CN110240491A - 一种高韧性的氧化锆瓷块 - Google Patents
一种高韧性的氧化锆瓷块 Download PDFInfo
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 103
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 95
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 19
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 238000010884 ion-beam technique Methods 0.000 claims description 9
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- 229910052727 yttrium Inorganic materials 0.000 claims 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 229910052845 zircon Inorganic materials 0.000 description 2
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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Abstract
本发明属于生物材料领域,具体涉及一种高韧性氧化锆瓷块及其制备方法。具体技术方案为:一种氧化锆瓷块,按质量分数,包括0~3%的氧化镧、1.5~12%的氧化钇、0~2.5%的碳化硅纳米晶须,及余量的氧化锆。所述氧化锆瓷块表面还原位沉积有氮化钛薄膜。使用本发明提供的配方和方法获得的氧化锆瓷块,断裂韧性高,且半透性优异,是理想的口腔用生物陶瓷材料。
Description
技术领域
本发明属于生物材料领域,具体涉及一种高韧性的氧化锆瓷块。
背景技术
氧化锆瓷块是一种生物陶瓷材料,属于绿色经济的范畴。按照医疗器械注册办法分类,全瓷义齿用氧化锆瓷块属于二类医疗器械,因具有良好的生物相容性、优良的机械性能和逼真的类牙体光学效果等优点,被誉为21世纪理想的义齿修复材料。随着人们生活水平的提高,健康意识的增强,口腔义齿修复去金属化已成为发展趋势,全瓷修复得到越来越多医生和患者的推崇。
目前市面上使用最广泛、性能最好的氧化锆义齿产品的断裂韧性为4.6MPa·m1/2~5.2MPa·m1/2(ST产品),ST产品具有性能好、强度高、润泽性接近天然牙等优点。经过市场反馈,发现市场上现有的全瓷义齿用ST产品存在一个共同缺陷:义齿加工厂对义齿进行制备的过程中,容易出现长桥断裂、薄牙崩边等现象而导致返工。
虽然现有技术中已经有一些提高氧化锆瓷块韧性的方法,如增加稳定剂等,但这些方法要不就提升效果不理想,要不就是以牺牲氧化锆瓷块的半透性为代价,无法满足消费者对义齿的美学需求。
综上,提供一种兼具优异的断裂韧性和优良的半透性的氧化锆瓷块,具有重要的现实意义。
发明内容
本发明的目的是提供一种高韧性氧化锆瓷块及其制备方法。
为实现上述发明目的,本发明所采用的技术方案是:一种氧化锆瓷块,按质量分数,包括0~3%的氧化镧、1.5~12%的氧化钇、0~2.5%的碳化硅纳米晶须,及余量的氧化锆。
优选的,所述氧化钇和碳化硅纳米晶须的质量比为1:1。
优选的,所述氧化锆瓷块表面设有氮化钛薄膜。
优选的,所述氮化钛薄膜的厚度为100~200nm。
相应的,一种氧化锆瓷块的制备方法,包括如下步骤:
(1)按质量分数,称取0~3%的氧化镧、1.5~12%的氧化钇,0~2.5%的碳化硅纳米晶须,及余量的氧化锆,充分混匀,获得混合粉体;
(2)将混合粉体预压制成型、等静压成型、预烧结、高温烧结,即获得所述氧化锆瓷块。
优选的,所述氧化钇和碳化硅纳米晶须的质量比为1:1。
优选的,所述步骤(2)中,完成预烧结后,取出氧化锆瓷块,进行如下步骤:
(3)冷却、清洗、干燥;
(4)对所述氧化锆瓷块进行Ti镀膜;
(5)随后将Ti镀膜后的氧化锆瓷块在N2氛围中进行高温烧结。
优选的,所述步骤(3)后,先使用低能离子束对干燥后的氧化锆瓷块进行溅射,随后再进行Ti镀膜。
优选的,所述低能离子束为:200~350eV、30~50mA的低能离子束。
本发明具有以下有益效果:
1、义齿一方面要求高韧性、避免崩边,另一方面要求良好的半透性以满足美学要求。但氧化锆瓷块的结晶过程某种程度上让高韧性和良好的半透性成为一对几乎不可兼得的性能。氧化锆瓷块在烧结过程中,结晶体从四方相逐渐向立方相转变,随着四方相含量的降低,氧化锆瓷块的断裂韧性也逐渐降低,同时半透性逐渐增加。现有技术中一般添加碱土和稀土金属氧化物作为稳定剂(例如氧化钇、氧化镁、氧化钙等)与氧化锆一起进行烧结,一定程度上阻碍四方相向立方相乃至单斜相转变。但增加氧化钇对提高韧性的效果非常有限,超过某一范围后,继续增加氧化钇,韧性不升反降;另一方面,氧化钇的含量与氧化锆的半透性呈正相关关系。因此,只简单地添加氧化钇,提高韧性帮助有限,也无法同时提高氧化锆瓷块的半透性和韧性。
添加碳化硅纳米晶须也可以一定程度上抑制四方相向立方相的转变,从而帮助提高氧化锆瓷块的韧性;碳化硅纳米晶须的晶须本身也可以起到一定的增韧作用,双重作用下共同提升氧化锆瓷块的韧性。另外,碳化硅纳米晶须可以帮助氧化锆瓷块内部形成氧化锆细晶粒,降低氧化锆晶体的晶粒直径。现有研究表明,晶粒直径与氧化锆瓷块的半透性有关,晶粒大小与可见光波长相近时,散射作用最明显,半透性最低,因此需要控制晶粒大小在可见光波长范围以外(0.38~0.77μm),但具体晶粒大小为多少时半透性最优并无定论。发明人研究发现,配合使用特定含量的氧化钇(低含量)和碳化硅纳米晶须,可以同时赋予氧化锆瓷块优异的韧性,及添加高含量氧化钇时才能获得的高半透性。
2、本发明还在制备时为氧化锆瓷块增镀了一层氮化钛保护薄膜。氮化钛具有良好的生物活性和优异的综合力学性能,可以进一步提高氧化锆瓷块的整体韧性。通过控制氮化钛的含量,还可一定程度上调控义齿的颜色。如果直接将氮化钛粉末添加到氧化锆瓷块原始粉体中,整体一起压制、烧结成型,虽然也可以最终提高氧化锆瓷块的韧性,但氮化钛粉末的引入会改变氧化钇和碳化硅纳米晶须对氧化锆瓷块结晶的影响效果,韧性提成效果反而还不如不增加氮化钛粉末时的效果。而如果在氧化锆瓷块整体完全烧结结束后再镀上氮化钛薄膜,一方面存在结合紧密性的问题,另一方面,直接进行氮化钛镀膜,厚度不易控制,还会一定程度上改变氧化锆瓷块的原定尺寸,后续使用时还需二次加工打磨,而打磨的过程又会损失一部分氮化钛薄膜,失去了镀膜意义。更重要的是,氧化锆瓷块的崩边主要发生于机械加工和高温烧结的过程中。增加适量氧化钇和碳化硅晶须的氧化锆瓷块,韧性已经显著提升,足以避免机械加工的崩边情况。而在氧化锆高温烧结过程中同时进行韧性加固,则可进一步避免高温烧结中出现的崩边情况。如果将镀膜步骤放在氧化锆瓷块整体完成烧结后再进行,则失去了对高温烧结中保护的意义。因此,本发明中,以氧化锆瓷块为反应基底、采用原位沉积法为氧化锆瓷块进行镀膜。
具体实施方式
一、本发明涉及的氧化锆瓷块配方
按质量分数,本发明提供的氧化锆瓷块配方包括:0~3%的氧化镧、1.5~12%的氧化钇、0~2.5%的碳化硅纳米晶须,及余量的氧化锆。所述氧化锆瓷块表面设置100~200nm的氮化钛薄膜。所述氧化锆、氧化镧和氧化钇均为纳米级。
二、本发明涉及的氧化锆瓷块的制备方法
在不增镀氮化钛保护薄膜的情况下,所述氧化锆瓷块的制备方法为:称取除氮化钛以外的各组分,混匀,预压制成型后,再等静压成型,随后进行预烧结、高温烧结,即完成制备。
如果需要增镀氮化钛保护薄膜,则具体制备方法如下:
(1)完成预烧结后,取出氧化锆瓷块,机械加工至所需形状和大小,随后将氧化锆瓷块依次经丙酮和酒精的超声清洗、干燥。
(2)使用低能离子束对清洗后的氧化锆瓷块进行溅射。
(3)在真空环境中,Ar氛围下,使用纯度为99.99%的Ti颗粒对氧化锆瓷块进行Ti镀膜,镀膜厚度为100~150nm。
(4)将完成Ti镀膜的氧化锆瓷块在N2氛围中进行高温烧结。烧结完成后,取出、冷却,再依次经丙酮和酒精的超声清洗、干燥,即完成。
下面结合具体实施例,对本发明进行进一步阐释。
实施例一:未进行氮化钛镀膜的氧化锆瓷块性能展示
1、按上述配方和方法制备39组氧化锆瓷块,每组设20个重复。各组氧化锆瓷块的具体配方如表1所示,表中数值均为质量分数,余量均为氧化锆粉末。以购自长沙彭登生物瓷块有限公司的ST氧化锆瓷块为对照组。需要说明的是,申请人并非只进行了表1的试验,而是因为篇幅限制,只选取了最具代表性的几组数据进行展示。
各组氧化锆瓷块的具体制备方法为:称取各组分,充分混匀后,在150MPa下保压10min,进行等静压成型;再在1050℃下保温2h,进行预烧结;从各组中分别取出10个重复,进行机械加工至为义齿的形状和尺寸;每组的另10个重复不进行机械加工处理。随后将各组各重复在1530℃下保温2h,高温烧结,完成制备(各组各重复的氧化锆瓷块,无论在机械加工过程中崩边与否,均继续进行高温烧结)。
表1各组氧化锆瓷块的配方
2、使用压痕法测定上述各组各重复的崩边率;其中,机械加工中已发生的崩边不计入高温烧结中,高温烧结中的崩边率只计算在高温烧结过程中再次发生崩边的氧化锆瓷块的数量及在整组中所占百分比。同时计算各组的断裂韧性和透光率;其中,透光率取每组20个重复的平均值,终产物的断裂韧性取每组未经机械加工的氧化锆瓷块的平均值。结果如表2所示。
表2各组氧化锆瓷块的性能展示
实施例二:增镀氮化钛的氧化锆瓷块性能展示
1、选择实施例一的组19的配方制备20组氧化锆瓷块:按实施例一的方法进行预烧结后,取出10组氧化锆瓷块,机械加工至义齿所需形状和尺寸,另外10组不进行机械加工。随后将各组氧化锆瓷块依次浸入丙酮和无水酒精中,进行超声清洗、干燥。
2、使用低能离子束对清洗后的各组氧化锆瓷块进行溅射清洗。具体溅射清洗条件为:使用300eV、50mA的低能离子束对氧化锆瓷块进行5min的溅射。
3、使用电子束蒸发镀膜机对溅射后的氧化锆瓷块进行Ti镀膜。控制真空度为6×10-4Pa,7kV,电子束流100mA;在Ar氛围下,使用纯度为99.99%的Ti颗粒对氧化锆瓷块进行Ti镀膜,使用FCM-Ⅱ型膜厚控制仪监控镀膜厚度,镀膜厚度为100nm。
4、将完成Ti镀膜的氧化锆瓷块在N2氛围中进行高温烧结,控制烧结温度1530℃、保温2h。烧结完成后,取出完成TiN镀膜的氧化锆瓷块,冷却,再依次经丙酮和酒精的超声清洗、干燥,即得各组实验组的氧化锆瓷块。
同时省略步骤2(溅射),制备对照组。制备完成后,使用刀尖用力重复刻划对照组和实验组的氧化锆瓷块表面。对照组的表层薄膜出现划痕,针对同一位置划拉5次左右,薄膜出现翘边和剥落的情况。实验组(随机从经机械加工和未经机械加工的组别中各抽取1块氧化锆瓷块进行)的薄膜粘结紧密,对同一位置划拉20次以上,未出现划痕、翘边和剥落情况。
使用实施例一的相同方法对各组氧化锆瓷块进行性能测试。机械加工过程中,未出现崩边断裂情况;将机械加工和未进行机械加工的各组氧化锆瓷块进行高温烧结,也未出现崩边断裂等情况。分别测定机械加工后和未进行机械加工的氧化锆瓷块的平均断裂韧性;并测定所有实验组的半透性,取平均值。经机械加工后,平均断裂韧性为19.83MPa·m1 /2,未经机械加工的,平均断裂韧性为20.11MPa·m1/2。平均半透性为48.53%。与市购产品及实施例一相比,断裂韧性显著提升,且半透性保持良好。
Claims (9)
1.一种氧化锆瓷块,其特征在于:按质量分数,包括0~3%的氧化镧、1.5~12%的氧化钇、0~2.5%的碳化硅纳米晶须,及余量的氧化锆。
2.根据权利要求1所述的氧化锆瓷块,其特征在于:所述氧化钇和碳化硅纳米晶须的质量比为1:1。
3.根据权利要求1所述的氧化锆瓷块,其特征在于:所述氧化锆瓷块表面设有氮化钛薄膜。
4.根据权利要求3所述的氧化锆瓷块,其特征在于:所述氮化钛薄膜的厚度为100~200nm。
5.一种氧化锆瓷块的制备方法,其特征在于,包括如下步骤:
(1)按质量分数,称取0~3%的氧化镧、1.5~12%的氧化钇,0~2.5%的碳化硅纳米晶须,及余量的氧化锆,充分混匀,获得混合粉体;
(2)将混合粉体预压制成型、等静压成型、预烧结、高温烧结,即获得所述氧化锆瓷块。
6.根据权利要求5所述的氧化锆瓷块的制备方法,其特征在于:所述氧化钇和碳化硅纳米晶须的质量比为1:1。
7.根据权利要求5所述的氧化锆瓷块的制备方法,其特征在于:所述步骤(2)中,完成预烧结后,取出氧化锆瓷块,进行如下步骤:
(3)冷却、清洗、干燥;
(4)对所述氧化锆瓷块进行Ti镀膜;
(5)随后将Ti镀膜后的氧化锆瓷块在N2氛围中进行高温烧结。
8.根据权利要求7所述的氧化锆瓷块的制备方法,其特征在于:所述步骤(3)后,先使用低能离子束对干燥后的氧化锆瓷块进行溅射,随后再进行Ti镀膜。
9.根据权利要求8所述的氧化锆瓷块的制备方法,其特征在于:所述低能离子束为:200~350eV、30~50mA的低能离子束。
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WO2024051651A1 (zh) * | 2022-09-05 | 2024-03-14 | 北京大学口腔医学院 | 一种高强度高韧性纳米氧化锆陶瓷材料及其制备方法与应用 |
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