CN116041084A - 一种仿生树脂渗透陶瓷材料及其制备方法 - Google Patents

一种仿生树脂渗透陶瓷材料及其制备方法 Download PDF

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CN116041084A
CN116041084A CN202310059539.3A CN202310059539A CN116041084A CN 116041084 A CN116041084 A CN 116041084A CN 202310059539 A CN202310059539 A CN 202310059539A CN 116041084 A CN116041084 A CN 116041084A
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张佳新
段光远
邢林林
张世强
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Aidite Qinhuangdao Technology Co ltd
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Abstract

本发明提供了一种仿生树脂渗透陶瓷材料及其制备方法,所述仿生树脂渗透陶瓷材料包括陶瓷骨架,所述陶瓷骨架内部设置有通道,所述通道内部填充有填充剂;所述填充剂包括树脂材料和纳米颗粒;所述仿生树脂渗透陶瓷材料分为上部的牙釉质部以及下部的牙本质部;所述通道贯穿牙本质部和牙釉质部,且沿所述牙本质部到所述牙釉质部的方向上,所述通道的直径逐渐变小;所述仿生树脂渗透陶瓷材料通过结构的优化设计,以及填充材料的协同调配,实现了强度、颜色均匀过渡,仿生效果好,具有较好的应用前景。

Description

一种仿生树脂渗透陶瓷材料及其制备方法
技术领域
本发明属于牙科修复技术领域,具体涉及一种仿生树脂渗透陶瓷材料及其制备方法。
背景技术
随着生活和科技水平的进步,人们对牙齿美观性与功能的要求不断提高,口腔修复技术持续发展的同时,口腔修复材料的种类也在不断更新。目前临床中常用的口腔修复材料有金属、牙科用复合树脂和陶瓷材料3大类。由于陶瓷材料具有美观性好、机械强度(硬度、耐磨度、压缩强度、挠曲强度)高、稳定性及氧化程度高、通透性强、良好的X射线投射等特点,因此在目前口腔修复中使用较为普遍。其中氧化锆类陶瓷材料以其优良的美学修复效果、良好的生物相容性日渐受到了医生与患者的青睐。然而氧化锆的基本力学参数与天然牙之间有很大的差异,特别是硬度和弹性模量明显大于牙釉质,氧化锆陶瓷修复体与天然牙在咀嚼运动的过程中产生摩擦磨损,可能造成天然牙的损伤。天然牙的磨耗是一个自然过程,但是由于天然牙的过度磨损可以引起机体自身器官的损伤,因此减少在使用过程中氧化锆修复体对天然牙的磨损是临床应用中迫切需要解决的问题。
CN106336216A公开了一种颜色呈梯度变化的氧化锆牙科陶瓷及其制备方法,包括以下步骤:(1)利用色差仪,将4-6种钇稳定氧化锆彩色粉体按不同质量分数比混合成混合粉体;(2)将混合粉体按照烧结颜色由浅到深的顺序依次加入成型模内分层叠加,进行干压成型;(3)将经干压成型的氧化锆牙科陶瓷片再进行冷等静压成型;(4)将经冷等静压成型的氧化锆牙科陶瓷片进行预烧结;(5)将预烧结后的颜色呈梯度变化的氧化锆牙科陶瓷素坯进行坯体修复;(6)进行陶瓷烧结,得到颜色呈梯度变化的氧化锆牙科陶瓷。这种方法制作的结构,因整体还是氧化锆,只是在同一方向上出现不同梯度效果,并不能从牙釉质和牙本质方向上形成均匀过度的仿生状态,整体的耐磨性依然很高,没有从根本上解决对对颌牙造成磨损的问题。
CN104774007A公开了一种牙科玻璃部分渗透的功能梯度氧化锆陶瓷材料,该氧化锆陶瓷材料由三层结构构成:(1)厚度为0.2mm的玻璃层,(2)厚度为0.3mm的玻璃渗透氧化锆功能梯度层,(3)厚度为0.5mm的致密氧化锆层;牙科玻璃部分渗透的功能梯度氧化锆陶瓷材料的玻璃-玻璃渗透氧化锆功能梯度层-氧化锆三层结构的弹性模量和硬度呈梯度均匀变化。该材料中引入了玻璃渗透的方式,但三层之间的过渡也是非线性过渡,不能真正的实现仿生效果。
综上所述,如何开发一种仿生效果好,可实现强度、颜色均匀过渡的树脂渗透陶瓷材料成为当前亟待解决的问题。
发明内容
针对现有技术存在的问题,本发明的目的在于提供一种仿生树脂渗透陶瓷材料及其制备方法,所述仿生树脂渗透陶瓷材料通过结构的优化设计,以及填充材料的协同调配,实现了强度、颜色均匀过渡,仿生效果好,具有较好的应用前景。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料包括陶瓷骨架,所述陶瓷骨架内部设置有通道,所述通道内部填充有填充剂;所述填充剂包括树脂材料和纳米颗粒;
所述仿生树脂渗透陶瓷材料分为上树脂含量低,而牙本质部分树脂含量较高,整体材料性能更接近天然牙齿,能够更好的保护对颌天然牙;其次,填充材料选用树脂与纳米颗粒的结合,有利于提高体系的抗固化收缩性,以及与陶瓷骨架的结合强度。
以下作为本发明优选的技术方案,但不作为本发明提供的技术方案的限制,通过以下技术方案,可以更好地达到和实现本发明的技术目的和有益效果。
作为本发明优选的技术方案,所述通道呈直线型和/或曲线型。
本发明中,仿生树脂渗透陶瓷材料可制作成各种形状,包括但不限于正方体,长方体或牙齿形态。
作为本发明优选的技术方案,所述牙本质部的通道规定为主通道,所述牙釉质部的通道规定为衍生通道,每一个主通道连接至少1个衍生通道,例如1个、2个、3个、4个或5个等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
作为本发明优选的技术方案,所述牙本质部的主通道包括第一开口和第二开口,所述第一开口位于所述牙本质部的底端,所述第二开口位于所述牙本质部的顶端。
作为本发明优选的技术方案,所述牙釉质的衍生通道包括第三开口和第四开口,所述第三开口与所述主通道连通,所述第四开口位于所述牙釉质部的顶端和/或侧面上。
作为本发明优选的技术方案,所述主通道的第一开口的直径独立地不超过10mm,例如2mm、3mm、4mm、5mm、6mm、7mm、8mm、9mm或10mm等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用,优选为5-10mm。
优选地,所述主通道的第二开口的直径独立地为2-8mm,例如2mm、3mm、4mm、5mm、6mm、7mm或8mm等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用,且小于第一开口直径。
作为本发明优选的技术方案,所述衍生通道的第三开口的直径独立地为0.5-8mm,例如0.5mm、1mm、2mm、3mm、4mm、5mm、6mm、7mm或8mm等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
优选地,所述衍生通道的第四开口的直径独立地为0.01-6mm,例如0.01mm、0.05mm、0.1mm、0.5mm、1mm、2mm、3mm、4mm、5mm或6mm等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用,且小于第三开口的直径。
本发明中,主通道和衍生通道的两端开口直径均需进行控制。若主通道开口直径过大,导致主通道过粗,树脂材料渗透过多,影响材料的力学性能下降;若主通道开口直径过小,导致通道过细,树脂材料渗透过少,形成的结构刚性太强,且会使树脂渗透的成功率降低。
若衍生通道直径过大,导致树脂材料渗透过多,耐磨性能会相应变差;若衍生通道直径过小,牙釉质部分材料接近纯陶瓷材料,耐磨性过强,容易对天然牙造成磨损,无法更好的保护对颌天然牙。
作为本发明优选的技术方案,所述陶瓷骨架的原料包括氧化锆、硅酸铝钠、长石、二硅酸锂或氧化铝中的任意一种或两种组合,所述组合典型但非限制性实例有:氧化锆、硅酸铝钠和长石的组合,硅酸铝钠、长石、二硅酸锂和氧化铝的组合,氧化锆和氧化铝的组合等。
作为本发明优选的技术方案,所述树脂材料包括热固性树脂。
优选地,所述纳米颗粒包括纳米级二氧化硅、纳米级玻璃粉、纳米级氧化锆、纳米级氧化铝或纳米级蒙脱土中的任意一种或至少两种的组合,所述组合典型但非限制性实例有:纳米级二氧化硅和纳米级氧化铝的组合,纳米级二氧化硅和纳米级玻璃粉的组合等。
优选地,所述纳米颗粒的添加量是所述树脂材料质量的0.5-90%,例如0.5%、1%、5%、10%、20%、30%、40%、50%、60%、70%、80%或90%等,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用,优选为60-75%。
本发明中,纳米颗粒的添加量不宜过多,否则会严重增加渗透工艺的难度,降低渗透效率。
第二方面,本发明提供了一种第一方面所述的仿生树脂渗透陶瓷材料的制备方法,所述制备方法包括:
采用增材制造或减材制造的方式加工出内部设置有通道的陶瓷骨架,然后进行树脂渗透,得到仿生树脂渗透陶瓷材料。
优选地,所述仿生树脂渗透陶瓷材料经过减材制造加工,得到齿科仿生修复体。
与现有技术相比,本发明具有以下有益效果:
本发明所述仿生树脂渗透陶瓷材料通过通道直径的变化设计,模拟了天然牙齿的结构,使牙釉质部分陶瓷含量高,树脂含量低,而牙本质部分树脂含量较高,整体材料性能更接近天然牙齿,能够更好的保护对颌天然牙;其次,填充材料选用树脂与纳米颗粒的结合,可提高体系的抗固化收缩性,以及与陶瓷骨架的结合强度。
附图说明
图1是本发明实施例1提供的一种仿生树脂渗透陶瓷材料的立体结构示意图。
图2是本发明实施例2提供的一种仿生树脂渗透陶瓷材料的正视结构示意图。
其中,1-陶瓷骨架,2-牙本质部,21-主通道,3-牙釉质部,31-衍生通道,4-树脂材料,5-纳米颗粒。
具体实施方式
为更好地说明本发明,便于理解本发明的技术方案,下面对本发明进一步详细说明。但下述的实施例仅是本发明的简易例子,并不代表或限制本发明的权利保护范围,本发明保护范围以权利要求书为准。
在一个具体实施方式中,本发明提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料包括陶瓷骨架1,所述陶瓷骨架1内部设置有通道,所述通道内部填充有填充剂;所述填充剂包括树脂材料4和纳米颗粒5;
所述仿生树脂渗透陶瓷材料分为上部的牙釉质部3以及下部的牙本质部2;
所述通道贯穿牙本质部2和牙釉质部3,且沿所述牙本质部2到所述牙釉质部3的方向上,所述通道的直径逐渐变小。
进一步地,所述通道呈直线型和/或曲线型。
进一步地,所述牙本质部2的通道规定为主通道21,所述牙釉质部3的通道规定为衍生通道31,每一个主通道21连接至少1个衍生通道31。
进一步地,所述牙本质部2的主通道21包括第一开口和第二开口,所述第一开口位于所述牙本质部2的底端,所述第二开口位于所述牙本质部2的顶端。
进一步地,所述牙釉质的衍生通道31包括第三开口和第四开口,所述第三开口与所述主通道21连通,所述第四开口位于所述牙釉质部3的顶端和/或侧面上。
进一步地,所述主通道21的第一开口的直径独立地不超过10mm,优选为5-10mm;所述主通道21的第二开口的直径独立地为2-8mm,且小于第一开口直径。
进一步地,所述衍生通道31的第三开口的直径独立地为0.5-8mm;所述衍生通道31的第四开口的直径独立地为0.01-6mm,且小于第三开口的直径。
进一步地,所述陶瓷骨架1的原料包括氧化锆、硅酸铝钠、长石、二硅酸锂或氧化铝中的任意一种或两种组合。
进一步地,所述树脂材料4包括热固性树脂;
进一步地,所述纳米颗粒5包括纳米级二氧化硅、纳米级玻璃粉、纳米级氧化锆、纳米级氧化铝或纳米级蒙脱土中的任意一种或至少两种的组合;所述纳米颗粒5的添加量是所述树脂材料4质量的0.5-85%。
以下为本发明典型但非限制性实施例:
实施例1:
本实施例提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料的立体结构示意图如图1所示,基于具体实施方中的仿生树脂渗透陶瓷材料,其中:
所述仿生树脂渗透陶瓷材料呈正方体;
所述通道呈直线型,且每一个主通道21连接1个衍生通道31;
主通道21的第一开口位于所述牙本质部2的底端,直径为3mm;第二开口位于所述牙本质部2的顶端,直径为1mm。
衍生通道31的第三开口与所述主通道21连通,直径为0.5mm;第四开口位于所述牙釉质部3的顶端,直径为0.3mm;
所述陶瓷骨架1的原料包括硅酸铝钠;
树脂材料4为丙烯酸类热固性树脂;所述纳米颗粒5为400nm的二氧化硅;所述纳米颗粒5的添加量是所述树脂材料4质量的75%。
实施例2:
本实施例提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料的正视结构示意图如图2所示,基于具体实施方中的仿生树脂渗透陶瓷材料,其中:
所述仿生树脂渗透陶瓷材料呈正方体;
所述通道包括曲线型,且每一个主通道21连接3个衍生通道31;
主通道21的第一开口位于所述牙本质部2的底端,直径包括5mm;第二开口位于所述牙本质部2的顶端,直径包括3mm。
衍生通道31的第三开口与所述主通道21连通,直径包括1mm;第四开口位于所述牙釉质部3的顶端和,直径包括0.5mm;
所述陶瓷骨架1的原料包氧化锆;
树脂材料4为丙烯酸酯类热固性树脂;所述纳米颗粒5为700nm的玻璃粉;所述纳米颗粒5的添加量是所述树脂材料4质量的60%。
实施例3:
本实施例提供了一种仿生树脂渗透陶瓷材料,基于具体实施方中的仿生树脂渗透陶瓷材料,其中:
所述仿生树脂渗透陶瓷材料呈正方体;
所述通道包括曲线型和直线型,且每一个主通道21连接5个衍生通道31;
主通道21的第一开口位于所述牙本质部2的底端,直径包括4mm;第二开口位于所述牙本质部2的顶端,直径包括3mm。
衍生通道31的第三开口与所述主通道21连通,直径包括2mm;第四开口位于所述牙釉质部3的顶端,直径包括1mm;
所述陶瓷骨架1的原料包括长石;
树脂材料4为丙烯酸酯类热固性树脂;所述纳米颗粒5为300nm的氧化铝和二氧化硅,二者质量比为1:1;所述纳米颗粒5的添加量是所述树脂材料4质量的75%。
实施例4:
本实施例提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料参照实施例1中的仿生树脂渗透陶瓷材料,区别仅在于:纳米颗粒5的添加量为树脂材料4质量的85%。
本实施例中,由于纳米颗粒5的添加量过多,虽然耐磨耗性能较好,但会导致树脂粘度过高,渗透效果变差,树脂不能充分形成贯穿渗透的效果。
对比例1:
本对比例提供了一种仿生树脂渗透陶瓷材料,所述仿生树脂渗透陶瓷材料参照实施例1中的仿生树脂渗透陶瓷材料,区别仅在于:不添加纳米颗粒5。
本对比例中,由于未添加纳米颗粒5,渗透效果显著,但渗透树脂体系经过固化后由于收缩作用,和陶瓷骨架之间出现局部分离的现象,且还会导致牙釉质层耐磨性差。
测定实施例1-4和对比例1所得仿生树脂渗透陶瓷材料的耐磨性性能,测试结果如表1所示。
测试方法:YY/T 0113-2015牙科学复合树脂耐磨耗性能测试方法,指标要求低于30mg/mm3
表1
Figure BDA0004061020510000091
Figure BDA0004061020510000101
综合上述实施例和对比例可以看出,本发明所述仿生树脂渗透陶瓷材料通过结构的优化设计,以及填充材料的协同调配,实现了强度、颜色均匀过渡,仿生效果好,具有较好的应用前景。
本发明通过上述实施例来说明本发明的产品和详细方法,但本发明并不局限于上述产品和详细方法,即不意味着本发明必须依赖上述产品和详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明操作的等效替换及辅助操作的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。

Claims (10)

1.一种仿生树脂渗透陶瓷材料,其特征在于,所述仿生树脂渗透陶瓷材料包括陶瓷骨架,所述陶瓷骨架内部设置有通道,所述通道内部填充有填充剂;所述填充剂包括树脂材料和纳米颗粒;
所述仿生树脂渗透陶瓷材料分为上部的牙釉质部以及下部的牙本质部;
所述通道贯穿牙本质部和牙釉质部,且沿所述牙本质部到所述牙釉质部的方向上,所述通道的直径逐渐变小。
2.根据权利要求1所述的仿生树脂渗透陶瓷材料,其特征在于,所述通道呈直线型和/或曲线型。
3.根据权利要求1或2所述的仿生树脂渗透陶瓷材料,其特征在于,所述牙本质部的通道规定为主通道,所述牙釉质部的通道规定为衍生通道,每一个主通道连接至少1个衍生通道。
4.根据权利要求1-3任一项所述的仿生树脂渗透陶瓷材料,其特征在于,所述牙本质部的主通道包括第一开口和第二开口,所述第一开口位于所述牙本质部的底端,所述第二开口位于所述牙本质部的顶端。
5.根据权利要求3或4所述的仿生树脂渗透陶瓷材料,其特征在于,所述牙釉质的衍生通道包括第三开口和第四开口,所述第三开口与所述主通道连通,所述第四开口位于所述牙釉质部的顶端和/或侧面上。
6.根据权利要求4或5所述的仿生树脂渗透陶瓷材料,其特征在于,所述主通道的第一开口的直径独立地不超过10mm,优选为5-10mm;
优选地,所述主通道的第二开口的直径独立地为2-8mm,且小于第一开口直径。
7.根据权利要求3或5所述的仿生树脂渗透陶瓷材料,其特征在于,所述衍生通道的第三开口的直径独立地为0.5-8mm;
优选地,所述衍生通道的第四开口的直径独立地为0.01-6mm,且小于第三开口的直径。
8.根据权利要求1-7任一项所述的仿生树脂渗透陶瓷材料,其特征在于,所述陶瓷骨架的原料包括氧化锆、硅酸铝钠、长石、二硅酸锂或氧化铝中的任意一种或两种组合。
9.根据权利要求1-8任一项所述的仿生树脂渗透陶瓷材料,其特征在于,所述树脂材料包括热固性树脂;
优选地,所述纳米颗粒包括纳米级二氧化硅、纳米级玻璃粉、纳米级氧化锆、纳米级氧化铝或纳米级蒙脱土中的任意一种或至少两种的组合;
优选地,所述纳米颗粒的添加量是所述树脂材料质量的0.5-85%,优选为60-75%。
10.一种如权利要求1-9任一项所述的仿生树脂渗透陶瓷材料的制备方法,其特征在于,所述制备方法包括:
采用增材制造或减材制造的方式加工出内部设置有通道的陶瓷骨架,然后进行树脂渗透,得到仿生树脂渗透陶瓷材料;
优选地,所述仿生树脂渗透陶瓷材料经过减材制造加工,得到齿科仿生修复体。
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CN114617656A (zh) * 2022-03-15 2022-06-14 济南大学 一种复合材料仿生义齿及其制造方法
CN115350335A (zh) * 2022-08-16 2022-11-18 爱迪特(秦皇岛)科技股份有限公司 一种牙科修复用仿生复合材料及其应用

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