CN113185281A - 一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料 - Google Patents

一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料 Download PDF

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CN113185281A
CN113185281A CN202110747833.4A CN202110747833A CN113185281A CN 113185281 A CN113185281 A CN 113185281A CN 202110747833 A CN202110747833 A CN 202110747833A CN 113185281 A CN113185281 A CN 113185281A
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ceramic material
titanium dioxide
magnesium alloy
ion implantation
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CN113185281B (zh
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朱剑熹
韩斐
刘俊彦
朱勇
罗浩
郭斌
胡懿郃
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Xiangya Hospital of Central South University
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Abstract

一种溶胶‑凝胶法制备而得的二氧化钛陶瓷材料,通过离子注入法在二氧化钛多孔陶瓷表面掺入稀土元素铈和钇。本质上,离子注入稀土元素可以起到封孔作用,离子注入后,在二氧化钛陶瓷表面或近表面区域形成了TiO2‑Ce‑Y复合陶瓷材料,提高了多孔二氧化钛的耐腐蚀性能。值得注意的是,稀土元素的注入量需控制在合理的范围,稀土元素注入量过多,则在二氧化钛陶瓷表面形成了Ce‑Y薄膜,稀土元素注入量过少,则无法起到合适的封孔效果,这都不利于多孔二氧化钛陶瓷材料耐腐蚀性能的提高。

Description

一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料
技术领域
本发明涉及陶瓷材料领域,具体涉及一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料。
背景技术
在骨科、口腔外科和胸外科等领域,需要用于骨折修复、胸部支撑的高强度材料称为骨固定材料。骨固定材料有针状、板状等许多种类,起到骨块间辅助连接作用。目前,广泛应用的不锈钢和钛合金的弹性模量都远高于人骨的弹性模量,由此产生的应力遮挡效应不利于骨的生长和愈合。镁合金与人骨的弹性模量接近,可有效缓解应力遮挡效应。镁合金在骨折愈合初期能够提供稳定的力学性能,逐渐降低其应力遮挡作用,使骨折部位承受逐步增大至生理水平的应力刺激,从而加速骨折愈合,防止局部骨质疏松和再骨折的发生。
然而,镁合金在人体内耐腐蚀性能较差,无法在相应的时间内起到足够的力学支撑作用,所以长期以来学者们都在研究如何提高镁合金的耐蚀性能。其中,表面改性是广泛应用的一类方法,镁合金的表面改性包括氟化物涂层、稀土转化膜、磷转化涂层、溶胶-凝胶涂层等。由于对温度要求低,可在常温下进行操作,溶胶-凝胶涂层备受青睐。但是,由于溶胶-凝胶法制备得到的多为多孔薄膜,其致密性较差,这使得在特定场景下溶胶-凝胶涂层的耐腐蚀性能无法满足使用需求。
发明内容
针对现有技术存在的问题,本发明旨在提供一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料,进一步提高现有的二氧化钛医用陶瓷材料的耐腐蚀性能,满足特定医用场景的使用需求。
一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料,制备过程包括以下步骤:
A.选取镁合金为衬底材料;
B.对镁合金进行预处理;
C.制备微弧氧化层;
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5-0.8mol/L,无水乙醇与蒸馏水的积比为1-2∶3-5,并添加溶液体积的3-6%丙三醇作为增稠剂,陈化20-24h;
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2000-2500转/min,而后在烘箱中干燥,干燥温度为180-200℃;
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400-450℃下退火2-2.5h;
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至不高于1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为50-80keV。
进一步地,所述镁合金为医用镁合金。
进一步地,步骤A中将镁合金切割为6×6×2mm的尺寸。
进一步地,所述预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%-15%的碳酸钠溶液,酸洗选用浓度为15%-20%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行。
进一步地,所述步骤C具体为以镁合金为阳极,在10-12A·dm-2的恒定电流密度、脉冲频率450-600Hz、占空比40-45%、终止电压350-400V,时间10-12min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠30-35g/L,氢氧化钾15-20g/L,氟化氢氨8-9g/L,磷酸二氢胺8-12g/L,甘油15-25ml/L,三乙醇胺60-80ml/L。
进一步地,所述Ce离子注入量为6×1013-6×1015ions/cm2,Y离子注入量为6×1013-6×1015ions/cm2
优选地,所述Ce离子注入量为4×1015ions/cm2,Y离子注入量为4×1015ions/cm2
为了提高溶胶-凝胶法制备而得的多孔二氧化钛陶瓷材料的耐腐蚀性能,本发明进一步对其进行离子注入处理,通过离子注入法在二氧化钛多孔陶瓷表面掺入稀土元素铈和钇。本质上,离子注入稀土元素可以起到封孔作用,离子注入后,在二氧化钛陶瓷表面或近表面区域形成了TiO2-Ce-Y复合陶瓷材料,提高了多孔二氧化钛的耐腐蚀性能。值得注意的是,稀土元素的注入量需控制在合理的范围,稀土元素注入量过多,则在二氧化钛陶瓷表面形成了Ce-Y薄膜,稀土元素注入量过少,则无法起到合适的封孔效果,这都不利于多孔二氧化钛陶瓷材料耐腐蚀性能的提高。
具体实施方式
下面通过具体实施例来验证本发明的技术效果,但是本发明的实施方式不局限于此。
实施例1
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为6×1015ions/cm2,Y离子注入量为6×1015ions/cm2
实施例2
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为4×1015ions/cm2,Y离子注入量为4×1015ions/cm2
实施例3
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为5×1014ions/cm2,Y离子注入量为5×1014ions/cm2
实施例4
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为6×1013ions/cm2,Y离子注入量为6×1013ions/cm2
对比例1
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为5×1020ions/cm2,Y离子注入量为5×1020ions/cm2
对比例2
溶胶-凝胶法制备二氧化钛陶瓷材料,包括以下步骤:
A.以医用镁合金为衬底材料,将镁合金切割为6×6×2mm的尺寸;
B.对镁合金进行预处理,预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%的碳酸钠溶液,酸洗选用浓度为15%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行;
C.制备微弧氧化层:以镁合金为阳极,在10A·dm-2的恒定电流密度、脉冲频率450Hz、占空比40%、终止电压400V,时间10min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠35g/L,氢氧化钾15g/L,氟化氢氨8g/L,磷酸二氢胺12g/L,甘油25ml/L,三乙醇胺80ml/L。
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5mol/L,无水乙醇与蒸馏水的积比为1∶3,并添加溶液体积的3%丙三醇作为增稠剂,陈化24h。
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2500转/min,而后在烘箱中干燥,干燥温度为180℃。
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400℃下退火2.5h。
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为80keV,Ce离子注入量为9×1010ions/cm2,Y离子注入量为9×1010ions/cm2
接下来,我们对实施例1-4以及对比例1-2所得到的二氧化钛陶瓷材料的耐腐蚀性能进行测试,并以未进行离子注入处理的二氧化钛陶瓷材料作为空白对照组,具体方法为:在模拟体液(SBF)中,37℃下将各实验样品进行封装,防止边缘效应,而后将其各自置于盛有模拟液的烧杯中,用保鲜膜封住烧杯口,放入37℃的恒温水浴锅中,每两天更新一次模拟体液,并记录样品开始发生腐蚀的情况。表1为各样品的耐腐蚀实验数据,其中“时间”表示样品开始发生腐蚀的时间。
表1 各实验样品的耐腐蚀实验数据
Figure DEST_PATH_IMAGE002
从表1可以看出,对溶胶-凝胶法制备而得的二氧化钛多孔陶瓷材料进行合适含量的离子注入稀土元素Ce和Y后,可以进一步提高其耐腐蚀性能。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。

Claims (7)

1.一种溶胶-凝胶法制备而得的二氧化钛陶瓷材料,其特征在于,制备过程包括以下步骤:
A.选取镁合金为衬底材料;
B.对镁合金进行预处理;
C.制备微弧氧化层;
D.配置二氧化钛溶胶:以无水乙醇和蒸馏水为混合溶剂制备钛酸四丁酯前驱体溶液,其中钛酸四丁酯的浓度为0.5-0.8mol/L,无水乙醇与蒸馏水的积比为1-2∶3-5,并添加溶液体积的3-6%丙三醇作为增稠剂,陈化20-24h;
E.制备二氧化钛陶瓷材料:将步骤D得到的溶胶旋涂于覆有微弧氧化层的镁合金表面,旋涂速度为2000-2500转/min,而后在烘箱中干燥,干燥温度为180-200℃;
F.将步骤E中的二氧化钛陶瓷材料放入真空退火炉中,于400-450℃下退火2-2.5h;
G.离子注入稀土元素:将退火后的二氧化钛陶瓷材料放入离子注入设备中,调节设备的真空度至不高于1×10-4Pa,选用稀土元素Ce和Y进行离子注入,其中离子电压为50-80keV。
2.一种如权利要求1所述的陶瓷材料,其特征在于:所述镁合金为医用镁合金。
3.一种如权利要求1所述的陶瓷材料,其特征在于:步骤A中将镁合金切割为6×6×2mm的尺寸。
4.一种如权利要求1所述的陶瓷材料,其特征在于:所述预处理包括脱脂、酸洗、清洗和烘干,其中脱脂选用浓度为10%-15%的碳酸钠溶液,酸洗选用浓度为15%-20%的盐酸溶液,清洗处理为无水乙醇超声清洗,烘干在氮气气氛下进行。
5.一种如权利要求1所述的陶瓷材料,其特征在于:所述步骤C具体为以镁合金为阳极,在10-12A·dm-2的恒定电流密度、脉冲频率450-600Hz、占空比40-45%、终止电压350-400V,时间10-12min的条件下,制备镁合金微弧氧化层,其中,电解液的组成为六偏磷酸钠30-35g/L,氢氧化钾15-20g/L,氟化氢氨8-9g/L,磷酸二氢胺8-12g/L,甘油15-25ml/L,三乙醇胺60-80ml/L。
6.一种如权利要求1所述的陶瓷材料,其特征在于:所述Ce离子注入量为6×1013-6×1015ions/cm2,Y离子注入量为6×1013-6×1015ions/cm2
7.一种如权利要求6所述的陶瓷材料,其特征在于:所述Ce离子注入量为4×1015ions/cm2,Y离子注入量为4×1015ions/cm2
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