，氧化硅SiO2：1.8027克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是800℃，烧结时间10小时，然后冷却至室温，取出样品；将预烧结的原料再次与0.7808克的氟化钙CaF2充分混合研磨均匀，将混合粉体进行压制成型，压制压力为10MPa；在空气气氛中再次煅烧，煅烧温度1200℃，煅烧时间5小时，自然冷却即得到生物陶瓷。
将制备好的氟硅酸钙陶瓷块体在模拟体液矿化1天～7天，矿化后对陶瓷体表面形貌、相结构和组分进行表征，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，并评价其生物活性。模拟体液的加入量和陶瓷体的表面积的比例为30毫升/平方厘米，每24小时换液一次。将矿化不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水轻轻清洗表面，然后60℃下干燥4～6小时，用扫描电子显微镜(SEM)观察表面形貌的变化。实验中，模拟体液含有与人体血浆相近的离子及离子团浓度。其组成为：
参见附图1，它是按本实施例1技术方案制备的矿化前的样品的X射线粉末衍射图谱，测试结果显示，采用高温固相法制备了纯相的氟硅酸钙生物陶瓷。
参见附图2，它是按本发明实施例1技术方案制备的样品及矿化3天后取出样品的红外光谱图，测试结果表明，样品在模拟体液矿化之后结构成分发生了改变，从红外图谱中显示有羟基磷灰石层在陶瓷表面生成。
参见附图3，它是按本发明实施例1技术方案制备的样品及矿化3天后取出样品的扫描电镜图，测试结果显示，与原有的陶瓷片(图A)比较，矿化后的氟硅酸钙陶瓷(图B)表面有了明显的变化，覆盖了一层羟基磷灰石层，说明氟硅酸钙具有良好的诱导羟基磷灰石在表面沉积的能力。
参见附图4，它是按本发明实施案例1技术方案制备得到的样品矿化3天后表面物质的X射线粉末衍射图谱，测试结果显示，有对应PDF卡片标号09-0432的物质生成，09-0432号物质即为羟基磷灰石，说明氟硅酸钙表面生成了羟基磷灰石晶体，表明氟硅酸钙具有良好的诱导矿化能力。
对陶瓷材料进行力学性能测试，具体步骤如下：将陶瓷块体材料按照GB/T 6569-2006/ISO14704：2000标准制成标准力学测试样品，测试其力学性能，跨距30毫米，三点弯曲法测试，样品数量为5个。力学性能测试结果显示，本实施例提供的样品抗弯强度为80.5MPa，弹性模量为50GPa。
实施例2：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取碳酸钙Ca(OH)2：5.1863克，硅酸H2SiO3：2.34克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是950℃，烧结时间4小时，然后冷却至室温，取出样品；将预烧结的原料再次与2.3424克氟化钙CaF2充分混合研磨均匀，继而进行压制成型，压制压力为15MPa，在空气气氛中再次煅烧，煅烧温度950℃，煅烧时间10小时，自然冷却即得到氟硅酸钙生物陶瓷。
将制备好的氟硅酸钙陶瓷放入模拟体液矿化7天，观察矿化后的表面形貌，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，评价其生物活性，氟硅酸钙陶瓷加入模拟体液30毫升/平方厘米。将矿化不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水清洗，然后在60℃下干燥6小时，采用X射线物相衍射图谱证实物相变化，用扫描电子显微镜观察表面形貌的变化。
参见附图5，它是按本实施例2技术方案制备的矿化前样品的X射线粉末衍射图谱，测试结果显示，制备得到了纯相的氟硅酸钙生物陶瓷。
参见附图6，它是按本发明实施例2技术方案制备的样品及矿化7天后取出样品在矿化前后测试得到的红外光谱对比图，测试结果表明，样品在模拟体液矿化之后结构成分发生了改变，显示有羟基磷灰石在陶瓷表面生成。
参见附图7，它是按本发明实施例2技术方案制备的样品及矿化7天后取出样品的扫描电镜图，测试结果显示，与材料的初始状态(图A)比较，矿化后的氟硅酸钙陶瓷(图B)表面形貌出现了明显的变化，覆盖了一层羟基磷灰石，且形成的羟基磷灰石层与图3B矿化3天的羟基磷灰石层比较更加致密，说明随着时间的延长稳定性越好，且不会出现降解的状况，氟硅酸钙具有良好的诱导羟基磷灰石在表面沉积的能力。
参见附图8，它是按本发明实施案例2技术方案制备得到的样品矿化7天后的X射线粉末衍射图谱，测试结果显示，氟硅酸钙表面生成的物质是纯相的羟基磷灰石，表明氟硅酸钙具有良好的矿化能力。
力学性能测试结果显示，本实施例提供的样品抗弯强度为70MPa，弹性模量为25GPa。
实施例3：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取草酸钙CaC2O4：10.248克，硅酸H2SiO3：2.34克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是900℃，烧结时间6小时，然后冷却至室温，取出样品研磨均匀；将预烧结的原料再次与1.5616克氟化钙CaF2充分混合研磨均匀，将混合粉体进行压制成型，压制压力为12MPa，在空气气氛中再次煅烧，煅烧温度1000℃，煅烧时间9小时，自然冷却即得到氟硅酸钙生物陶瓷。
将制备好的氟硅酸钙陶瓷放入模拟体液矿化1天，观察矿化后的表面形貌变化，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，评价其生物活性。氟硅酸钙陶瓷加入模拟体液30毫升/平方厘米。将矿化了不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水清洗，然后在60℃下干燥4小时，采用X射线物相衍射证实物相变化，用扫描电子显微镜观察表面形貌的变化。所得到的氟硅酸钙陶瓷，其主要的结构性能和生物矿化能力与实施例1相似。
力学性能测试结果显示，本实施例提供的样品抗弯强度为60MPa，弹性模量为22.5GPa。
实施例4：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取氧化钙CaO：4.206克，氧化硅SiO2：1.8027克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是830℃，烧结时间9小时，然后冷却至室温，取出样品；将预烧结的原料再次与1.952克氟化钙CaF2充分混合研磨均匀，将混合粉体进行压制成型，压制压力为13MPa，在空气气氛中再次煅烧，煅烧温度1100℃，煅烧时间6小时，自然冷却即得到氟硅酸钙生物陶瓷。
将制备好的氟硅酸钙陶瓷放入模拟体液矿化3天，观察矿化后的表面形貌，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，评价其生物活性。氟硅酸钙陶瓷加入模拟体液30毫升/平方厘米，将矿化不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水清洗，然后在60℃下干燥5小时，采用X射线物相衍射证实物相变化，用扫描电子显微镜观察表面形貌的变化。所得到的氟硅酸钙陶瓷，其主要的结构性能和生物矿化能力与实施例2相似。
力学性能测试结果显示，本实施例提供的样品抗弯强度为90MPa，弹性模量为75GPa。
实施例5：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取硝酸钙Ca(NO3)2·4H2O：20.072克，氧化硅SiO2：1.8027克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是870℃，烧结时间5小时，然后冷却至室温，取出样品；将预烧结的原料再次与1.1712克氟化钙CaF2充分混合研磨均匀，将混合粉体进行压制成型，压制压力为14MPa，在空气气氛中再次煅烧，煅烧温度980℃，煅烧时间7小时，自然冷却即得到氟硅酸钙生物陶瓷。
将制备好的氟硅酸钙陶瓷放入模拟体液矿化7天，观察矿化后的表面形貌变化，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，评价其生物活性。氟硅酸钙陶瓷加入模拟体液30毫升/平方厘米。将矿化不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水清洗，然后在60℃下干燥4小时，采用X射线物相衍射证实物相变化，用扫描电子显微镜观察表面形貌的变化。所得到的氟硅酸钙陶瓷，其主要的结构性能和生物矿化能力与实施例2相似。
力学性能测试结果显示，本实施例提供的样品抗弯强度为76MPa，弹性模量为46GPa。
实施例6：
(1)根据Ca10Si3O15F2中元素的摩尔比，称取氧化钙CaO：3.365克，氧化硅SiO2：1.8027克，在玛瑙研钵中研磨并混合均匀后，选择空气气氛预烧结，烧结温度是920℃，烧结时间7小时，然后冷却至室温，取出样品；将预烧结的原料再次与3.1232克氟化钙CaF2充分混合研磨均匀，将混合粉体进行压制成型，压制压力为14MPa，在空气气氛中再次煅烧，煅烧温度1050℃，煅烧时间6小时，自然冷却即得到氟硅酸钙生物陶瓷。
将制备好的氟硅酸钙陶瓷放入模拟体液矿化3天，观察矿化后的表面形貌变化，判断氟硅酸钙陶瓷表面是否有类骨磷灰石层形成，评价其生物活性。氟硅酸钙陶瓷加入模拟体液30毫升/平方厘米。将矿化不同时间段的氟硅酸钙陶瓷从模拟体液中取出，用去离子水清洗，然后在60℃下干燥4小时，采用X射线物相衍射证实物相变化，用扫描电子显微镜观察表面形貌的变化。所得到的氟硅酸钙陶瓷，其主要的结构性能和生物矿化能力与实施例1相似。
力学性能测试结果显示，本实施例提供的样品抗弯强度为61MPa，弹性模量为38GPa。
Claims (7)
1.一种具有生物活性的陶瓷材料的制备方法，其特征在于，具体步骤如下：
（1）将含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物为原料，按照Ca10Si3O15F2的化学计量比称取各原料，研磨混合均匀，得到两者混合物；
（2）将步骤（1）得到的含钙离子Ca2+和硅离子Si4+的混合物在空气气氛下进行烧结，烧结温度为：750～950℃，烧结时间为：3～10小时；自然冷却，研磨混合均匀；
（3）将步骤（2）得到的粉体混合物与含有氟离子F-的化合物研磨均匀，压制成陶瓷片，压制压力为10MPa～15 MPa，压制好后进行煅烧，煅烧温度为：900～1200℃，烧结时间为：3～15小时，自然冷却，研磨混合均匀，得到生物陶瓷材料。
2.根据权利要求1所述的具有生物活性的陶瓷材料的制备方法，其特征在于：所述的含有钙离子Ca2+的化合物为碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙的一种；所述含有硅离子Si4+的化合物为二氧化硅或硅酸中的一种；所述的含有氟离子F-的化合物为氟化钙。
3.根据权利要求1所述的具有生物活性的陶瓷材料的制备方法，其特征在于：所述含有钙离子Ca2+的化合物有两种，其中一种是氟化钙，氟化钙提供的钙占总钙量的10vol%～40vol%，另一种来源于碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙中的一种。
4.根据权利要求1所述的具有生物活性的陶瓷材料的制备方法，其特征在于，步骤（2）的烧结温度为800～950℃，烧结时间为4～10小时；步骤（3）的煅烧温度为950～1200℃，煅烧时间为5～10小时。
5.根据权利要求1所述的具有生物活性的陶瓷材料的制备方法，其特征在于，步骤（2）的烧结温度为830℃，烧结时间为9小时；步骤（3）中，压制压力为13MPa，煅烧温度为1100℃，煅烧时间为6小时。
6.一种具有生物活性的陶瓷材料，其特征在于，其由权利要求1-5任一所述的制备方法制备而成。
7.一种如权利要求6所述的具有生物活性的陶瓷材料的应用，其特征在于，将具有生物活性的陶瓷材料置于模拟体液中进行矿化后，在其表面得到稳定的类骨羟基磷灰石，可以用于骨修复、骨缺损填充和牙齿修复填充。
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