CN106278250A - 一种无铅正温度系数热敏电阻陶瓷的制备方法 - Google Patents

一种无铅正温度系数热敏电阻陶瓷的制备方法 Download PDF

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CN106278250A
CN106278250A CN201610749886.9A CN201610749886A CN106278250A CN 106278250 A CN106278250 A CN 106278250A CN 201610749886 A CN201610749886 A CN 201610749886A CN 106278250 A CN106278250 A CN 106278250A
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朱兴文
任慧茹
牛伟鉴
李晨
姜亦杨
姜文中
周晓
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University of Shanghai for Science and Technology
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Abstract

本发明涉及一种大气氛下烧结的高居里温度、高升阻比、低室温电阻率无铅正温度系数热敏电阻陶瓷的制备方法的制备方法,该方法采用以下配方:x(Bi1/2Na1/2)TiO3 yCaTiO3‑(1‑x‑y)BaTiO3+aLi2CO3+bSb2O3粉体,其中,x=0.01~0.12,y=0~0.20,a=0~0.5 mol%,b=0~0.20 mol%,Nb2O5、La2O3、Sm2O3、Nd2O3化合物中的一种或多种为半导化剂;Al2O3和TiO2为烧结助剂,采用的工艺是:将上述所列材料压制的圆片在大气气氛中1250‑1380℃下保温10~30分钟烧结,使其充分烧结和实现固相反应;对烧结后的圆片表面进行研磨,上电极,制得PTCR陶瓷材料。该陶瓷材料的室温电阻率低至30Ω•cm,居里温度Tc高达155℃,升阻比高达106以上。该无铅材料已达到实用化要求。

Description

一种无铅正温度系数热敏电阻陶瓷的制备方法
技术领域
[0001] 本发明涉及一种大气气氛下烧结的高居里温度(Tc>150°C)、高升阻比(R max/Rmin> 1.0X106)、低室温电阻率(P:~30Ω · cm)无铅正温度系数热敏电阻陶瓷的制备方法。
背景技术
[0002] 铁电BaTi〇3的居里温度TcSl20°C,通过添加适量施主杂质可使其半导化同时具有 正温度系数热敏电阻效应(PTC效应hPTC材料在汽车、家电、通信、自动化控制等领域具有 广泛的应用。目前广泛使用的PTC加热元件均采用BaTi〇3-PbTi〇3体系,T C越高,材料中的铅 含量越多。用量最大的空调加热用PTC元件,居里温度在250°C左右,元件中PbO的含量超过 30wt%。众所周知,重金属元素 Pb对人体有毒害作用,对环境的影响尤甚。据估计,1克铅会 导致1平方米的土壤污染,这种污染是长期性的,今后对废弃含铅PTC元件的处置将面临较 大难题。因此,开发高Tc温度无铅PTC材料对目前的经济及社会发展有重要意义。
[0003] PTCR材料的无铅化研究始于上世纪80年代末,以铁电(Na,Bi)Ti〇3(简称BNT)与 BaTi03固溶,获得(Ba,Bi,Na)Ti03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°C。研究表明,在大气气氛下烧结,随(Na,Bi)Ti0 3固溶量的增 加,PTC材料的室温电阻率急剧上升至绝缘。而在非氧化气氛如N2或在还原气氛下烧结,即 使BNT含量达30mo 1 %,PTCR材料的电阻率仍可达到实用化要求。但需要气氛保护的烧结制 造方法增加了工艺成本。本发明将在BNT - BaTi03二元系PTCR材料的基础上引入第三 元--CaTi03,并添加 Li2C03作为助烧剂,以期在大气气氛中烧结制备一种室温电阻率在30 Ω · cm左右、居里温度在150°C附近、升阻比最高达到106以上的无铅PTC材料。
发明内容
[0004] 本发明的目的在于提供一种大气氛下烧结的高居里温度(Tc>150°C)、高升阻比 (UU1.0 X 1〇6)、低室温电阻率(P:~30 Ω · cm)无铅正温度系数热敏电阻陶瓷的制备 方法。
[0005] 为达到上述目的,本发明采用下述技术方案:
[0006] -种无铅正温度系数热敏电阻陶瓷的制备方法,其特征在于该方法的具体步骤 为:
[0007] a.将x(Bii/2Nai/2)Ti〇3-yCaTi〇3-(l-x-y)BaTi〇3+aLi2⑶ 3+bSb2〇3粉体,其中,x = 0·01~0· 12,y = 0~0· 20,a = 0~0· 5mol %,b = 0~0· 20mol% ;Nb2〇5、La2〇3、Sm2〇3、Nd2〇3化合 物中的一种或多种为半导化剂,其掺入量为所述粉体的〇. 05~0.50atom% ;再掺入所述粉 体的0~0.50atom%的AI2O3和0~3.5atom%的Ti〇2为烧结助剂,以玛瑙球和酒精或去离子 水为介质,球磨12~72小时,烘干后得到混合粉末;
[0008] b .在步骤a所得混合粉末中加入该混合粉末重量的3.0~12 .Owt %的浓度为 1 Owt %的聚乙烯醇PVA水溶液,造粒;
[0009] C.将步骤b所得颗粒压制成的圆片;
[0010] d.将步骤c所得圆片在1250-1380°C温度下、保温10~30分钟,即得到无铅正温度 系数热敏电阻陶瓷。
[00Ί1 ] 上述的半导化剂为Nb2〇5、La2〇3、Sm2〇3、M2O3化合物中的至少一种。
[0012] 上述的CaTi03和(BivAavdTiOs粉体由如下方法获得:按原子比Bi203 :Na20:Ti02 =0.5:0.5:1.0和按原子比CaC03:Ti02 = 1.0:1.0的比例称取两组分析纯的原料,以玛瑙球 和酒精为介质,将上述两组原料分别混合,在磨机中球磨3~72小时,将烘干后混合料分别 放在980 °C和1400 °C温度下充分煅烧,煅烧时间为0.5~4.0小时,分别获得(B i 1/2Na1/2) T i 03 和CaTi03粉体。
[0013] 与现有技术相比,本发明的有益效果是:本发明在空气气氛下制备的PTCR无铅陶 瓷材料的电性能可以实现以下参数要求:居里温度Tc>150°C,室温电阻率〈30Ω · cm,PTC升 阻比Rmx/Ul ·8 X 106,电阻温度系数a>34%/°C。
附图说明
[0014] 图 1 · BNT = 4 · Omo 1 %、Ca2+ = 0~20mo 1 % 样品的R-T 曲线;
[0015] 图 2.BNT = 6.0mol%、Ca2+ = 0 ~20mol% 样品的 R-T 曲线;;
[0016] 图3.1^1 = 4.〇111〇1%、〇&2+ = 6.〇1]1〇1%、1^+ = 0~0.31]1〇1%样品的1?-T曲线;
[0017] 图4.不同Sb含量试样(Sb3+ = 0~0.15mol%)样品的R-T曲线。
具体实施方式
[0018] 结合以下具体实施实例,对本发明作进一步详细说明。
[0019] 实施例1
[0020] 按0 · 〇4(Bii/2Nai/2)Ti〇3-yCaTi〇3_(0 · 96-y)BaTi03+0 · 165mol %Nb2〇5+0 · 167mol % 八1203+1.0111〇1%1102+0.2111〇1%1^2〇)3进行配料,其中7 = 0.02、0.04、0.06、0.08、0.10、0.12、 0.14、0.16、0.18、0.20,按分子式中的摩尔比计算重量后称重,称量质量如下表1:
[0021] 表1.配料表一(单位:g)
Figure CN106278250AD00041
[0023] 按照配料表一中的配方称重,预合成BNT、CaTi03后再按比例加入BaTi03、Nb 205、 八1203、1102、1^2〇)3,以玛瑙球和去离子水为介质,球磨24小时,烘干后的粉末加8的%的浓度 为1 Owt %的聚乙烯醇(PVA)造粒,以1 OMPa的压力压制Φ 10 X 2 · Omm的圆片,保压15s,将压制 好的圆片在空气气氛下进行烧结,烧结温度为1350Γ,并在该温度下保温lOmin,使其充分 烧结和实现固相反应;烧结后的样品经表面打磨光滑以后,于超声波里冲洗8min,以Ag-Zn 浆料电极涂覆,并将电极在490 °C烧结保温8min,将电极固化,最终获得PTCR陶瓷样品。以2 °C/min的升温速率加热陶瓷样品,测得其电阻-温度特性,其结果如表2和图1所示。
[0024]表2.不同Ca含量试样的电性能
Figure CN106278250AD00051
[0026] 结论:引入第三元CaTi03可大幅降低样品室温电阻率,同时提高材料的PTC效应。 Ca2+含量为0.06mol时,PTC性能最好:室温电阻率低至36Ω · cm,居里温度达148°C,升阻比 高达1.87E+06,非线性系数约16.8%
[0027] 实施例2
[0028] 按0 · 〇6(Bii/2Nai/2)Ti〇3-yCaTi〇3_(0 · 94-y)BaTi03+0 · 165mol %Nb2〇5+0 · 167mol % 八1203+1.0111〇1%1102+0.2111〇1%1^2〇)3进行配料,7 = 0.02、0.04、0.06、0.08、0.10、0.12、 0.14、0.16、0.18、0.20,按分子式中的摩尔比计算重量后称重,称量质量如下表3:
[0029] 表3.配料表二(单位:g)
Figure CN106278250AD00052
Figure CN106278250AD00061
[0032] 按照配料表二中的配方称重,预合成BNT、CaTi03后再按比例加入BaTi03、Nb 205、 八1203、1102、1^ 2〇)3,以玛瑙球和去离子水为介质,球磨24小时,烘干后的粉末加8的%的浓度 为10wt %的聚乙烯醇(PVA)造粒,以1 OMPa的压力压制Φ 10 X 2 · 0mm的圆片,保压15s,将压制 好的圆片在空气气氛下进行烧结,烧结温度为1330Γ,并在该温度下保温lOmin,使其充分 烧结和实现固相反应;烧结后的样品经表面打磨光滑以后,于超声波里冲洗8min,以Ag-Zn 浆料电极涂覆,并将电极在490 °C烧结保温8min,将电极固化,最终获得PTCR陶瓷样品。以2 °C/min的升温速率加热陶瓷样品,测得其电阻-温度特性,其结果如表4和图2所示。
[0033] 表4. BNT含量0.06试样的电性能
Figure CN106278250AD00062
[0035] 结论:随着Ca2+含量的增加,室温电阻率上升,居里温度、升阻比下降。从中可以看 出,Ca 2+含量为0.02mol时,PTC性能最好:室温电阻率低至176Ω · cm,居里温度达154°C,升 阻比高达8.98E+05,非线性系数约24.2%。与实施例1相比,材料的居里温度上升了6°C,室 温电阻上升了约5倍。
[0036] 实施例3
[0037] 按0 · 〇4(Bii/2Nai/2)Ti〇3-〇 · 06CaTi03-0 · 90BaTi〇3+aLi2C〇3+0 · 165mol %Nb2〇5+ 0.167mol %Ah〇3+l. Omol %Ti〇2进行配料,其中a = 0~0.003,按分子式中的摩尔比计算重 量后称重,称量质量如下表5:
[0038] 表5.配料表三(单位:g)
Figure CN106278250AD00063
Figure CN106278250AD00071
[0040] 按照配料表三中的配方称重,预合成BNT、CaTi〇3后再按比例加入BaTi〇3、Nb2〇5、 八1203、1102、1^2〇)3,以玛瑙球和去离子水为介质,球磨24小时,烘干后的粉末加8的%的浓度 为10wt %的聚乙烯醇(PVA)造粒,以1 OMPa的压力压制Φ 10 X 2 · 0mm的圆片,保压15s,将压制 好的圆片在空气气氛下进行烧结,烧结温度为1350Γ,并在该温度下保温lOmin,使其充分 烧结和实现固相反应;烧结后的样品经表面打磨光滑以后,于超声波里冲洗8min,以Ag-Zn 浆料电极涂覆,并将电极在490 °C烧结保温8min,将电极固化,最终获得PTCR陶瓷样品。以2 °C/min的升温速率加热陶瓷样品,测得其电阻-温度特性,其结果如表6和图3所示。
[0041]表6.不同Li含量试样的电性能
Figure CN106278250AD00072
[0043]结论:添加 Li2C03,使得样品具有良好的PTC性能。随着Li含量的增加,室温电阻增 大,非线性系数减小。综合来看,Li含量约0.2mol%时,样品性能最好:室温电阻率低至36 Ω·cm,居里温度、升阻比分别高达148°C、1.87E+06,同时非线性系数约16.8%
[0044] 实施例4
[0045] 按
[0046] 0 · 〇4(Bii/2Nai/2)Ti〇3-〇 · 06CaTi03-0 · 90BaTi03+0 · 2mol %Li2C〇3+bSb2〇3+ 0· 165mol%Nb2〇5+0.167mol%Al2〇3+l .Omol%Ti〇2进行配料,b = 0~0· 15mol%,按分子式中 的摩尔比计算重量后称重,称量质量如下表7:
[0047] 表7.配料表四(单位:g)
Figure CN106278250AD00073
[0049] 按照配料表四中的配方称重,预合成BNT、CaTi03后再按比例加入BaTi03、Nb 205、 △1203、1^02、1^2〇)3、313 203,以玛瑙球和去离子水为介质,球磨24小时,烘干后的粉末加8¥七% 的浓度为l〇wt%的聚乙烯醇(PVA)造粒,以lOMPa的压力压制Φ10Χ2·0πιπι的圆片,保压15s, 将压制好的圆片在空气气氛下进行烧结,烧结温度为1330Γ,并在该温度下保温lOmin,使 其充分烧结和实现固相反应;烧结后的样品经表面打磨光滑以后,于超声波里冲洗8min,以 Ag-Zn浆料电极涂覆,并将电极在490 °C烧结保温8min,将电极固化,最终获得PTCR陶瓷样 品。以2°C/min的升温速率加热陶瓷样品,测得其电阻-温度特性,其结果如表8和图4所示。 [00 50] 表8.不同Sb2〇3含量试样的电性能
Figure CN106278250AD00081
[0053]结论:上述样品是在1330°C下烧结的,从中可以看出,添加少量Sb203有助于降低烧 结温度,提高样品PTC性能。其中,Sb2〇3含量为0.0 lmol %时,样品PTC性能最好,室温电阻率 低至33Ω · cm,居里温度达146°C,升阻比高达4.02E+05,非线性系数约17.1%。

Claims (3)

1. 一种无铅正温度系数热敏电阻陶瓷的制备方法,其特征在于该方法的具体步骤为: a. 将x(Bii/2Nai/2)Ti〇3-yCaTi〇3-(l-x-y)BaTi〇3+aLi2C〇3+bSb2〇3粉体,其中,χ = 0·01 ~ 0· 12,y = 0~0 · 20,a = 0~0· 5mol%,b = 0~0 · 20mol% ;Nb2〇5、La2〇3、Sm2〇3、Nd2〇3化合物中的 一种或多种为半导化剂,其掺入量为所述粉体的0.05~0.50atom% ;再掺入所述粉体的0~ 0.50atom%的Al2〇3和0~3.5atom%的Ti02为烧结助剂,以玛瑙球和酒精或去离子水为介 质,球磨12~72小时,烘干后得到混合粉末; b. 在步骤a所得混合粉末中加入该混合粉末重量的3.0~12. Owt %的浓度为10wt %的 聚乙烯醇PVA水溶液,造粒; c. 将步骤b所得颗粒压制成的圆片; d. 将步骤c所得圆片在1250-1380°C温度下、保温10~30分钟,即得到无铅正温度系数 热敏电阻陶瓷。
2. 根据权利要求1所述的无铅正温度系数热敏电阻陶瓷的制备方法,其特征在于所述 的半导化剂为Nb2〇5、La2〇3、Sm2〇3、M2O3化合物中的至少一种。
3. 根据权利要求1所述的无铅正温度系数热敏电阻陶瓷的制备方法,其特征在于所述 的CaTi03和(BimNav〗)Ti0 3粉体由如下方法获得:按原子比Bi2〇3: Na20: Ti02 = 0.5:0.5:1.0 和按原子比CaC03:Ti02 = l .0:1.0的比例称取两组分析纯的原料,以玛瑙球和酒精为介质, 将上述两组原料分别混合,在磨机中球磨3~72小时,将烘干后混合料分别放在980°C和 1400°C温度下充分煅烧,煅烧时间为0.5~4.0小时,分别获得(Bi 1/2Na1/2)Ti03和CaTi03粉 体。
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