CN115893845A - 玻璃陶瓷组合物及其制备方法和应用 - Google Patents
玻璃陶瓷组合物及其制备方法和应用 Download PDFInfo
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- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 21
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 12
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 10
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Abstract
本发明公开了一种玻璃陶瓷组合物及其制备方法和应用。本发明提供的玻璃陶瓷组合物按质量百分比计,包括:SiO2 58‑72%;Al2O3 0‑4%;Na2O0‑5%;K2O 3‑8%;Li2O 8‑17%;P2O5 2.5‑5%、MgO 0‑2%、B2O3 0‑2.5%;ZnO0‑5%;ZrO2 0‑3%,可制备出晶相为偏硅酸锂、结晶度>50%、晶粒尺寸为30‑60nm、硬度为500‑590kgf/mm2的偏硅酸锂玻璃陶瓷;成分中无需引入高配比氧化锆含量,可磨削至0.2mm厚度,无崩边产生。
Description
技术领域
本发明属于牙齿修复材料技术领域,具体涉及一种玻璃陶瓷组合物及其制备方法和应用。
背景技术
二硅酸锂玻璃陶瓷由于具有良好的机械性能和突出的美学效果,被广泛应用于牙科修复领域。目前,其应用到的主要有贴面、牙桥、牙冠、嵌体、种植基台等。由于二硅酸锂玻璃陶瓷的强度较高,采用CAD/CAM机加工磨削成型难度较大,严重影响车针寿命。业内常采用先将基质玻璃结晶生成偏硅酸锂玻璃陶瓷,然后对其进行成型加工,最后再将成型好的偏硅酸锂玻璃陶瓷进行热处理,得到二硅酸锂玻璃陶瓷。由于偏硅酸锂玻璃陶瓷的强度小于二硅酸锂玻璃陶瓷,因此,成型加工相对容易。
但在实际生产中,由于偏硅酸锂与二硅酸锂常常会伴随的生成,不可控的二硅酸锂的生成会导致玻璃陶瓷的强度提升,常常导致车针折断,影响磨削效率,提高加工成本。为避免此情况,业内厂家常采用降低结晶温度,生产低结晶度的偏硅酸锂玻璃陶瓷。低结晶度的玻璃陶瓷虽可降低强度利于磨削,但由于玻璃相占比较高,其制品韧性较差,在加工贴面或牙冠时,其边缘易崩裂。为解决此问题,业内部分厂家通过提高基质玻璃中的氧化锆含量来提高韧性,但较少的锆含量难以增强韧性,较高的锆含量(质量百分比>10%)虽可以增强韧性改善磨削性能,但其对玻璃的熔制要求过高,成本投入较大。另一方面,氧化锆密度大,难熔化,其常会导致锆沉积,影响产品的均匀性。因此目前亟需一种低成本且磨削时边缘不易崩裂的玻璃陶瓷。
发明内容
为了克服上述现有技术的缺陷,本发明提出了一种玻璃陶瓷组合物及其制备方法和应用,解决玻璃陶瓷制品磨削时边缘易崩裂的行业痛点。具体技术方案如下:
一种玻璃陶瓷组合物,所述玻璃陶瓷组合物按质量百分比计,包括:SiO2 58-72%;Al2O3 0-4%;Na2O 0-5%;K2O 3-8%;Li2O 8-17%;P2O5 2.5-5%、MgO 0-2%、B2O3 0-2.5%;ZnO 0-5%;ZrO2 0-3%。
本发明提供的玻璃陶瓷组合物,SiO2为主要的网络形成剂,可使得网络结构稳定化,构成了玻璃陶瓷的主体结构,也是构成晶相的主要成分。玻璃陶瓷组合物中,SiO2含量过低会导致晶相种类的变化,同时也会弱化玻璃陶瓷的整体性能,SiO2含量不应低于58wt%。但较高的SiO2含量,又会导致熔制成型困难,且晶相还会形成SiO2的固溶体。故综合考虑,将SiO2的含量控制在58-72wt%之间。
在一些实施例中,含有Al2O3,对玻璃陶瓷的透性调节有一定作用,其含量越高,透性较好;但Al2O3属于极难熔氧化物,能快速提高玻璃高温粘度,致使玻璃澄清均化难度加大,气泡缺陷不易排出,故控制其含量低于4wt%。
玻璃陶瓷前驱体中含有碱金属氧化物R2O,主要为Na2O、K2O和Li2O;其中Na2O主要起降低玻璃陶瓷熔融体的粘度,促使前驱体的熔化和澄清。但Na2O含量的过多又会增大负热膨胀系数(CTE),导致力学性能的改变,故Na2O含量控制为0-5wt%。
K2O有利于增强玻璃陶瓷的光泽性,其含量不低于3%。不限于理论,本发明人实验发现,较高的K2O含量可抑制二次烧结时二硅酸锂的生成,不利于偏硅酸锂的最终转化,导致齿科成品性能下降。因此,K2O含量控制为3-8wt%。
Li2O为晶相的主要组成成分,其含量过低时,晶相无法形成,其最小含量需大于8wt%;但太高的Li2O又会使得结晶不受控制,导致玻璃在成型时析晶,导致缺陷产生,影响后续工艺。
P2O5可降低成核活化能,利于玻璃的结晶化,为玻璃陶瓷的成核剂。P2O5含量过低,玻璃较难晶化,故P2O5含量至少为2.5wt%;但P2O5含量过高,会使玻璃分相严重,影响玻璃陶瓷的透过性,故需要求P2O5含量至多为5wt%。
在一些实施例中,含有碱土金属氧化物RO,R2+为Mg2+和Zn2+,其能提高玻璃的化学稳定性和机械强度。本发明中,MgO含量限制为0-2wt%;ZnO为0-5wt%;
B2O3属于网络形成体氧化物,可降低玻璃高温熔融粘度,改善熔化特性,利于玻璃成分在高温下的均质化。但高含量的B2O3,极易导致玻璃分相,产生缺陷。其含量控制为0-2.5wt%。
进一步地,所述玻璃陶瓷组合物中各组分的质量百分比满足以下关系:
30%<(SiO2+Al2O3+ZrO2)-R2O<60%,其中,R2O为Na2O、K2O与Li2O的质量百分比之和;
2%<SiO2/(Li2O+P2O5)<6%;
7%<Li2O-P2O5<13.5%;
0.2%<(ZrO2+ZnO+Na2O+Al2O3)/Li2O<0.8%。
特别的,研究发现,当组合物中含量(SiO2+Al2O3+ZrO2)-R2O低于30wt%时,玻璃体整体黏度较低,为结晶质子移动提供了异常方便的流动环境,导致晶化工艺较难控制,影响结晶的均匀性,同时也导致偏硅酸锂更容易往二硅酸锂转化;当(SiO2+Al2O3+ZrO2)-R2O<60wt%时,整体黏度变大,结晶物质的整体所需温度上升,为匹配义齿工厂或医院的快速烧结炉,需保证二次烧结温度控制在900℃以下。因此,控制(SiO2+Al2O3+ZrO2)-R2O的范围为30-60wt%。
另外,为最大限度的控制偏硅酸锂的结晶度,需保证SiO2/(Li2O+P2O5)>2;过低时,成分中过量的Li2O与P2O5,会诱导二硅酸锂的直接生成,导致偏硅酸锂的晶相占比较少;过高时,由于过量的SiO2会在二次烧结时(T>800℃)形成SiO2的固溶体,导致最终的产品晶相增加,影响最终性能。
同样的,为避免二次烧结时,Li3PO4晶相的形成,导致最终的产品晶相增加,需限制7%<Li2O-P2O5<13.5%。
由于齿科产品对最终牙齿的透过率有要求,较高的透过率会显得过于透亮不真实,过低的透过率又显得过烧,无亮泽感。为此,需限制0.2%<(ZrO2+ZnO+Na2O+Al2O3)/Li2O<0.8%。
进一步地,为了使玻璃陶瓷制品的颜色与天然牙齿的颜色相似,所述玻璃陶瓷组合物还包括1-6%着色剂和/或荧光剂。
进一步地,所述着色剂和/或荧光剂为TiO2、La2O3、V2O5、CeO2、Er2O3、Y2O3、Nd2O3、Pr2O3、Mn2O3、NiO或Fe2O3中的一种或多种。
本发明还提供上述玻璃陶瓷组合物的制备方法,包括以下步骤:
S1、将上述玻璃陶瓷组合物的各组分按比例称取并混合得到混合料,将所述混合料进行熔化和退火;
S2、进行晶化热处理:升温速率3-10℃/min,升温至核化温度500-570℃,保温时间为5-30min;然后升温速率3-5℃/min,升温至晶化温度700-730℃,保温时间为5-20min;
S3、降温,得到玻璃陶瓷组合物。
进一步地,步骤S1中所述熔化步骤包括:将所述混合料放入坩埚中,在1400-1500℃的温度范围内熔化2-4小时。
本发明还提供一种根据上述制备方法制得的玻璃陶瓷制品。
进一步地,所述玻璃陶瓷制品的晶相为偏硅酸锂,所述玻璃陶瓷组合物的结晶度>50%。
进一步地,所述玻璃陶瓷制品的晶粒为颗粒状,晶粒的平均粒径为30-60nm。
具体地,所述玻璃陶瓷制品经磨削加工后,其可在快速烧结炉中830-850℃保温5-10分钟,完成义齿的烧结。
具体地,所述玻璃陶瓷制品经二次烧结后,其挠曲强度>350Mpa;
具体地,所述玻璃陶瓷制品经二次烧结后,其断裂韧性>2.2Mpa.m1/2;
具体地,所述玻璃陶瓷制品经二次烧结后,其晶相为板状互锁的二硅酸锂,结晶度>80%。
本发明还提供上述玻璃陶瓷组合物或根据上述制备方法制得的玻璃陶瓷制品在齿科材料中的应用,例如制备义齿、贴面、嵌体、冠修复等。
本发明与现有技术相比,具有如下优点:
本发明通过优化玻璃陶瓷组合物的配比,并结合相匹配的工艺制度,无需引入高配比氧化锆含量,通过控制二硅酸锂的生成,提高偏硅酸锂玻璃陶瓷的结晶度,从而改善玻璃陶瓷组合物的磨削性能。本发明可制备出晶相为偏硅酸锂,结晶度>50%,晶粒尺寸为30-60nm,硬度为500-590kgf/mm2的偏硅酸锂玻璃陶瓷;其成分无需引入高配比氧化锆含量,可磨削至0.2mm厚度,无崩边产生;其在快速烧结炉中830-850℃保温5-10分钟,可制备出晶相为二硅酸锂,结晶度>80%,挠曲强度>350MPa,断裂韧性>2.2Mpa.m1/2的玻璃陶瓷义齿产品。本发明的产品,热处理的整体保温时间短,磨削效率高,对车针的折损少,产品的崩边情况少,成本低,极具竞争优势,有较大的应用的前景。
附图说明
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明的实施例2样品未二次烧结时的扫描电子显微镜(SEM)图;
图2为本发明的实施例1-4样品未二次烧结时的磨削效果;
图3为本发明的实施例3样品,在快速烧结炉中840℃,保温5min后的扫描电子显微镜(SEM)图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
性能测试方法与标准:
(1)平均晶粒尺寸:利用SEM扫描电镜进行测定,在SEM扫描电镜下进行表面扫描,观察到颗粒的直径,并通过加总所有晶粒剖面的平均直径尺寸,除以SEM影像中的晶粒数。
(2)晶相含量:将XRD衍射峰与数据库图谱进行对比确定晶相,通过Rietveld方法计算结晶相衍射强度在整体图谱强度中所占比例得出结晶度及非晶含量。
(3)维氏硬度:GB/T 16534-2009《精细陶瓷室温硬度试验方法》,采用维氏硬度计测量,加载力为200g,加载时间为10S。
(4)磨削效果:采用智能牙雕机。
(5)挠曲强度:GB 30367-2013《牙科学陶瓷材料》,采用万能试验机测试。
(6)断裂韧性:GB 30367-2013《牙科学陶瓷材料》,采用万能试验机,四点弯曲测试。
实施例1-8通过如下方法制备:首先,将各组分按表1中比例进行称量并混合均匀,将均匀的混合料放入铂制或铂铑制的坩埚中,在电炉内1450℃的温度范围内进行3小时熔化,搅拌3次使其均匀后,降至适当的温度并浇铸到模具中,将浇铸成型的玻璃块放入450℃的退火炉内进行退火,退火完成后随炉冷却至常温取出。将退火后的玻璃制品放入晶化炉内进行晶化热处理,晶化热处理的工艺条件如表2,得到玻璃陶瓷制品,测试结果见表3。
表1.实施例1-8样品成分
表2.实施例1-8热处理工艺条件
表3.实施例1-8测试结果
图1为实施例2样品未二次烧结时的扫描电子显微镜(SEM)图,其晶粒平均尺寸为30-60nm;
图2中1-4#依次是实施例1-4样品未二次烧结时的磨削效果,边缘壁厚为0.2mm;
图3为实施例3样品,在快速烧结炉中840℃,保温5min后的扫描电子显微镜(SEM)图,其晶型为板状。
对比例1
对比例1与实施例1的区别仅在于核化温度不同,对比例1的核化温度为450℃,测得对比例1样品的晶相中偏硅酸锂很低、结晶度为38%、晶粒尺寸52nm、维氏硬度为446kgf/mm2、磨削0.2mm厚度牙出现崩边、二次烧结后挠曲强度306MPa、二次烧结后断裂韧性为1.5Mpa.m1/2、二次烧结后结晶度为58%。
对比例2
对比例2与实施例1的区别仅在于核化温度不同,对比例2的核化温度为600℃,测得对比例2样品的晶相为偏硅酸锂与二硅酸锂、结晶度为62%、晶粒尺寸30nm、维氏硬度为635kgf/mm2,硬度过高,磨削时出现车针断裂,影响车针寿命、磨削效果为0.2mm、二次烧结后挠曲强度377MPa、二次烧结后断裂韧性为2.3Mpa.m1/2、二次烧结后结晶度为>80%。
对比例3
对比例3与实施例1的区别仅在于晶化温度不同,对比例3的晶化温度为650℃,测得对比例3样品的晶相为偏硅酸锂、结晶度为43%、晶粒尺寸37nm、维氏硬度为487kgf/mm2、磨削0.2mm厚度牙出现崩边、二次烧结后挠曲强度343MPa、二次烧结后断裂韧性为1.95Mpa.m1/2、二次烧结后结晶度为76%。
对比例4
对比例4与实施例1的区别仅在于晶化温度不同,对比例4的晶化温度为750℃,测得对比例4样品的晶相为偏硅酸锂与二硅酸锂、结晶度为72%、晶粒尺寸65nm、维氏硬度为667kgf/mm2、硬度过高,磨削成0.2mm过程中出现车针断裂,影响车针寿命,二次烧结后挠曲强度382MPa、二次烧结后断裂韧性为1.3Mpa.m1/2、二次烧结后结晶度为>80%。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物按质量百分比计,包括:SiO258-72%;Al2O3 0-4%;Na2O 0-5%;K2O 3-8%;Li2O 8-17%;P2O5 2.5-5%、MgO 0-2%、B2O30-2.5%;ZnO 0-5%;ZrO2 0-3%。
2.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物中各组分的质量百分比满足下列关系:
30%<(SiO2+Al2O3+ZrO2)-R2O<60%,其中,R2O为Na2O、K2O与Li2O的质量百分比之和。
3.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物中各组分的质量百分比满足下列关系:
2%<SiO2/(Li2O+P2O5)<6%。
4.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物中各组分的质量百分比满足下列关系:
7%<Li2O-P2O5<13.5%。
5.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物中各组分的质量百分比满足下列关系:
0.2%<(ZrO2+ZnO+Na2O+Al2O3)/Li2O<0.8%。
6.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物还包括1-6wt%着色剂和/或荧光剂。
7.根据权利要求1所述的玻璃陶瓷组合物,其特征在于,所述玻璃陶瓷组合物的晶相为偏硅酸锂,所述玻璃陶瓷组合物的结晶度>50%。
8.一种玻璃陶瓷组合物的制备方法,其特征在于,包括以下步骤:
S1、将各组分按权利要求1-7任一项所述的玻璃陶瓷组合物的比例称取并混合得到混合料,将所述混合料进行熔化和退火;
S2、进行晶化热处理:按升温速率3-10℃/min,升温至核化温度500-570℃,保温时间为5-30min;然后按升温速率3-5℃/min,升温至晶化温度700-730℃,保温时间为5-20min;
S3、降温,得到玻璃陶瓷组合物。
9.根据权利要求8所述的玻璃陶瓷组合物的制备方法,其特征在于,所述S1中所述熔化步骤包括:将所述混合料放入坩埚中,在1400-1500℃的温度范围内熔化2-4小时。
10.权利要求1-7任一项所述的玻璃陶瓷组合物在齿科材料中的应用。
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