CN115141038A - 一种增强粘接能力的氧化锆陶瓷粘接面改性方法 - Google Patents
一种增强粘接能力的氧化锆陶瓷粘接面改性方法 Download PDFInfo
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Abstract
本发明涉及一种增强粘接能力的氧化锆陶瓷粘接面改性方法。所述改性方法为:在氧化锆修复体胚体粘接面涂覆氟磷灰石微晶玻璃,形成以氧化锆修复体胚体为主体,从内到外依次为玻璃/锆混合层、氟磷灰石玻璃层的氧化锆陶瓷修复体。本发明在未烧结的氧化锆修复体胚体粘接面涂覆氟磷灰石微晶玻璃,形成了表面是氟磷灰石玻璃层、下面是玻璃/锆混合层,主体是氧化锆的材料结构,增加其粘接能力和机械强度,本发明方法对氧化锆陶瓷在临床上更为广泛的应用具有重要意义。
Description
技术领域
本发明涉及一种增强粘接能力的氧化锆陶瓷粘接面改性方法,属于牙科修复材料技术领域。
背景技术
牙体缺损是口腔修复中的常见病和多发病,氧化锆因为具有优越的机械性能、美观性能和良好的生物相容性,所以该材料在口腔医学领域中应用越来越广泛,如制作嵌体、全冠、种植体及基台等,其中应用最为广泛的是氧化锆全冠。因为氧化锆晶体具有化学惰性,所以其表面不能被氢氟酸酸蚀等常规处理玻璃陶瓷表面的方式处理,因此丧失粘接力是氧化锆修复体常见失败的原因之一。目前对于增加氧化锆粘接效果的处理方式有很多种,如喷砂、强酸酸蚀、激光处理和硅涂层等。但是目前常见的处理方式有以下缺点:喷砂处理后有微裂纹进而可能会影响强度,强酸酸蚀过程复杂且危险,激光处理可能会影响其结构改变,单纯硅涂层增加粘接的效果不明显,所以氧化锆表面的处理方式一直是研究的热点。
近年来玻璃渗透氧化锆是一种氧化锆表面改性且可以有效增加粘接效果的处理方式,常见的方法是将二硅酸锂玻璃渗透到烧结的氧化锆表面,在氧化锆表面形成一层硅酸锂玻璃层,进而可以使氧化锆同玻璃陶瓷一样粘接前酸蚀、硅烷化处理,保证有良好的粘接效果。目前,玻璃渗透方法多是在已经完全烧结或者半烧结的锆表面涂二硅酸锂玻璃陶瓷,因为完全烧结的氧化锆表面致密,很难与表面的玻璃形成混合层,所以二者之间的结合界面可能会出现裂隙、剥脱或者应力集中的可能,进而影响氧化锆的机械性能和粘接性能。因此,探究一种在不改变氧化锆机械性能的前提下,对氧化锆进行玻璃渗透,使两者之间形成良好的结合,同时增加其粘接性能的的方法是很有临床意义的。
发明内容
针对现有技术的不足,本发明提供一种增强粘接能力的氧化锆陶瓷粘接面改性方法。
本发明的技术方案如下:
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,所述改性方法为:在氧化锆修复体胚体粘接面涂覆氟磷灰石微晶玻璃,形成以氧化锆修复体胚体为主体,从内到外依次为玻璃/锆混合层、氟磷灰石玻璃层的氧化锆陶瓷修复体。
根据本发明优选的,所述氧化锆修复体胚体为通过计算机辅助设备切削冷压成型的未烧结的氧化锆胚体盘而成;其化学成分包括:质量百分比≥99%的ZrO2·HfO2·Y2O3,质量百分比为4.5~6%的Y2O3,质量百分比≤0.5%的Al2O3。这种未烧结的氧化锆胚体盘是目前计算机辅助切削修复体的原料,因为这是将氧化锆颗粒冷压成型的,尚未烧结结晶,在扫描电镜下呈现出疏松多孔的状态。
根据本发明优选的,所述氟磷灰石微晶玻璃,按质量百分比计,包括组分:54.6%SiO2、14.4%Al2O3、8.6%Na2O、4.2%K2O、4.0%P2O5、1.5%ZrO2、0.7%F、0.2%Li2O、6.0%CaO、1.0%TiO2、0.8%CeO2、3.0%ZnO、1.0%B2O3。所述氟磷灰石微晶玻璃使用时为粉状。
根据本发明优选的,所述玻璃/锆混合层的玻璃含量有表层至深层逐渐减少直至消失。
根据本发明优选的,所述氟磷灰石玻璃层的厚度为25~35μm。
根据本发明优选的,所述增强粘接能力的氧化锆陶瓷粘接面改性方法,具体包括步骤如下:
(1)将冷压成型未烧结的氧化锆修复体胚体超声震荡清理3~8min,然后在红外线干燥灯下干燥20~40min;
(2)将氟磷灰石微晶玻璃和蒸馏水混合配制成浓度为400~600mg/mL的氟磷灰石微晶玻璃浆液,将氟磷灰石微晶玻璃浆液均匀地涂覆在氧化锆修复体胚体的粘接面,然后在红外线干燥灯下干燥20~40min,得到涂覆好的氧化锆;
(3)将涂覆好的氧化锆在1450~1580℃下烧结1.5~2.5h,得到改性后的氧化锆陶瓷。
根据本发明优选的,步骤(1)中,所述超声震荡清理时间为5min,干燥时间为30min。
根据本发明优选的,步骤(2)中,所述氟磷灰石微晶玻璃浆液的浓度为500mg/mL,干燥时间为30min。
根据本发明优选的,步骤(3)中,所述烧结温度为1530℃,烧结时间为2h。
本发明的有益效果为:
本发明在未烧结的氧化锆修复体胚体粘接面涂覆氟磷灰石微晶玻璃,形成了表面是氟磷灰石玻璃层、下面是玻璃/锆混合层,主体是氧化锆的材料结构。通过将氟磷灰石作为氧化锆渗透材料进行表面改性,可将氧化锆粘接面改性成为氟磷灰石玻璃陶瓷,进而增加其粘接能力。同时在未烧结的疏松多孔的氧化锆胚体表面渗透,可形成的玻璃/锆混合层作为表面氟磷灰石玻璃层和氧化锆主体之间的过渡层,可以有效的增加两者的结合性能且能传递应力进而增加氧化锆的机械强度,本发明方法对氧化锆陶瓷在临床上更为广泛的应用具有重要意义。
附图说明
图1是未烧结氧化锆修复体胚体和烧结后氧化锆扫描电镜照比较图。
图2是氟磷灰石微晶玻璃渗透氧化锆修复体胚体过程示意图。
图3是氟磷灰石微晶玻璃渗透氧化锆后的扫描电镜。
图4是实验机械强度对比图。
图5是剪切强度测试和疲劳试验结果图。
图6是不同浓度氟磷灰石微晶玻璃渗透后获得不同厚度玻璃的扫描电镜图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例中所用原材料及设备均为常规市购产品。
实施例1
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,包括步骤如下:
(1)将未烧结的氧化锆修复体胚体超声震荡清理5min,然后在红外线干燥灯下干燥30min;
(2)将氟磷灰石微晶玻璃和蒸馏水混合配制成浓度为500mg/mL的氟磷灰石微晶玻璃浆液,用毛笔将氟磷灰石微晶玻璃浆液均匀地涂覆在氧化锆修复体胚体粘接面,均匀涂刷一层,,然后在红外线干燥灯下干燥30min,得到涂覆好的氧化锆;
(3)将涂覆好的氧化锆放置在氧化锆烧结炉中,于1530℃下烧结2h,得到改性后的氧化锆陶瓷。
其中,所述氧化锆修复体胚体为通过计算机辅助设备切削冷压成型的未烧结的氧化锆胚体盘而成;其化学成分包括:质量百分比≥99%的ZrO2·HfO2·Y2O3,质量百分比为4.5~6%的Y2O3,质量百分比≤0.5%的Al2O3。这种未烧结的氧化锆胚体盘是目前计算机辅助切削修复体的原料,因为这是将氧化锆颗粒冷压成型的,尚未烧结结晶,在扫描电镜下呈现出疏松多孔的状态。
所述氟磷灰石微晶玻璃,按质量百分比计,包括组分:54.6%SiO2、14.4%Al2O3、8.6%Na2O、4.2%K2O、4.0%P2O5、1.5%ZrO2、0.7%F、0.2%Li2O、6.0%CaO、1.0%TiO2、0.8%CeO2、3.0%ZnO、1.0%B2O3。所述氟磷灰石微晶玻璃使用时为粉状。
本发明首先采用的是冷压成型未烧结的氧化锆胚体作为主体,未烧结氧化锆胚体和烧结后氧化锆扫描电镜照如图1所示。由图1可知,未烧结的氧化锆表面疏松多孔,为氟磷灰石微晶玻璃渗透提供了可能,而烧结后的氧化锆表面结构致密,很难再将氟磷灰石微晶玻璃渗入其中。然后通过将氟磷灰石作为氧化锆渗透材料进行表面改性,可将氧化锆表面改性成为氟磷灰石玻璃陶瓷,具体渗透过程如图2所示。氟磷灰石微晶玻璃渗透氧化锆后,完成改性的氧化锆陶瓷的断面冠可见氟磷灰石玻璃陶瓷和氧化锆之间形成了良好相互交错,形成了良好的混合层,将表面的玻璃酸蚀掉之后的扫描电镜也证明两者之间存在了良好的混合。
实施例2
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,步骤如实施例1所述,不同之处在于,所述氟磷灰石微晶玻璃浆液的浓度为400mg/mL。
实施例3
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,步骤如实施例1所述,不同之处在于,所述氟磷灰石微晶玻璃浆液的浓度为600mg/mL。
对比例1
一种二硅酸锂玻璃渗透到烧结完成氧化锆表面改性的方法,包括步骤如下:
将二硅酸锂玻璃粉混合成浆液,粉刷涂布在已经完成烧结结晶或者半结晶的氧化锆修复体表面,然后通过低温烧结的方式进行二次烧结,将二硅酸锂玻璃烧结到氧化锆表面。
本发明与其相比主要有两点不同:一是采用的氟磷灰石微晶玻璃,它既能将表面改性为玻璃增加粘接效果,同时可发挥氟磷灰石中氟元素抗龋的潜在作用;二是渗透时机是在未烧结的胚体表面,此时氧化锆表面疏松多孔,较结晶后的致密锆表面更易渗透其中,形成玻璃/锆混合层以避免在两者之间形成间隙,以达到应力传递,增加机械强度的作用。
对比例2
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,步骤如实施例1所述,不同之处在于,所述氟磷灰石微晶玻璃浆液的浓度为200mg/mL。
对比例3
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,步骤如实施例1所述,不同之处在于,所述氟磷灰石微晶玻璃浆液的浓度为300mg/mL。
对比例4
一种增强粘接能力的氧化锆陶瓷粘接面改性方法,步骤如实施例1所述,不同之处在于,所述氟磷灰石微晶玻璃浆液的浓度为700mg/mL。
试验例
1、将实施例1的氧化锆陶瓷、未处理氧化锆和喷砂氧化锆进行机械强度、剪切强度测试和疲劳试验,结果如图4和图5所示。
机械强度测试方法:将三组样本加工成2*2*25mm的长条,进行单轴三点弯曲实验。通过实验结果可以出氟磷灰石微晶玻璃渗透氧化锆的机械强度较其余两种方法有所增强,说明该发明可以增强氧化锆的机械强度。
剪切强度测试方法:将三组样本加工成10*10*2mm的薄片,包埋至直径25mm的PVC管内,将50μm厚的双面胶打一直径3mm的圆孔粘在样本上,然后按照常规玻璃陶瓷修复体粘接的方式氢氟酸酸蚀1min,吹干,涂布粘接剂,将一直径4.4mm的树脂柱粘接在样本的圆孔上,光固化40秒。然后利用万能测试机进行剪切粘接强度测试,记录最大破坏载荷。
疲劳试验为将粘接好的样本放在5℃和555的热循环器中进行热循环5000次,每次停留时间为20秒,传递时间为3秒,以此来模拟疲劳实验。
由图4可知,与未处理氧化锆和喷砂氧化锆相比,实施例1所制备氧化锆陶瓷的机械强度明显提高,说明氟磷灰石微晶玻璃渗透氧化锆后形成的玻璃/锆混合层作为表面氟磷灰石玻璃层和氧化锆主体之间的过渡层,可以有效的增加两者的结合性能且能传递应力进而增加氧化锆的机械强度。
由图5可知,与未处理氧化锆和喷砂氧化锆相比,实施例1所制备氧化锆陶瓷的剪切强度明显提高,且进行疲劳试验后,其粘接强度仍未见明显降低,说明通过将氟磷灰石作为氧化锆渗透材料进行表面改性,可将氧化锆表面改性成为氟磷灰石玻璃陶瓷,进而增加其粘接能力。
2、对实施例1~3和对比例2~4制备的改性后的氧化锆陶瓷进行电镜扫描,结果如图6所示。由图6可知,当氟磷灰石微晶玻璃浆液的浓度为400~600mg/mL时,氟磷灰石微晶玻璃浆液能充分覆盖氧化锆表面,使得氟磷灰石玻璃层的厚度为25~35μm。特别是氟磷灰石微晶玻璃浆液的浓度为500mg/mL时,可以得到既能完全覆盖氧化锆表面,厚度又可薄至30μm氟磷灰石微晶玻璃层,这样既能增加其粘接性能,又不至于影响修复体的就位适合性。
Claims (8)
1.一种增强粘接能力的氧化锆陶瓷粘接面改性方法,其特征在于,所述改性方法为:在氧化锆修复体胚体粘接面涂覆氟磷灰石微晶玻璃,形成以氧化锆修复体胚体为主体,从内到外依次为玻璃/锆混合层、氟磷灰石玻璃层的氧化锆陶瓷修复体。
2.如权利要求1所述的改性方法,其特征在于,所述氧化锆修复体胚体为通过计算机辅助设备切削冷压成型的未烧结的氧化锆胚体盘而成;其化学成分包括:质量百分比≥99%的ZrO2·HfO2·Y2O3,质量百分比为4.5~6%的Y2O3,质量百分比≤0.5%的Al2O3。
3.如权利要求1所述的改性方法,其特征在于,所述氟磷灰石微晶玻璃,按质量百分比计,包括组分:54.6%SiO2、14.4%Al2O3、8.6%Na2O、4.2%K2O、4.0%P2O5、1.5%ZrO2、0.7%F、0.2%Li2O、6.0%CaO、1.0%TiO2、0.8%CeO2、3.0%ZnO、1.0%B2O3。
4.如权利要求1所述的改性方法,其特征在于,所述氟磷灰石玻璃层的厚度为25~35μm。
5.如权利要求1所述的改性方法,其特征在于,所述增强粘接能力的氧化锆陶瓷粘接面改性方法,具体包括步骤如下:
(1)将冷压成型未烧结的氧化锆修复体胚体超声震荡清理3~8min,然后在红外线干燥灯下干燥20~40min;
(2)将氟磷灰石微晶玻璃和蒸馏水混合配制成浓度为400~600mg/mL的氟磷灰石微晶玻璃浆液,将氟磷灰石微晶玻璃浆液均匀地涂覆在氧化锆修复体胚体的粘接面,然后在红外线干燥灯下干燥20~40min,得到涂覆好的氧化锆;
(3)将涂覆好的氧化锆在1450~1580℃下烧结1.5~2.5h,得到改性后的氧化锆陶瓷修复体。
6.如权利要求5所述的改性方法,其特征在于,步骤(1)中,所述超声震荡清理时间为5min,干燥时间为30min。
7.如权利要求5所述的改性方法,其特征在于,步骤(2)中,所述氟磷灰石微晶玻璃浆液的浓度为500mg/mL,干燥时间为30min。
8.如权利要求5所述的改性方法,其特征在于,步骤(3)中,所述烧结温度为1530℃,烧结时间为2h。
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