CN112110740B - 一种原位反应制备氧化铝基复合生物陶瓷材料的方法及其制得的产品 - Google Patents

一种原位反应制备氧化铝基复合生物陶瓷材料的方法及其制得的产品 Download PDF

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CN112110740B
CN112110740B CN202011031530.4A CN202011031530A CN112110740B CN 112110740 B CN112110740 B CN 112110740B CN 202011031530 A CN202011031530 A CN 202011031530A CN 112110740 B CN112110740 B CN 112110740B
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汪永清
洪毓鸿
白明敏
施德太
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Jingdezhen Ceramic Institute
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Abstract

本发明公开了一种原位反应制备氧化铝基复合生物陶瓷材料的方法，以氧化铝、3mol％Y2O3稳定氧化锆和硝酸镨为原料，经球磨混料、加热旋转干燥而得到前驱物粉料；然后将所述前驱物粉料进行造粒、干压成型得到的陶瓷生坯，在空气气氛下以5～15℃/min升温至1400～1600℃，保温时间为0.5～1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。此外，还公开了利用上述制备方法制得的产品。本发明工艺简便，采用常压低温烧结，原位合成的增韧相均匀分散且与基体界面结合良好，显微结构均匀，致密度高，从而具有优异的力学性能，并适合于工业化大批量生产。

Description

一种原位反应制备氧化铝基复合生物陶瓷材料的方法及其制 得的产品
技术领域
本发明涉及医用生物材料技术领域，尤其涉及一种原位反应制备氧化铝基复合生物陶瓷材料的方法及其制得的产品。
背景技术
氧化铝(Al2O3)陶瓷硬度高，并具有优异的耐磨及耐腐蚀性、生物相容性及生物惰性，因此被认为是较理想的人工关节假体，但也存在着脆性高及可靠性低等结构陶瓷所固有的缺点，使得其作为生物陶瓷在应用上受到了限制。
单相氧化铝陶瓷的强度通常在400～500MPa，断裂韧性在3～4MPa·m1/2左右。然而，在常温下材料呈现出脆性或者韧性是受到材料的成分、结构、受力环境和条件等多因素综合影响的，而材料内部不同的显微结构在宏观外力作用下，也会表现出不同的力学性能。因此，通过对材料断裂机理的研究，借以有效调控材料的显微结构并最终实现材料性能的改善已成为材料科学研究中一项重要的研究内容。
近年来的研究主要通过两种方法来提高陶瓷材料的韧性和可靠性：一是通过引入新工艺制备陶瓷材料，从而控制陶瓷材料的微观结构，减少内部缺陷尺寸，来提高陶瓷材料机械性能。二是采用各种增韧方法来改善陶瓷材料对外加应力的分散机制，从而使材料对缺陷的敏感性降低。
研究发现：在氧化铝基体中引入SiC晶须，可以大幅度提高材料的断裂韧性，但由于晶须在批量生产、分散以及后续的烧结过程中，结构容易被破坏，而且加入的晶须与基体在化学上的相容性和物理上的热膨胀系数存在差异，因此需要对晶须进行表面改性；同时还由于成型密度低，不易烧结致密，需采用特殊的烧结方法，所以此方法的应用受到了限制。而原位生长板状晶免去了因使用晶须在工艺上造成的困难，相对于单相氧化铝陶瓷虽然在力学性能上有大幅改善，但仍存在着液相和晶种在氧化铝基体中不易均匀分散、与基体的结合性能不好、需要热压烧结等问题，不利于实现工业化大批量生产。
发明内容
本发明的目的在于克服现有技术的不足，提供一种工艺简便、烧结温度低、增韧相均匀分散且与基体界面结合良好的原位反应制备氧化铝基复合生物陶瓷材料的方法，以获得力学性能优异的生物陶瓷材料，并适合于工业化大批量生产。本发明的另一目的在于提供利用上述原位反应制备氧化铝基复合生物陶瓷材料的方法制得的产品。
本发明的目的通过以下技术方案予以实现：
本发明提供的一种原位反应制备氧化铝基复合生物陶瓷材料的方法，包括以下步骤：
(1)按照质量比3Y-ZrO2∶(Al2O3+Pr2O3)＝1∶4～9，其中Al2O3∶Pr2O3＝15～89∶1，以无水乙醇为介质，将氧化铝、3mol％Y2O3稳定氧化锆和硝酸镨进行湿法球磨混料，得到前驱物浆料；
(2)采用旋转蒸发干燥仪对所述前驱物浆料进行加热旋转干燥后，过筛得到前驱物粉料；
(3)将所述前驱物粉料进行造粒、干压成型，得到陶瓷生坯；
(4)所述陶瓷生坯在空气气氛下以5～15℃/min升温至1400～1600℃，保温时间为0.5～1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
为进一步控制所得生物陶瓷的基体粒径，本发明所述步骤(1)中加入聚丙烯酸或聚丙烯酸铵作为分散剂，所述分散剂的用量为氧化铝固含量的1～3wt％。此外，所述步骤(1)中球磨的转速为300～400r/min，球磨时间为6～10h。
上述方案中，本发明所述步骤(2)前驱物浆料以50～80℃的水浴温度持续加热旋转干燥1～4h。
为进一步提高陶瓷生坯的致密度，本发明所述步骤(3)造粒中加入聚乙烯醇作为粘结剂，其加入量为前驱物粉料的0.5～1.5wt％，以浓度为5％的聚乙烯醇水溶液形式加入。
利用上述原位反应制备氧化铝基复合生物陶瓷材料的方法制得的产品，由Al2O3基体、均匀分散在Al2O3基体中的ZrO2晶粒和原位合成的增韧相板状六铝酸镨晶粒构成，并且所述板状六铝酸镨晶粒内有弥散的氧化锆颗粒。
上述方案中，本发明所述板状六铝酸镨晶粒的长度为0.5～0.8μm，长径比为5～10。
本发明具有以下有益效果：
(1)本发明所选用的硝酸镨作为镨源，在烧结过程中与氧化铝原位固相反应生成板状六铝酸镨晶粒，通过湿法球磨保证了前驱物中的均匀分布，同时借助旋转蒸发仪可以有效克服在传统烘箱干燥中发生的偏析。
(2)本发明中板状六铝酸镨晶粒在烧结过程中原位生长，与Al2O3基体界面结合紧密，既避免了直接加入板状晶对致密度及力学性能的不良影响，又不会出现通过引入玻璃相各向异性生长而造成的大量晶间气孔，还可以控制板状晶的生成数量。
(3)本发明中板状晶在断裂过程中为台阶状穿晶断裂，同时板状晶内有弥散的氧化锆颗粒起到裂纹钉扎、偏转的作用，避免了传统板状晶的脆性穿晶平面断裂，提高了材料的强度(抗弯强度为620～850MPa)和韧性(断裂韧性为4～7MPa·m1/2)。
(4)本发明采用常压低温烧结，显微结构均匀，致密度高，力学性能优异。
(5)本发明所采用的制备工艺简单，降低了生物陶瓷的制备成本，适合于工业化批量生产。
附图说明
下面将结合实施例和附图对本发明作进一步的详细描述：
图1是本发明实施例制备的氧化铝基复合生物陶瓷材料的XRD图谱；
图2是本发明实施例制备的氧化铝基复合生物陶瓷材料的扫描电镜断口形貌图。
具体实施方式
实施例一：
本实施例一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其步骤如下：
(1)称取89g氧化铝、10g 3mol％Y2O3稳定氧化锆、1g硝酸镨、0.89g聚丙烯酸，以50mL无水乙醇为介质，加入行星式球磨罐中以300r/min转速球磨混合8h，得到前驱物浆料；
(2)将上述前驱物浆料倒入旋转蒸发干燥仪以60℃的水浴温度持续加热旋转干燥2h后，过100目筛得到前驱物粉料；
(3)上述前驱物粉料用浓度为5％的聚乙烯醇水溶液(聚乙烯醇的用量为混合粉料的0.5wt％)造粒，然后在20MPa压力下干压成型而得到陶瓷生坯；
(4)上述陶瓷生坯在高温炉中空气气氛下，以10℃/min升温至1500℃，保温1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
实施例二：
本实施例一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其步骤如下：
(1)称取79g氧化铝、20g 3mol％Y2O3稳定氧化锆、1g硝酸镨、1.58g聚丙烯酸，以50mL无水乙醇为介质，加入行星式球磨罐中以350r/min转速球磨混合8h，得到前驱物浆料；
(2)将上述前驱物浆料倒入旋转蒸发干燥仪以60℃的水浴温度持续加热旋转干燥1h后，过100目筛得到前驱物粉料；
(3)上述前驱物粉料用浓度为5％的聚乙烯醇水溶液(聚乙烯醇的用量为混合粉料的1wt％)造粒，然后在20MPa压力下干压成型而得到陶瓷生坯；
(4)上述陶瓷生坯在高温炉中空气气氛下，以10℃/min升温至1600℃，保温1h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
实施例三：
本实施例一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其步骤如下：
(1)称取75g氧化铝、20g 3mol％Y2O3稳定氧化锆、5g硝酸镨、2.25g聚丙烯酸，以50mL无水乙醇为介质，加入行星式球磨罐中以400r/min转速球磨混合8h，得到前驱物浆料；
(2)将上述前驱物浆料倒入旋转蒸发干燥仪以60℃的水浴温度持续加热旋转干燥2h后，过100目筛得到前驱物粉料；
(3)上述前驱物粉料用浓度为5％的聚乙烯醇水溶液(聚乙烯醇的用量为混合粉料的1.5wt％)造粒，然后在20MPa压力下干压成型而得到陶瓷生坯；
(4)上述陶瓷生坯在高温炉中空气气氛下，以15℃/min升温至1550℃，保温1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
实施例四：
本实施例一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其步骤如下：
(1)称取77g氧化铝、20g 3mol％Y2O3稳定氧化锆、3g硝酸镨、0.77g聚丙烯酸，以50mL无水乙醇为介质，加入行星式球磨罐中以400r/min转速球磨混合10h，得到前驱物浆料；
(2)将上述前驱物浆料倒入旋转蒸发干燥仪以60℃的水浴温度持续加热旋转干燥3h后，过100目筛得到前驱物粉料；
(3)上述前驱物粉料用浓度为5％的聚乙烯醇水溶液(聚乙烯醇的用量为混合粉料的0.5wt％)造粒，然后在20MPa压力下干压成型而得到陶瓷生坯；
(4)上述陶瓷生坯在高温炉中空气气氛下，以5℃/min升温至1500℃，保温1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
实施例五：
本实施例一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其步骤如下：
(1)称取77g氧化铝、20g 3mol％Y2O3稳定氧化锆、3g硝酸镨、0.77g聚丙烯酸，以50mL无水乙醇为介质，加入行星式球磨罐中以400r/min转速球磨混合10h，得到前驱物浆料；
(2)将上述前驱物浆料倒入旋转蒸发干燥仪以60℃的水浴温度持续加热旋转干燥2h后，过100目筛得到前驱物粉料；
(3)上述前驱物粉料用浓度为5％的聚乙烯醇水溶液(聚乙烯醇的用量为混合粉料的0.5wt％)造粒，然后在20MPa压力下干压成型而得到陶瓷生坯；
(4)上述陶瓷生坯在高温炉中空气气氛下，以10℃/min升温至1550℃，保温1.5h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料。
本发明实施例制备的氧化铝基复合生物陶瓷材料，如图1所示，其特征衍射峰与Al2O3标准卡片(JCPDS编号97-005-2024)、ZrO2标准卡片(JCPDS编号97-007-9197)、Pr0.833Al11.833O19标准卡片(JCPDS编号97-007-4317)相一致，表明晶粒发育良好，不存在杂质相。ZrO2晶粒以及原位合成的增韧板状Pr0.833Al11.833O19晶粒均匀分散在Al2O3基体中。
如图2所示，板状Pr0.833Al11.833O19晶粒的长度约为0.6μm，长径比约为8。板状晶在基体中分散均匀，且与基体界面结合良好，板状晶粒内有弥散的氧化锆颗粒。从图2中还可以看出，所制备的陶瓷材料的断裂方式为：在基体上以沿晶断裂为主、在自增韧板状晶处为先裂纹桥连和板状晶拔出，超过板状晶断裂极限后发生穿晶断裂。这种混合断裂模式能显著消耗裂纹扩展的能量，从而有效提高生物陶瓷材料的力学性能。
本发明实施例制备的陶瓷材料经磨削、抛光等工艺得到成品样品，采用三点弯曲法，用WOW-20电子万能试验机以跨度30mm，十字头速度0.5mm/min，对4mm×3mm×30mm试样进行弯曲强度(σ)测试。每个试样用金刚石膏(3μm)抛光，边缘倒角(约45°)。样品的抗弯强度由下式给出：
Figure BDA0002703859850000061
式中，σ为抗弯强度(MPa)，F为断裂载荷(N)，b为试样宽度(mm)，h为试样厚度(mm)，L为跨距(mm)。
根据GB/T 23806—2009单边预裂纹梁(SEPB)法，对尺寸为3mm×4mm×36mm的试样进行断裂韧性试验。在其中心引入一个切口深度A相对长度为A/W≈0.4的尖锐V形切口，以获得用于断裂韧性评估的单边V形切口梁(SEVNB)结构。对每种材料共5个试样进行测试，结果为平均值。
测得的性能指标如表1所示。
表1本发明实施例制备的陶瓷材料的性能指标
Figure BDA0002703859850000062

Claims (2)

1.一种原位反应制备氧化铝基复合生物陶瓷材料的方法，其特征在于包括以下步骤：
(1) 按照质量比3Y-ZrO2∶(Al2O3+Pr2O3)＝1∶4～9，其中Al2O3∶Pr2O3＝15～89∶1，以无水乙醇为介质，将氧化铝、3mol%Y2O3稳定氧化锆、硝酸镨和分散剂进行湿法球磨混料，球磨的转速为300～400 r/min，球磨时间为6～10 h，得到前驱物浆料；所述分散剂为聚丙烯酸或聚丙烯酸铵，其用量为氧化铝固含量的1～3 wt%；
(2) 采用旋转蒸发干燥仪对所述前驱物浆料以50～80℃的水浴温度持续加热旋转干燥1～4 h后，过筛得到前驱物粉料；
(3) 将所述前驱物粉料加入聚乙烯醇作为粘结剂进行造粒，粘结剂的加入量为前驱物粉料的0.5～1.5 wt%，以浓度为5%的聚乙烯醇水溶液形式加入，经干压成型，得到陶瓷生坯；
(4) 所述陶瓷生坯在空气气氛下以5～15℃/min升温至1400～1600℃，保温时间为0.5～1.5 h，随炉冷却后即制得原位生长板状晶增韧的氧化铝基复合生物陶瓷材料；所述陶瓷材料由Al2O3基体、均匀分散在Al2O3基体中的ZrO2晶粒和原位合成的增韧相板状六铝酸镨晶粒构成；所述板状六铝酸镨晶粒的长度为0.5～0.8 μm、长径比为5～10，其断裂过程中为台阶状穿晶断裂，板状晶粒内有弥散的氧化锆颗粒起到裂纹钉扎、偏转的作用；所述陶瓷材料的抗弯强度为620～850 MPa、断裂韧性为4～7 MPa∙m1/2。
2.利用权利要求1所述原位反应制备氧化铝基复合生物陶瓷材料的方法制得的产品。
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