CN113149636A - 低铅ptc材料 - Google Patents

低铅ptc材料 Download PDF

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CN113149636A
CN113149636A CN202010011759.5A CN202010011759A CN113149636A CN 113149636 A CN113149636 A CN 113149636A CN 202010011759 A CN202010011759 A CN 202010011759A CN 113149636 A CN113149636 A CN 113149636A
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ptcr
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朱兴文
姜文中
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Jiangsu Jun Porcelain Technology Co ltd
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Abstract

本发明涉及一种低铅高居里温度的正温度系数热敏电阻(PTCR)陶瓷材料的制备方法。以Bi2O3、Na2CO3、PbO(或Pb3O4)、TiO2、BaCO3等为原料，通过固相反应法分别制备(Bi1/2Na1/2)TiO3、PbTiO3和BaTiO3粉体。所获得的粉体按一定的比例混合固溶，同时掺入Nb2O5、La2O3、Y2O3等中的一种或多种作为半导化剂，掺杂少量MnO2、MnCO3或Mn(NO3)2中的一种或多种为调节剂，外加适量Li2CO3、Al2O3和TiO2为烧结助剂。经过混合、造粒、成型、烧结等工艺获得低铅含量、高居里温度(>190℃)的PTCR陶瓷样品PTCR。

Description

低铅PTC材料
技术领域
本发明涉及一种低铅含量、高居里温度(>190℃)的正温度系数热敏电阻 (PTCR)陶瓷材料的制备方法，属于电子材料工艺技术领域。
背景技术
铁电BaTiO3的居里温度Tc为120℃，PTCR材料的Tc可通过SrTiO3或PbTiO3与BaTiO3固溶来调节。目前广泛使用的高居里点PTCR陶瓷均采用BaTiO3－ PbTiO3体系，Tc越高，材料中的铅含量越多。用量最大的空调加热用PTCR元件，居里温度在250℃左右，元件中PbO的含量超过30wt％。从环保的角度看， Pb对人体和环境有害。因此，研究开发低铅甚至无铅化系PTCR材料对国民经济及社会发展有着重要意义。
PTCR材料的无铅化研究始于上世纪80年代末，以铁电(Na,Bi)TiO3(简称 BNT)与BaTiO3固溶，获得(Ba,Bi,Na)TiO3系高温PTCR材料。BNT是一种具有复合钙钛矿结构的驰豫型铁电体，其居里温度为320℃，可与BaTiO3无限固溶，因而备受关注。研究表明，用BNT取代PbTiO3来制备PTCR材料时，随着 (Na,Bi)TiO3固溶量从10mol％上升至45mol％时，材料的Tc仅从180℃升至209℃，即使(Na,Bi)TiO3固溶量高达80mol％，其铁电转变温度也只有220℃左右，而此时该材料性能恶化，失去PTC效应，因此BNT-BaTiO3体系的无铅PTCR材料遭遇了一定的发展瓶颈，无法达到实用化的要求。本发明将在BNT－BaTiO3二元系PTCR材料的基础上低含量引入第三元—PbTiO3，使PTCR材料的居里温度和室温电阻率等性能达到实用化要求，同时PTCR材料低铅化的发展可大幅度减少其对环境的危害。
发明内容
本发明的目的在于提供一种低铅含量、高居里温度(>190℃)的正温度系数热敏电阻(PTCR)陶瓷材料的制备方法。
为达到上述目的，本发明采用下述技术方案：
一种低铅含量、高居里温度(>190℃)的正温度系数热敏电阻(PTCR)陶瓷材料的制备方法，其特征在于具有以下的配方和工艺步骤：
a.该材料的配方为：x(Bi1/2Na1/2)TiO3-yPbTiO3-(1-x-y)BaTiO3(简写为 BNPBT，其中x＝0.05～0.50,y＝0.01～0.15)，并掺入Nb2O5、La2O3、Sb2O3、 Sm2O3、Nd2O3等化合物中的一种或多种为半导化剂，掺入总量为0.05～0.80 atom％；同时掺杂0～0.15atom％的MnO2、MnCO3或Mn(NO3)2中的一种或多种为PTCR效应调节剂；外加0～0.5atom％Li2CO3、0～0.50atom％ Al2O3和0～3.5atom％TiO2为烧结助剂。
b.分别按原子比Bi2O3：Na2O：TiO2＝0.5：0.5：1.0和PbO：TiO2＝1.0：1.0 的比例分别称取上述分析纯原料，原料的重量纯度在99.5％以上；以玛瑙球和酒精为介质，按料：球：酒精＝1：(1～3)：(0.7～2.5)(重量)的比例将上述原料分别球磨3～72小时，烘干后分别在950±100℃和1000±100℃温度下固相反应0.5～4.0小时，获得(Bi1/2Na1/2)TiO3和PbTiO3粉体。
c.按a所列的材料配方分别称取上述材料，按料：球：去离子水＝1：(1～3)： (0.7～2.0)(重量)的比例球磨12～72小时，烘干后加3.0～12.0wt％的PVA (浓度10wt％)造粒，以10±5MPa的压力压制Φ10×2.0mm的圆片。
d.所压制的圆片在N2气氛中1200-1350℃下保温15～120分钟烧结。烧结样品的表面经研磨后以Ag-Zn浆料金属化，获得高居里温度低铅PTCR陶瓷样品。结合以下具体实施实例，对本发明作进一步详细说明。
通过本发明方法制备的Tc>190℃的低铅PTCR陶瓷材料可达到如下性能：室温电阻率低至1×103Ω·cm，居里温度Tc在190～260℃，升阻比最高达5×104，非线性系数α达5～15％。
结合以下具体实施实例，对本发明作进一步详细说明。
实施例1
按0.30(Bi1/2Na1/2)TiO3-yPbTiO3-(0.7-y)BaTiO3+0.05atom％Nb2O5+0.167 atom％Al2O3+1.0atom％TiO2+0.1atom％Li2CO3(简写为BN30PBT，其中 y＝0.01～0.15)分子式组成，换算出所需各粉料的质量，然后准确称量，称量质量如下表1：
表1.配料表一(单位：g)
编号 BNT BaTiO<sub>3</sub> PbTiO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Al<sub>2</sub>O<sub>3</sub> TiO<sub>2</sub> Li<sub>2</sub>CO<sub>3</sub>
BN30PBT-00 15.8888 40.8086 0 0.0332 0.0426 0.1997 0.01847
BN30PBT-01 15.8888 40.2257 0.7577 0.0328 0.0426 0.1997 0.01847
BN30PBT-03 15.8888 39.0597 2.2730 0.0322 0.0426 0.1997 0.01847
BN30PBT-05 15.8888 37.8937 3.7883 0.0316 0.0426 0.1997 0.01847
BN30PBT-07 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.01847
BN30PBT-09 15.8888 35.5618 6.8190 0.0302 0.0426 0.1997 0.01847
BN30PBT-11 15.8888 34.3958 8.3343 0.0296 0.0426 0.1997 0.01847
BN30PBT-13 15.8888 33.2299 9.8497 0.0290 0.0426 0.1997 0.01847
BN30PBT-15 15.8888 32.0639 11.3651 0.0284 0.0426 0.1997 0.01847
去离子水中球磨(料：球：水＝1：2.5：1.5)24小时，烘干后加8wt％的 PVA(浓度10wt％)造粒，以10MPa的压力压制Φ10×2.0mm的圆片。所压制的圆片在N2气氛中1300℃下保温60分钟烧结。烧结样品的表面经研磨后以Ag-Zn浆料金属化。以1℃/min的升温速率加热陶瓷样品，测试其电阻－温度特性，所得结果如表2所示：
表2.PTCR陶瓷样品性能与BNT含量的关系
Figure BDA0002357400050000031
实施例2
按x(Bi1/2Na1/2)TiO3-0.07PbTiO3-(0.93-x)BaTiO3+0.05atom％Nb2O5+0.167atom％Al2O3+1.0atom％TiO2+0.1atom％Li2CO3(简写为BNPBT07，其中 x＝0.05～0.50)分子式组成，换算出所需各粉料的质量，然后准确称量，称量质量如下表3：
表3.配料表二(单位：g)
编号 BNT BaTiO<sub>3</sub> PbTiO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Al<sub>2</sub>O<sub>3</sub> TiO<sub>2</sub> Li<sub>2</sub>CO<sub>3</sub>
BNPBT07-05 2.6482 51.3023 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-10 5.2960 48.3874 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-15 7.9442 45.4725 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-20 10.5924 42.5576 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-25 13.2406 39.6427 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-30 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-35 18.5369 33.8129 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-40 21.1850 30.8980 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-45 23.8332 27.9831 5.3036 0.0309 0.0426 0.1997 0.01847
BNPBT07-50 26.4814 25.0682 5.3036 0.0309 0.0426 0.1997 0.01847
去离子水中球磨(料：球：水＝1：2.5：1.5)24小时，烘干后加8wt％的 PVA(浓度10wt％)造粒，以10MPa的压力压制Φ10×2.0mm的圆片。所压制的圆片在N2气氛中1300℃下保温60分钟烧结。烧结样品的表面经研磨后以 Ag-Zn浆料金属化。以1℃/min的升温速率加热陶瓷样品，测试其电阻－温度特性，所得结果如表4所示：
表4.PTCR陶瓷样品性能与BNT含量的关系
Figure BDA0002357400050000041
Figure BDA0002357400050000051
实施例3
按0.30(Bi1/2Na1/2)TiO3-0.07PbTiO3-0.63BaTiO3+0.05atom％Nb2O5+0.167 atom％Al2O3+1.0atom％TiO2+0.1atom％Li2CO3+m atom％MnO2(简写为 BN30PBT07M，其中m＝0.02～0.15)分子式组成，换算出所需各粉料的质量，然后准确称量，称量质量如下表5：
表5.配料表三(单位：g)
编号 BNT BaTiO<sub>3</sub> PbTiO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Al<sub>2</sub>O<sub>3</sub> TiO<sub>2</sub> MnO<sub>2</sub> LiCO<sub>3</sub>
BN30PBT07M-00 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0 0.01847
BN30PBT07M-02 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0043 0.01847
BN30PBT07M-04 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0087 0.01847
BN30PBT07M-07 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0152 0.01847
BN30PBT07M-10 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0217 0.01847
BN30PBT07M-12 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0261 0.01847
BN30PBT07M-15 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.0326 0.01847
去离子水中球磨(料：球：水＝1：2.5：1.5)24小时，烘干后加8wt％的 PVA(浓度10wt％)造粒，以10MPa的压力压制Φ10×2.0mm的圆片。所压制的圆片在N2气氛中1300℃下保温60分钟烧结。烧结样品的表面经研磨后以 Ag-Zn浆料金属化。以1℃/min的升温速率加热陶瓷样品，测试其电阻－温度特性，所得结果如表6所示：
表6.PTCR陶瓷样品性能与BNT含量的关系
Figure BDA0002357400050000052
Figure BDA0002357400050000061
实施例4
按0.30(Bi1/2Na1/2)TiO3-0.07PbTiO3-0.63BaTiO3+(n atom％Nb2O5+l atom％La2O3+s atom％Sb2O3)+0.167atom％Al2O3+1.0atom％TiO2+0.1atom％Li2CO3(简写为BN30PBT07NLS，其中n＝0.05～0.30，l＝0～0.1，s＝0～0.10)分子式组成，换算出所需各粉料的质量，然后准确称量，称量质量如下表7：
表7.配料表三(单位：g)
编号 BNT BaTiO<sub>3</sub> PbTiO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> La<sub>2</sub>O<sub>3</sub> Sb<sub>2</sub>O<sub>3</sub> Al<sub>2</sub>O<sub>3</sub> TiO<sub>2</sub> Li<sub>2</sub>CO<sub>3</sub>
BN30PBT07NLS-01 15.8888 36.7278 5.3036 0.0618 0 0 0.0426 0.1997 0.01847
BN30PBT07NLS-02 15.8888 36.7278 5.3036 0.0997 0 0 0.0426 0.1997 0.01847
BN30PBT07NLS-03 15.8888 36.7278 5.3036 0.0665 0.0815 0 0.0426 0.1997 0.01847
BN30PBT07NLS-04 15.8888 36.7278 5.3036 0.0997 0.0815 0 0.0426 0.1997 0.01847
BN30PBT07NLS-05 15.8888 36.7278 5.3036 0.0997 0 0.0437 0.0426 0.1997 0.01847
BN30PBT07NLS-06 15.8888 36.7278 5.3036 0.1662 0.0815 0.0437 0.0426 0.1997 0.01847
BN30PBT07NLS-07 15.8888 36.7278 5.3036 0.2659 0.0815 0.0437 0.0426 0.1997 0.01847
去离子水中球磨(料：球：水＝1：2.5：1.5)24小时，烘干后加8wt％的 PVA(浓度10wt％)造粒，以10MPa的压力压制Φ10×2.0mm的圆片。所压制的圆片在N2气氛中1300℃下保温60分钟烧结。烧结样品的表面经研磨后以 Ag-Zn浆料金属化。以1℃/min的升温速率加热陶瓷样品，测试其电阻－温度特性，所得结果如表8所示：
表8.PTCR陶瓷样品性能与BNT含量的关系
Figure BDA0002357400050000062
Figure BDA0002357400050000071
实施例5
按0.30(Bi1/2Na1/2)TiO3-0.07PbTiO3-0.63BaTiO3+0.05atom％Nb2O5+0.167 atom％Al2O3+t atom％TiO2+0.1atom％Li2CO3(简写为BN30PBT07T，其中 t＝0.5～3.5，)分子式组成，换算出所需各粉料的质量，然后准确称量，称量质量如下表7：
表7.配料表三(单位：g)
编号 BNT BaTiO<sub>3</sub> PbTiO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Al<sub>2</sub>O<sub>3</sub> TiO<sub>2</sub> Li<sub>2</sub>CO<sub>3</sub>
BN30PBT07T-01 15.8888 36.7278 5.3036 0.0309 0.0426 0.0998 0.01847
BN30PBT07T-02 15.8888 36.7278 5.3036 0.0309 0.0426 0.1997 0.01847
BN30PBT07T-03 15.8888 36.7278 5.3036 0.0309 0.0426 0.2995 0.01847
BN30PBT07T-04 15.8888 36.7278 5.3036 0.0309 0.0426 0.3993 0.01847
BN30PBT07T-05 15.8888 36.7278 5.3036 0.0309 0.0426 0.4992 0.01847
BN30PBT07T-06 15.8888 36.7278 5.3036 0.0309 0.0426 0.5990 0.01847
BN30PBT07T-07 15.8888 36.7278 5.3036 0.0309 0.0426 0.6988 0.01847
去离子水中球磨(料：球：水＝1：2.5：1.5)24小时，烘干后加8wt％的 PVA(浓度10wt％)造粒，以10MPa的压力压制Φ10×2.0mm的圆片。所压制的圆片在N2气氛中1325℃下保温60分钟烧结。烧结样品的表面经研磨后以 Ag-Zn浆料金属化。以1℃/min的升温速率加热陶瓷样品，测试其电阻－温度特性，所得结果如表8所示：
表8.PTCR陶瓷样品性能与BNT含量的关系
Figure BDA0002357400050000072
Figure BDA0002357400050000081

Claims (1)

1.一种低铅含量、高居里温度(>190℃)的正温度系数热敏电阻（PTCR）陶瓷材料的制备方法，其特征在于具有以下的配方和工艺步骤：
a．该材料的配方为：x(Bi1/2Na1/2)TiO3- yPbTiO3-(1-x-y)BaTiO3（简写为BNPBT，其中x=0.05~0.50, y=0.01~0.15），并掺入Nb2O5、La2O3、Sb2O3、Sm2O3、Nd2O3等化合物中的一种或多种为半导化剂，掺入总量为0.05~0.80 atom%；同时掺杂0~0.15 atom% 的MnO2、MnCO3或Mn(NO3)2中的一种或多种为PTCR效应调节剂；外加0 ~0.5 atom%Li2CO3、0~0.50 atom% Al2O3和0~3.0 atom% TiO2为烧结助剂
b．分别按原子比Bi2O3：Na2O：TiO2＝0.5：0.5：1.0和PbO：TiO2＝1.0：1.0的比例分别称取上述分析纯原料，原料的重量纯度在99.5%以上；以玛瑙球和酒精为介质，按料：球：酒精＝1：(1~3)：(0.7~2.5)（重量）的比例将上述原料分别球磨3~72小时，烘干后分别在950±100℃和1000±100℃温度下固相反应0.5~4.0小时，获得(Bi1/2Na1/2)TiO3和PbTiO3粉体
c．按a所列的材料配方分别称取上述材料，按料：球：去离子水＝1：(1~3)：(0.7~2.0)（重量）的比例球磨12~72小时，烘干后加3.0~12.0wt% 的PVA（浓度10wt%）造粒，以10±5MPa的压力压制Φ10×2.0mm的圆片
d．所压制的圆片在N2气氛中1200-1350℃下保温15~120分钟烧结，烧结样品的表面经研磨后以Ag-Zn浆料金属化，获得高居里温度低铅PTCR陶瓷材料。
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CN114133237A (zh) * 2021-10-28 2022-03-04 江苏钧瓷科技有限公司 一种ptc加热器零功率陶瓷片的制作方法

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