CN116161956B - 一种铌酸钾钠/氧化锆复合陶瓷及其制备方法与应用 - Google Patents
一种铌酸钾钠/氧化锆复合陶瓷及其制备方法与应用 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 27
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- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
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- 239000002994 raw material Substances 0.000 claims description 12
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- 235000015895 biscuits Nutrition 0.000 claims description 10
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- 238000009694 cold isostatic pressing Methods 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
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- 239000000203 mixture Substances 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 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 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于功能陶瓷材料技术领域,涉及一种铌酸钾钠/氧化锆复合陶瓷及其制备方法与应用。所述铌酸钾钠/氧化锆复合陶瓷具有下列所示化学通式:(Na0.5K0.5NbO3)x(Y0.06Zr0.94O1.97)(1‑x);其中,0.04≤x≤0.12。本发明的KNN/3Y‑TZP复合陶瓷具有晶粒细、韧性好、压电性能优异的优点,可以应用于口腔种植体,在获得韧性的同时依靠压电性能刺激骨生长,具有修复患处的作用。
Description
技术领域
本发明属于功能陶瓷材料技术领域,具体地,涉及一种铌酸钾钠/氧化锆复合陶瓷及其制备方法与应用。
背景技术
口腔种植体作为人工牙根用于种植义齿修复,已在口腔临床上广泛使用。其中,陶瓷种植体,特别是氧化锆陶瓷,相较于早期的钛金属种植体,具有不易变色、不引起过敏的优点,因此成为了首选。然而,其生物力学特性、断裂韧性并不理想,长期存活率较低的缺点,导致了其在种植体应用中有较大的限制。另一方面,种植牙也应该兼顾口腔康复的功能,包括有助于恢复患者的口腔功能和面部形态,促进骨修复与种植体的融合。
压电材料具有与人体骨相同的压电效应,可将机械应力产生的形变转化为电效应,产生微电流,然后刺激成骨。而且在植入后,可以不需要外加电源,依靠机体自身的活动将骨组织的力传导至材料而产生压电效应,产生适合的电刺激促进骨生长。同时,在荷载作用下,压电效应会引起畴壁运动,使裂纹尖端的能量耗散,由此认为压电陶瓷的加入可以提高陶瓷的韧性。
因此,如何将无铅压电陶瓷与氧化锆陶瓷烧结复合,制成可靠的种植体,在提高韧性的同时增加骨修复功能,是具有重要生产实践意义的问题。
发明内容
针对上述问题,本发明的目的在于提出一种无铅铌酸钾钠(KNN)压电陶瓷与四方多晶氧化锆(3Y-TZP)陶瓷的复合体及其制备技术。
为了实现上述目的,本发明提供一种铌酸钾钠/氧化锆复合陶瓷,具有下列所示化学通式:
(Na0.5K0.5NbO3)x(Y0.06Zr0.94O1.97)(1-x);
其中,x表示KNN占所述复合陶瓷的摩尔比,0.04≤x≤0.12,优选地,0.06≤x≤0.08。
根据本发明的实施例,混合粉体中KNN的含量可为5mol%,7mol%,10mol%,由此可以制备得到具有上述化学组成的复合陶瓷,并且该配比范围下可以进一步使复合陶瓷获得更好的压电性能及韧性。相应地,所述复合陶瓷具有下列之一所示的化学组成:
(Na0.5K0.5NbO3)0.05(Y0.06Zr0.94O1.97)0.95;
(Na0.5K0.5NbO3)0.07(Y0.06Zr0.94O1.97)0.93;
(Na0.5K0.5NbO3)0.10(Y0.06Zr0.94O1.97)0.90。
本发明的铌酸钾钠/氧化锆复合陶瓷具有50~80pC/N的压电常数d33。
进一步地,其具有7.0~11MPa*m1/2的断裂韧性、13~18.5GPa的维氏硬度和220~290的弹性模量。
本发明的所述复合陶瓷由钠源、钾源、铌源的混合物经球磨、预烧结、二次球磨,然后与3Y-TZP粉体混合球磨、干压成型、冷等静压、放电等离子烧结(SPS)、抛光制备得到。
所述钠源例如为Na2CO3,所述钾源例如为K2CO3,所述铌源例如为Nb2O5。
本发明的第二方面提供一种制备所述铌酸钾钠/氧化锆复合陶瓷的方法,包括以下步骤:
将预定比例的原料混合并进行球磨,得到混合粉料,其中,所述原料包括Na2CO3、K2CO3和Nb2O5;
将混合粉料进行预烧结,得到经过预烧结的粉料;
将经过预烧结的粉料进行二次球磨并烘干,得到KNN原始粉料;
将KNN原始粉料与3Y-TZP粉体按照一定的比例混合球磨,得到混合粉体;
将混合粉体进行干压成型和冷等静压处理,得到陶瓷素坯;
将陶瓷素坯进行烧结,然后抛光,最终得到所述复合陶瓷。
根据本发明一种具体实施方式,所述球磨、二次球磨和混合球磨的条件各自独立地包括:在球磨罐中、采用无水乙醇作为介质进行球磨,以得到成分均匀且细化的粉体,球磨的时间为6~24小时。由此可以进一步提高复合陶瓷的综合性能。
根据本发明一种具体实施方式,所述预烧结是在空气中850~900℃的温度下进行的。由此可以使得碳化物和氧化物中的碳元素和部分氧元素烧蚀掉,以便制备得到具有上述化学组成的复合陶瓷。
根据本发明一种具体实施方式,所述干压成型是在30-60MPa下进行的;所述冷等静压是在200-300MPa的压力下进行的。
根据本发明一种具体实施方式,所述烧结采用放电等离子烧结(SPS)技术,升温速率为85~120℃/min,烧结温度为850~1050℃。由此可以进一步获得稳定的性能优异的复合陶瓷。
本发明的第三方面提供铌酸钾钠/氧化锆复合陶瓷在制备口腔种植体中的应用。
与现有技术相比,本发明具有如下优点和显著进步:
(1)断裂韧性较钇稳定氧化锆陶瓷显著增加;
(2)具有一定的压电性能,有助于微电流产生以刺激骨生长;
(3)使用SPS烧结技术,可以获得纳米尺寸晶粒。
本发明的KNN/3Y-TZP复合陶瓷具有晶粒细、韧性好(7.0~11MPa*m1/2的断裂韧性、13~18.5GPa的维氏硬度和220~290的弹性模量)、压电性能优异(50~80pC/N)的优点,可以应用于口腔种植体,在获得韧性的同时依靠压电性能刺激骨生长,具有修复患处的作用。
本发明的其它特征和优点将在随后具体实施方式部分予以详细说明。
附图说明
通过结合附图对本发明示例性实施方式进行更详细的描述,本发明的5上述以及其它目的、特征和优势将变得更加明显。
图1为各实施例和对比例所制得的样品的压电常数d33测试结果。
图2为各实施例和对比例所制得的样品的断裂韧性测试结果。
图3为各实施例和对比例所制得的样品的维氏硬度测试结果。
图4为各实施例和对比例所制得的样品的弹性模量测试结果。
0图5(a)-(f)为各实施例和对比例所制得的样品表面SEM图:(a)对比例
一,(b)对比例二,(c)实施例一,(d)实施例二,(e)实施例三,(f)实施例四。
具体实施方式
5下面将更详细地描述本发明的优选实施方式。虽然以下描述了本发明的优选实施方式,然而应该理解,可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。
所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
0下面参考具体实施例,对本发明进行描述,需要说明的是,这些实施
例仅仅是描述性的,而不以任何方式限制本发明。
一般方法
原料:称取预定比例分析纯的Na2CO3、K2CO3、Nb2O5。
5制备方法:
1、KNN粉体制备:
1)将上述配好的原料加入到以无水乙醇为介质的球磨罐中,球磨12~24h,烘干后得到混合粉料;
2)将混合粉料在空气中以850-900℃的温度预烧4h;
3)将经过预烧后的粉料再次球磨12~24h并烘干;
4)将经过预烧结的粉料进行二次球磨,时间为6~12h,烘干后得到KNN原始粉料;
2、复合粉体混合:
将一定量KNN原始粉料与3Y-TZP粉体按照预定比例,加入到以无水乙醇为介质的球磨罐中,球磨12~24h,烘干后得到均匀复合粉体;
3、陶瓷素坯制备:
1)将经过球磨后的复合粉在50MPa下干压成型为直径30mm、厚度2.5mm的圆片;
2)在250MPa下进行冷等静压,保压时间为2min,得到复合陶瓷素坯;
4、SPS烧结:
将冷等静压后的复合素坯使用SPS技术进行烧结,升温速率为110℃/min,烧结温度为1025℃,烧结时间20min;
由此制备得到具有通式为(Na0.5K0.5NbO3)x(Y0.06Zr0.94O1.97)(1-x)的铌酸钾钠/氧化锆复合陶瓷,其中,0.03≤x≤0.07;其中x为KNN占复合体总量的摩尔比。
5、测试
将烧结后的复合陶瓷片切割、减薄、抛光,测试力学性能;
将烧结后的陶瓷片上银电极,在80℃的硅油中,电场强度为3~4kV/mm的直流电场下极化30min,测试电学性能。
实施例一:
原料:4.7696g Na2CO3,6.2195g K2CO3,24.1929g Nb2O5和34.9414g3Y-TZP。
制备方法:依照“一般方法”中的所有步骤制备得到复合陶瓷,其中KNN粉体与3Y-TZP粉体分别称取1.8593g与34.9414g。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.05(Y0.06Zr0.94O1.97)0.95的KNN/3Y-TZP复合陶瓷。SEM见图5(c)。
实施例二:
原料:4.7696g Na2CO3,6.2195g K2CO3,24.1929g Nb2O5和34.2058g3Y-TZP。
制备方法:依照“一般方法”中的所有步骤制备得到复合陶瓷,其中KNN粉体与3Y-TZP粉体分别称取2.6031g与34.2058g。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.07(Y0.06Zr0.94O1.97)0.93的KNN/3Y-TZP复合陶瓷。SEM见图5(d)。
实施例三:
原料:4.7696g Na2CO3,6.2195g K2CO3,24.1929g Nb2O5和33.1024g3Y-TZP。
制备方法:依照“一般方法”中的所有步骤制备得到复合陶瓷,其中KNN粉体与3Y-TZP粉体分别称取3.71865g与33.1024g。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.10(Y0.06Zr0.94O1.97)0.90的KNN/3Y-TZP复合陶瓷。SEM见图5(e)。
实施例四:
原料:4.7696g Na2CO3,6.2195g K2CO3,24.1929g Nb2O5和34.2058g3Y-TZP。
制备方法:依照“一般方法”中的KNN粉体制备、复合粉体混合(KNN2.6031g,3Y-TZP34.2058g)、陶瓷素坯制备步骤制备复合陶瓷素坯;后续使用常压烧结,烧结温度为1150℃,保温时间为2h,制备得到复合陶瓷。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.07(Y0.06Zr0.94O1.97)0.93的KNN/3Y-TZP常规烧结复合陶瓷。SEM见图5(f)。
对比例一:
原料:4.7696g Na2CO3,6.2195g K2CO3,24.1929g Nb2O5和35.6770g3Y-TZP。
制备方法:依照“一般方法”中的所有步骤制备得到复合陶瓷,其中KNN粉体与3Y-TZP粉体分别称取1.1156g与35.6770g。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.03(Y0.06Zr0.94O1.97)0.97的KNN/3Y-TZP复合陶瓷。SEM见图5(a)。
对比例二:
原料:36.7804g 3Y-TZP。
制备方法:依照“一般方法”中的复合粉体混合、陶瓷素坯制备、SPS烧结的步骤直接制备得到3Y-TZP陶瓷。
由此,制备得到具有通式为(Na0.5K0.5NbO3)0.00(Y0.06Zr0.94O1.97)1.00的3Y-TZP陶瓷。SEM见图5(b)。
测试例:
分别对实施例一至四以及对比例一至二制备的KNN/3Y-ZTP复合陶瓷压电常数d33、断裂韧性、维氏硬度和弹性模量进行测定,对表面微观形貌进行表征。测试结果见图1至图4。
由图1至图4可以看出,当0.04≤x≤0.12时,KNN/3Y-TZP复合陶瓷压电性能与机械性能均随x增大而逐渐增大,且在x=0.07时获得优异于3Y-TZP的机械性能。在此区间外,无法获得较好的综合性能。原因是SPS烧结技术可在较低的烧结温度下获得具有纳米尺寸晶粒的致密块体,从而实现良好的复合性能;但KNN含量过大时,固溶效果变差,导致晶粒增大从而性能降低;KNN含量过小时,未实现压电性能与机械性能的协同优化。
以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
Claims (11)
1.一种铌酸钾钠/氧化锆复合陶瓷,具有下列所示化学通式:
(Na0.5K0.5NbO3)x(Y0.06Zr0.94O1.97)(1-x);
其中,0.04≤x≤0.12。
2.根据权利要求1所述的铌酸钾钠/氧化锆复合陶瓷,其特征在于,0.06≤x≤0.08。
3.根据权利要求1所述的铌酸钾钠/氧化锆复合陶瓷,其特征在于,具有下列之一所示的化学组成:
(Na0.5K0.5NbO3)0.05(Y0.06Zr0.94O1.97)0.95;
(Na0.5K0.5NbO3)0.07(Y0.06Zr0.94O1.97)0.93;
(Na0.5K0.5NbO3)0.10(Y0.06Zr0.94O1.97)0.90。
4.根据权利要求1所述的铌酸钾钠/氧化锆复合陶瓷,其特征在于,其具有50~80 pC/N的压电常数d 33。
5.根据权利要求1所述的铌酸钾钠/氧化锆复合陶瓷,其特征在于,其具有7.0~11MPa·m1/2的断裂韧性、13~18.5 GPa的维氏硬度和220~290的弹性模量。
6.根据权利要求1所述的铌酸钾钠/氧化锆复合陶瓷,其特征在于,所述复合陶瓷由钠源、钾源、铌源的混合物经球磨、预烧结、二次球磨,然后与3Y-TZP粉体混合球磨、干压成型、冷等静压、放电等离子烧结、抛光制备得到。
7.一种制备权利要求1~6任一项所述铌酸钾钠/氧化锆复合陶瓷的方法,其特征在于,包括以下步骤:
将预定比例的原料混合并进行球磨,得到混合粉料,其中,所述原料包括Na2CO3、K2CO3和Nb2O5;
将混合粉料进行预烧结,得到经过预烧结的粉料;
将经过预烧结的粉料进行二次球磨并烘干,得到KNN原始粉料;
将KNN原始粉料与3Y-TZP粉体按照一定的比例混合球磨,得到混合粉体;
将混合粉体进行干压成型和冷等静压处理,得到陶瓷素坯;
将陶瓷素坯进行烧结,然后抛光,最终得到所述复合陶瓷。
8.根据权利要求7所述的方法,其特征在于,所述球磨、二次球磨和混合球磨的条件各自独立地包括:在球磨罐中、采用无水乙醇作为介质进行球磨,以得到成分均匀且细化的粉体,球磨的时间为6~24小时。
9.根据权利要求7所述的方法,其特征在于,所述预烧结是在空气中850~900 ℃的温度下进行的;所述干压成型是在30-60 MPa下进行的;所述冷等静压是在200-300 MPa的压力下进行的。
10.根据权利要求7所述的方法,其特征在于,所述烧结采用放电等离子烧结技术,升温速率为85~120 ℃/min,烧结温度850~1050 ℃。
11.权利要求1~6任一项所述的铌酸钾钠/氧化锆复合陶瓷在制备口腔种植体中的应用。
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