CN106757302A - 一种铌酸钾钠单晶及其制备方法 - Google Patents
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000001238 wet grinding Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- WSSKLPBIOYSPEX-UHFFFAOYSA-N [Bi].[Na].[K] Chemical compound [Bi].[Na].[K] WSSKLPBIOYSPEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
Abstract
本发明提供一种铌酸钾钠单晶及其制备方法,以K2CO3、Na2CO3和Nb2O5作为原料,按照摩尔比为0.52:0.48:1进行配料,经过以下步骤:所用原料称量配料前均置于烘箱中烘干;按照摩尔比称取原料装入球磨瓶中球磨;将球磨后产物取出,烘干,压片,预烧;然后以无水乙醇为介质二次球磨后烘干;将烘干的粉料过筛后,压制成圆坯,然后烧结获得单晶;将铌酸钾钠单晶从陶瓷基体中取出即可得到纯的铌酸钾钠单晶。本发明的优点是:采用无籽固相晶体生长技术在不掺杂其他元素的情况下,通过改变原料的比例、烧结温度、时间以及坯体尺寸,可以得到不同尺寸的纯的铌酸钾钠单晶。
Description
技术领域
本发明涉及铁电压电单晶材料,具体是一种铌酸钾钠单晶及其制备方法。
背景技术
铌酸钾钠(K0.5Na0.5NbO3,KNN)系压电陶瓷因具有压电性能高、频率常数大、居里温度高及组成元素对人体友好等特点,正成为国内外该领域的研究热点之一,被认为是很有前途替代以 PbZrO3-PbTiO3(PZT)体系为代表的含铅压电陶瓷的无铅压电材料之一。一般,按陶瓷的结晶形态,陶瓷可分为多晶与单晶两大类。单晶陶瓷因为不受晶粒大小、晶粒取向、晶界与气孔率等的影响,从而比多晶陶瓷拥有更加优异的性能,如具有更加优异的介电、压电与光学性能等。传统的陶瓷固相烧结技术能克服传统单晶生长法的缺点,是制备陶瓷最简便、易控制材料质量也是成本最低的常用技术。如何将这种多晶材料制备工艺的优势与单晶材料的结构性能优点相结合,创立、发展一种制备过程简便、成本低廉、性能优异的KNN基压电单晶的生长新技术和新方法,具有重要的研究意义和应用价值。
2009年,发明人在针对KNN基无铅压电陶瓷掺杂改性的研究过程中发现:在KNN基陶瓷中,采用传统的陶瓷制备工艺就可以在常规条件下制备出大尺寸的KNN单晶。[1] 江民红,刘心宇,邓满姣,陈国华. 铌酸钾钠织构陶瓷与铌酸钾钠单晶的制备方法. 中国,发明专利,申请号:201010247474.8;2. Minhong Jiang, Clive A. Randall, HanzhengGuo,GuanghuiRao, RongTu, ZhengfeiGu, Gang Cheng, Xinyu Liu, Jinwei Zhang, andYongxiang Li, Seed-Free Solid-State Growth of Large Lead-Free PiezoelectricSingle Crystals: (Na1/2K1/2)NbO3, Journal of the American Ceramic Society,2015, 98 (10):2988–2996.]。该现有技术与传统的晶体生长技术相比,该方法操作简便、设备简单,成本低,生长晶体组分的均匀性好、体系多样,适合生长组分熔点不同、宽范围溶解度、挥发性强、冷却阶段易发生破坏性相变的晶体。
现有技术存在以下问题: KNN单晶的无籽固相生长需要通过掺杂微量含铋(Bi)元素的复合氧化物才能实现,铋元素比较贵重,而且高扩散系数的铋的存在是KNN单晶介电损耗较高的原因之一,因此探索无铋铌酸钾钠单晶的生长技术具有重要意义。
发明内容
为了解决上述技术问题,本发明的目的是提供一种铌酸钾钠单晶及其制备方法。通过改变铌酸钾钠中K、Na的摩尔比,采用无籽固相生长技术制备出纯的不含铋元素的铌酸钾钠单晶。
实现本发明铌酸钾钠单晶的具体技术方案包括如下步骤:
步骤(1)所用原料Na2CO3、K2CO3、Nb2O5在称量配料前均置于烘箱中烘干,烘干温度为120℃,烘干时间为4~6 h;
步骤(2)按照摩尔比0.52:0.48:1称取K2CO3、Na2CO3和Nb2O5原料装入HDPE材质的球磨瓶中,以无水乙醇为介质球磨24 h;
步骤(3)将球磨后产物取出,烘干,压片,预烧,预烧的温度为750℃,预烧的时间为6 h;
步骤(4)然后以无水乙醇为介质二次球磨12~16 h后烘干;
步骤(5)将烘干的粉料过100目筛后,在100 MPa的压力下压制成直径为14 mm,厚度为2~3 mm的圆坯;
步骤(6)将压制好的圆坯烧结获得单晶,烧结的温度可以是1125至1135℃中的1125℃、1130℃或1135℃,烧结时保温时间为6 h以上。
步骤(7)经上述步骤获得的铌酸钾钠单晶处于陶瓷基体中,将铌酸钾钠单晶从陶瓷基体中取出即可得到纯的铌酸钾钠单晶。
本发明与现有技术相比的优点是:经实验证明,采用无籽固相晶体生长技术在不掺杂其他元素,特别是铋元素的情况下,通过改变K、Na的比例,按照Na2CO3、K2CO3、Nb2O5摩尔比为0.52:0.48:1可以制备纯的铌酸钾钠单晶。
附图说明
图1为实施例中步骤(7)制备的铌酸钾钠单晶样品;
图2为实施例中从陶瓷基体中取下的铌酸钾钠单晶;
图3为实施例中制备的铌酸钾钠单晶样品粉末的XRD图谱。
具体实施方式
本发明通过实施例对本发明内容作进一步详细说明,但不是对本发明的限制。
实施例
铌酸钾钠单晶的制备方法包括如下步骤:
步骤(1)所用原料Na2CO3、K2CO3、Nb2O5在称量配料前均置于烘箱中烘干,烘干温度为120℃,烘干时间为6 h;
步骤(2)按照摩尔比0.52:0.48:1称取K2CO3、Na2CO3和Nb2O5原料装入HDPE材质的球磨瓶中,以无水乙醇为介质球磨24 h;
步骤(3)将球磨后产物取出,烘干,压片,在750℃条件下预烧6 h;
步骤(4)然后以无水乙醇为介质二次球磨16 h后烘干;
步骤(5)将烘干的粉料过100目筛后,在100 MPa的压力下压制成直径为14 mm,厚度为3mm的圆坯;
步骤(6)将压制好的圆坯在1130℃下保温21 h烧结;
步骤(7)经上述步骤获得的铌酸钾钠单晶处于陶瓷基体中,如图1所示,深色部分即为铌酸钾钠单晶,将铌酸钾钠单晶从陶瓷基体中取出即可得到纯的铌酸钾钠单晶,如图2所示。
将所得铌酸钾钠单晶样品进行分析,得到的铌酸钾钠单晶样品粉末的XRD图谱如图3所示。
Claims (5)
1.一种铌酸钾钠单晶,其特征在于:所述铌酸钾钠单晶以K2CO3、Na2CO3和Nb2O5作为原料,按照摩尔比为0.52:0.48:1进行配料,经配料、湿磨、烘干、预烧、二次球磨、压制成型、烧结步骤,制备出K0.52Na0.48NbO3单晶。
2.根据权利要求1所述的铌酸钾钠单晶的制备方法,其特征在于包括以下步骤:
步骤(1)所用原料Na2CO3、K2CO3、Nb2O5在称量配料前均置于烘箱中在120℃条件下,烘干4~6 h;
步骤(2)按照摩尔比称取K2CO3、Na2CO3和Nb2O5原料装入HDPE材质的球磨瓶中,以无水乙醇为介质球磨24 h;
步骤(3)将球磨后产物取出,烘干,压片,预烧;
步骤(4)然后以无水乙醇为介质二次球磨12~16 h后烘干;
步骤(5)将烘干的粉料过100目筛后,在100 MPa的压力下压制成直径为14 mm,厚度为2~3 mm的圆坯;
步骤(6)将压制好的圆坯烧结获得单晶;
步骤(7)经上述步骤获得的铌酸钾钠单晶处于陶瓷基体中,将铌酸钾钠单晶从陶瓷基体中取出即可得到纯的铌酸钾钠单晶。
3.根据权利要求2所述的制备方法,其特征在于:所述步骤(2)原料的摩尔比为0.52:0.48:1。
4.根据权利要求2所述的制备方法,其特征在于:所述步骤(3)预烧的温度为750℃,预烧的时间为6 h。
5.根据权利要求2所述的制备方法,其特征在于:所述步骤(6)烧结的温度在1125至1135℃,烧结时保温时间为6 h以上。
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CN114507901A (zh) * | 2021-12-30 | 2022-05-17 | 山东大学 | 包含铌酸钾钠单晶的非线性光学器件 |
CN116477944A (zh) * | 2022-12-02 | 2023-07-25 | 湖南大学 | 一种铌酸钾钠基无铅压电陶瓷及其制备方法和应用 |
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CN114507901A (zh) * | 2021-12-30 | 2022-05-17 | 山东大学 | 包含铌酸钾钠单晶的非线性光学器件 |
CN116477944A (zh) * | 2022-12-02 | 2023-07-25 | 湖南大学 | 一种铌酸钾钠基无铅压电陶瓷及其制备方法和应用 |
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