CN1237265A - 正特性半导体陶瓷的制造方法 - Google Patents

正特性半导体陶瓷的制造方法 Download PDF

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CN1237265A
CN1237265A CN98801276A CN98801276A CN1237265A CN 1237265 A CN1237265 A CN 1237265A CN 98801276 A CN98801276 A CN 98801276A CN 98801276 A CN98801276 A CN 98801276A CN 1237265 A CN1237265 A CN 1237265A
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semiconductor
moles
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CN1145980C (zh
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高桥千寻
佐藤茂树
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TDK Corp
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TDK Corp
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Abstract

本发明的正特性半导体陶瓷的制造方法,由于其构成为准备以实质上不含有Si的BaTiO3为主成分的钛酸钡系半导体的主组合物的焙烧物,分别准备Ba2TiSi2O8和BanTimOn+2m(1≤n≤4,2≤m≤13,n< m)的添加组合物,在使上述主组合物的焙烧物和上述添加组合物进行配比混合后,进行正式烧结,故所得到的产品不仅电学特性优良,而且电学特性不易受制造条件的变动的影响,可以保证稳定的质量这样的极其卓越的效果。

Description

正特性半导体陶瓷的制造方法
技术领域
本发明涉及在例如低温发热体或彩色电视的自动消磁装置中使用，且具有正的温度系数(PTC:Positive Temperature Coefficient)的钛酸钡系半导体陶瓷(PTC热敏电阻)的制造方法，特别是涉及对于制造条件的变动而特性的离散性少的正特性半导体陶瓷的制造方法。
技术背景
众所周知，具有钙钛矿型晶体构造的钛酸钡BaTiO3，采用微量掺入稀土类或铌、锑等的半导体化剂的办法将使之半导体化，且在居里点以上的温度下将表现出电阻值急剧上升的PTC(PositiveTemperature Coefficient)的现象。
近些年来，对这一异常现象的解释和在应用方面的研究非常活跃，钛酸钡系的半导体陶瓷组合物，作为种种的发热体或开关器件、传感器、彩电的自动消磁装置等等已经实用化。
作为制造这样的钛酸钡系的半导体陶瓷组合物的方法，例如有①把氧化物或碳酸盐等用作原料进行了规定的配合后，进行烧结的固相反应法，和②把金属醇盐用作原料由液相进行合成的液相反应法等。液相反应法与固相反应法比较，尽管具有易于得到质量均匀且稳定的陶瓷组合物的优点，但是制造工序复杂而且造价高。从这种观点来看，一般使用固相反应法。
但是，若用固相反应法，则因固相反应所产生的陶瓷组合物的制造条件，例如，原料的混合状态、烧结温度和气氛的条件等，会对产品的电学特性有很大的影响。因此，为了在数量众多的制造批号的范围内保证均一的质量，就必须严密地管理各个制造工序中的制造条件，这在廉价提供优质产品方面就成了问题。
本发明就是在这样的状况之下发明的，其目的是提供一种正特性半导体陶瓷的制造方法，这种方法使所得到的半导体陶瓷产品电学特性当然要优良，同时可以供给电学特性难于受制造条件变动的影响，且具备稳定的质量的产品。
作为与本申请有关的在先技术，已分别公开了①在使含有半导体化剂的钛酸钡系半导体材料和(Ba(2-x)Ax)TiSi2O8(A：由从Li、Na、K构成的组中选择的至少一种)进行配合后，烧结成半导体陶瓷的制造方法(特开平4-311002号公报)和②向以钛酸钡为主成分，加入微量半导体化元素或Si、Mn、Al构成的组合物A中，加入以BaTinOn+1(n=2、3、4)表示的组合物B(对于1摩尔的组合物A加入0.1～4.0摩尔％)的热敏电阻的制造方法(特开平7-297009号公报)。但是，用这些方法得到的产品，不论哪一种其特性都易于受制造条件的变动的影响，作为其结果，产品特性易于离散的问题依然没能消除。特别是在上述①的技术中加入的Li、Na、K有助长特性离散的倾向。此外，在上述②的技术中加入的Al有使温度系数下降的倾向。
发明的公开
为了解决上述课题，本发明的正特性半导体陶瓷的制造方法包括：准备以实质上不含有Si的BaTiO3为主成分的钛酸钡系半导体的主组合物的焙烧物，分别准备Ba2TiSi2O8和BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的添加组合物，在使上述主组合物的焙烧物和上述添加组合物进行配比混合后，进行正式烧结。
作为更优选的方案，本发明的构成为使上述添加组合物是分别用热处理使之进行反应后的反应物。
此外，作为更优选的方案，本发明的构成为对于100摩尔上述钛酸钡系半导体的主组合物，上述Ba2TiSi2O8的含有量为0.25～3摩尔，上述BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的含有量为0.03～6.5摩尔。
此外，作为更优选的方案，本发明的构成为对于100摩尔上述钛酸钡系半导体的主组合物，上述Ba2TiSi2O8的含有量为0.35～2摩尔，上述BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的含有量为0.1～4摩尔。
此外，作为本发明的优选方案，其构成为在上述主组合物中含有用来使之半导体化的半导体化剂。
此外，作为本发明的优选的方案，其构成为在上述主组合物中作为特性改良剂含有Mn。
此外，作为本发明的优选方案，其构成为使得上述主组合物的焙烧在焙烧温度1000～1400℃下进行。
此外，作为本发明的优选方案，其构成为使得利用上述添加组合物的热处理所产生的反应，在反应温度1000～1400℃下进行处理。
此外，作为本发明的优选方案，其构成为使上述添加组合物在平均粒径0.1～3.0微米的颗粒状态下进行配合。
此外，作为本发明的优选方案，其构成为在大气中，在烧结温度1300～1400℃下处理上述正式烧结。
附图的简单说明
图1的曲线图示出了在本发明的样品和比较例的样品中的焙烧温度和电阻率之间的关系。
实施本发明的最佳方案
以下，对本发明的优选实施方案详细地进行说明。本发明的正特性半导体陶瓷的制造方法，首先，先准备好实质上不含有Si的BaTiO3为主成分的钛酸钡系半导体的主组合物的焙烧物。其次，再分别制作准备好Ba2TiSi2O8和BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的各添加组合物。各添加组合物可以是借助于预热使之反应后的反应物(例如，焙烧物状态)，也可以是反应前的仅仅是混合物的状态，但为了更为显著地引出本发明的效果，理想的方法是前者的先准备好借助于预热处理使之反应后的反应物(例如，焙烧物的状态)。用来形成反应物的热处理条件，可以根据原料的状态适当地进行选择。
制作上述主组合物的焙烧物和上述添加组合物的顺序没有什么特别限制，先制作哪一种都行。然后，按规定的量使之混合后，进行正式烧结制造正特性半导体陶瓷。
如上所述，采用先制作好规定组成的主组合物的焙烧物和上述2种添加组合物，然后，按规定量进行混合后进行正式烧结的办法得到的半导体陶瓷产品，不仅电学特性优良，而且电学特性不易受制造条件的变动的影响，可以保证质量稳定性。
上述钛酸钡系半导体的主组合物的焙烧物，含于其主组合物中的ABO3型钛酸钡中的A/B(摩尔比)通常可以设定为使之变成1，但如果是可以展现本发明的作用效果的范围的话，则可以多少偏离A/B=1。在这里，A表示Ba、Ca、Pb等2价元素，B表示Ti、Zr、Sn等的4价元素。
在主组合物中，含有用来使之半导体化的半导体化剂。作为半导体化剂优选Y、稀土类元素(La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)、Nb、Ta、W、Sb、Bi、Th中的一种以上，特别是从原料价格方面来看，优选Y、La、Ce、Nb、Ta和Sb中的一种以上。
在主组合物中，还可以以部分置换以BaTiO3为主成分的钙钛矿型氧化物的Ba、Ti等的构成元素的形式含有这些元素。
半导体化剂在主组合物中的含有率，换算成氧化物后，通常优选为0.03～0.5重量％的范围。
在主组合物中，作为特性改性剂优选含有Mn。由于含有Mn，可以增大电阻温度系数。在主组合物中，也可以一部分置换以BaTiO3为主成分的钙钛矿型氧化物的Ba、Ti等的构成元素的形式含有Mn。Mn在主组合物中的含有率，换算成MnO后，为0.1重量％以下，特别优选0.01～0.05重量％左右。
在主组合物中实质上使之不含有Si是必要的。因为我们要想得到无特性离散的、质量稳定的产品。即使是作为杂质含有Si的情况下，最好其含有率在500ppm以下。
本发明中的主组合物，在根据主组合物的组成对原料进行配合后，进行焙烧制造。作为这种情况下的原料，可以使用氧化物或复合氧化物。除此之外，还可以使用借助于烧结将变成这些氧化物或复合氧化物的各种化合物，例如，可以从碳酸盐、草酸盐、硝酸盐、氢氧化物、有机金属化合物等化合物中适当地选择使用。这些原料，通常作成为平均粒径为0.1～3微米左右的粉末进行使用。
作为主组合物中的BaTiO3钙钛矿型氧化物的原料，可以使用BaCO3、TiO2等。除此之外，还可以根据需要添加SrCO3,CaCO3等。
此外，作为半导体化剂的原料，例如可以使用Y2O3、La2O3、Ce2O3、Nb2O5、Ta2O5、Sb2O5等。
此外，为改善特性，作为优选添加Mn的原料，可以使用MnCO3、Mn(NO3)2水溶液等。
混合可以是干式混合也可以是湿式混合，在湿式混合时可以在干燥之后进行焙烧。
焙烧最好在焙烧温度1000～1400℃下进行。若温度过低，则不能充分地生成BaTiO3钙钛矿相。若温度过高，则难于粉碎。更为理想的焙烧温度，为了使在该温度变动时对电学特性的影响少，可以定为使未反应的TiO2减少的1100～1400℃。用焙烧中的所谓最高温度保持时间表示，焙烧时间通常定为0.5～6个小时左右。焙烧的升降温速度可以定为100℃/小时～500℃/小时。此外，焙烧气氛定为氧化性气氛，通常可在大气中进行。
本发明中的第1添加组合物是Ba2TiSi2O8。该添加组合物，可以采用根据组成对原料进行配合(配合得使Ba过剩)并进行混合，再用热处理使之反应(例如，焙烧)的办法制得。
原料可以从与上述主组合物相同的化合物中进行适当选择后使用，作为Ba和Ti源，可以举出BaCO3、TiO2等。作为Si源，可以使用SiO2等。这些原料的混合可以是干式混合也可以是湿式混合，在用湿式混合时，可以在干燥后得到用热处理而产生的反应物。
这种情况下的热处理进行的反应，理想的是在反应温度1000～1400℃下进行。若温度过低，则不能充分地生成均一的相。若温度过高，则难于粉碎。除此之外的热处理的反应条件，可以定为与上述主组合物的情况相同。此外，Ba2TiSi2O8相的生成，用X线衍射(XRD)进行确定，在X线衍射图的25～30deg的范围内，可以作为(211)面峰值进行确定。
本发明中的第2添加组合物是BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)。该添加组合物，可以采用根据组成对原料进行配合(配合得使Ti过剩)并进行混合，再用热处理使之反应(例如，焙烧)的办法制得。原料可以从与上述主组合物相同的化合物中进行适当选择后使用，作为Ba和Ti源，可以举出BaCO3、TiO2等。
至于原料的混合方式和热处理的反应条件等，可以按照上述第1添加组合物(Ba2TiSi2O8)的情况进行。BanTimOn+2m可以用X线衍射(XRD)进行确定，它是一种可以在X线衍射图的25～30deg的范围内确定的钛酸钡系的化合物，n＜m，即是一种Ti过剩相。
把这样制成的主组合物的焙烧物和Ba2TiSi2O8及BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的各添加组合物(理想的是用预热处理使之反应后的反应物(例如，焙烧物))按规定量配比进行混合。在这种情况下，作为更优选的方案，处于通过热处理而使之反应后的反应物的状态的添加组合物，理想的是预先粉碎好。粉碎可以是干式粉碎也可以是温式粉碎。在用湿式粉碎时，在粉碎后要预先干燥。粉碎后的各个添加组合物平均粒径理想的是0.1～0.3微米左右。
在进行配比之际，作为第1添加组合物的Ba2TiSi2O8，对于钛酸钡系半导体的主组合物100摩尔，含有0.25～3.0摩尔，最好含有0.35～2摩尔。若该值不到0.25摩尔或者超过了3摩尔，则或者作为产品的烧结性变坏，或者不会半导体化，对产品特性本身带来不好的影响。此外，作为第2添加组合物的上述BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的化合物，对于钛酸钡系半导体的主组合物100摩尔，含有0.03～6.5摩尔，最好含有0.1～4摩尔。若该值不到0.03摩尔或者超过了6.5摩尔，则或者作为产品的烧结性变坏，或者不会半导体化，对产品特性本身带来不好的影响。
举一个具体的混合方法的例子，向上述主组合物的焙烧物中，按规定的量添加配合上述那样地粉碎后的各个添加组合物，进行粉碎混合。粉碎混合通常优选湿式，然后进行干燥。这样得到的混合粉碎物的平均粒径为0.5～2.0微米是令人满意的。
这样形成的混合粉碎物材料，在形成为规定形状的成型体后，进行正式烧结。为了形成易于得到的成型体，可以向上述混合粉碎物材料中添加粘接剂。作为粘接剂，例如聚乙烯醇(PVA)等用起来就很合适。粘接剂的添加量，通常，对于混合粉碎物材料定为0.5～5.0重量％左右。
正式烧结在氧化性气氛中进行，特别优选在大气中进行，烧结温度优选为1300～1400℃。若烧结温度过低，则作为产品的陶瓷的电阻率不能变小，半导体化变得不充分。而若烧结温度过高，则易于引起异常颗粒生长。
此外，正式烧结的烧结时间，用烧结时的最高温度保持时间表示，通常定为0.5～4.0小时左右。焙烧的升降温速度可以定为100℃/小时～500℃/小时左右。
在本发明中，由于已经预先把主组合物的钛酸钡系半导体(特别是已把上述A/B作成为1)制成为焙烧物，再对该焙烧物加入Ba2TiSi2O8及BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的各添加组合物(理想的是处于反应后的化合物的状态)，故可以得到对于例如主组合物的焙烧条件、焙烧气氛等的制造条件的变动产质量量特性的离散极其之少的正特性半导体陶瓷。烧结体的平均粒径虽然因组成和烧结条件而异，但通常约为1～100微米左右。粒径可以从镜面研磨和腐蚀后的烧结体断面的光学显微镜照片或扫描显微镜(SEM)照片求得。在烧结体中SiO2主要存在于被钙钛矿层的晶粒围起来的区域即三相共存点内，半导体化剂主要存在于晶粒内，Mn在优选添加量的范围内存在晶粒内而与粒界无关。
在本发明中，与目的和用途相对应，可以得到规定的特性的正特性半导体陶瓷。举一个例子说，在室温(25℃)下的室温电阻率ρ25为10～400Ω.cm(优选40～100Ω.cm)，电阻温度系数α为10～20％/℃的陶瓷。
此外，电阻率ρ25，是在温度25℃的气氛下，用在直径14mm，厚度2.5mm左右的圆盘状的半导体陶瓷的两个主面上分别涂上In-Ga合金形成了电极的样品进行测定的值。电阻温度系数α是边使样品的温度变化边测定电阻，把电阻变成为最小电阻值的2倍时的温度定为T1，把电阻变成为最小电阻值的200倍时的温度定为T2，用下式(1)求得。
α=[4.606/(T2-T1)]×100………式(1)
用本发明的制造方法得到的正特性半导体陶瓷可以在自控式加热器(恒温发热体)、温度传感器、彩电的消磁或过流防止等用途中使用。
以下，给出具体的实施例，更为详细地说明本发明。
[实施例1]
主要组合物的制作
准备BaCO3(平均粒径1微米)、SrCO3(平均粒径1微米)、TiO2(平均粒径1微米)、Y2O3(平均粒径3微米)、Mn(NO3)2水溶液(0.1摩尔水溶液)，对它们用下述表1所示的配比进行配合。之后，用球磨机进行湿式混合并进行干燥之后，用示于表1的焙烧条件进行焙烧，得到主组合物的焙烧物。主组合物的Ba的一部分可以用Sr、Ca、Y这些元素置换，由表1的配比可知，表1中的主组合物的上述A/B之比为1。
添加组合物的制作
(1)添加组合物Ba2TiSi2O8的制作
准备BaCO3(平均粒径1微米)、TiO2(平均粒径1微米)、SiO2(平均粒径3微米)，使它们按下述表1所述的配合比率进行配合。然后，用球磨机进行湿式混合并使之干燥后，进行热处理，得到Ba2TiSi2O8反应物。热处理在热处理温度为1150℃，热处理时间为120分钟(保持时间)，在大气中的热处理气氛下进行。在用球磨机对该反应物进行了湿式粉碎后，进行干燥得到Ba2TiSi2O8添加组合物。该添加组合物的平均粒径为1微米。(2)添加组合物BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的制作
准备BaCO3(平均粒径1微米)、TiO2(平均粒径1微米)，使它们按下述表1所述的配合比率进行配合。然后，用球磨机进行湿式混合并使之干燥后，进行热处理，得到BanTimOn+2m反应物。热处理在热处理温度为1150℃，热处理时间为120分钟(保持时间)，在大气中的热处理气氛下进行。在用球磨机对该反应物进行了湿式粉碎后，进行干燥得到BanTimOn+2m添加组合物。该添加组合物的平均粒径为1微米。在表1中，样品№17，用n=1,m=2表示的化合物占大部分，样品№18，用n=2,m=5表示的化合物占大部分，样品№19，用n=2,m=9表示的化合物占大部分，除此之外的样品，用n=4,m=13表示的化合物占大部分。
半导体陶瓷材料的制作
对于主组合物以表1所示的比率配合上述添加组合物，用球磨机边进行温式粉碎边混合4个小时后，使之干燥制作半导体陶瓷材料。该材料的平均粒径为1微米。表1中的conc.1是对钛酸钡系半导体的主组合物100摩尔，把Ba2TiSi2O8的摩尔含有量表示为摩尔％的结果，表1中的conc.2是对钛酸钡系半导体的主组合物100摩尔，把BanTimSin+2m的摩尔含有量表示为摩尔％的结果。
半导体陶瓷的制作
作为粘接剂还可以向上述半导体陶瓷材料中加入2重量％的聚乙烯醇(PVA)进行粒子的制造，再用冲压机成型为圆片状，在大气中，在1350℃正式烧结2小时(保持时间)，制成直径14mm、厚度2.5mm的圆片状的半导体陶瓷样品(样品号№1～24)。
在这样制得的半导体陶瓷样品的两个主面上，分别涂上In-Ga合金，测定作为电学特性的室温下的电阻率ρ25。已经确定所得到的半导体陶瓷样品具有正的温度系数(PTC:Positive TemperatureCoefficient)。
结果示于下述表1。
        表1(之一)
        主组成物组成样品       的细目(配比量)                       主组成物的焙烧条件  Ba2TiSi2On(配比量)BanTimO(n+2m)(配比量)室温电阻率No.         氧化物换算量(摩尔)                                    氧化物换算量(摩尔)Conc.1氧化物换算量(摩尔)Conc.2    ρ25
 BaO    SrO    CaO    YO3/2 TiO2  MnO                         BaO    TiO2  SiO2(摩尔％)BaO    TiO2 (摩尔％) (Ω.cm)1    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56  0.015  0.048  0.370    902    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.015  0.008  0.015  0.75  0.012  0.040  0.310    833    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.006  0.003  0.006  0.28  0.010  0.031  0.240    924    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56  0.010  0.031  0.240    535    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.006  0.003  0.006  0.28  0.007  0.023  0.180   1026    0 765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.017  0.009  0.017  0.85  0.010  0.031  0.240    627*  0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.004  0.002  0.004  0.20  0.018  0.059  0.450  ＞1068    0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.056  0.028  0.056  2.80  0.012  0.040  0.310   20239    0.765  0.200  0.030  0.005  1.000  0.001  1170℃.110分.大气中  0.015  0.008  0.015  0.75  0.012  0.040  0.310    8710   0.765  0.200  0.030  0.005  1.000  0.001  1130℃.110分.大气中  0.015  0.008  0.015  0.75  0.012  0.040  0.310    8011* 0.765  0.200  0.030  0.005  1.000  0.001  1170℃.110分.大气中  0.002  0.001  0.002  0.12  0.001  0.003  0.020    5312* 0.765  0.200  0.030  0.005  1.000  0.001  1130℃.110分.大气中  0.002  0.001  0.002  0.12  0.001  0.003  0.020    13*号表示本发明范围外的样品(比较例样品)
       表1(之一)
        主组成物组成样品       的细目(配比量)                    主组成物的焙烧条件    Ba2TiSi2On(配比量)BanTimO(n+2m)(配比量)室温电阻率No.        氧化物换算量(摩尔)                                    氧化物换算量(摩尔)Conc.1氧化物换算量(摩尔)conc.2   ρ25
 BaO    SrO    CaO    YO3/2 TiO2  MnO                         BaO    TiO2  SiO2(摩尔％)  BaO     TiO2   (摩尔％)  (Ω.cm)13   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.CO2中  0.015  0.008  0.015  0.75    0.012   0.040     0.310     8614   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.N2中   0.015  0.008  0.015  0.75    0.012   0.040     0.310     8015* 0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.CO2中  0.002  0.001  0.002  0.12   3×10-4 0.001     0.008     4016* 0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.N2中   0.002  0.001  0.002  0.12   3×10-4 0.001     0.008     1217   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.015  0.008  0.015  0.75    0.028   0.056     2.820     8318   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.015  0.008  0.015  0.75    0.018   0.046     0.913     8819   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.015  0.008  0.015  0.75    0.008   0.035     0.391     9220* 0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.070  0.035  0.070  3.50    0.012   0.040     0.310    ＞10621   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56    0.200   0.650     5.000    156022   0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56    0.252   0.819     6.300    242023* 0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56    0.288   0.936     7.200    ＞10524* 0.765  0.200  0.030  0.005  1.000  0.001  1150℃.110分.大气中  0.011  0.006  0.011  0.56   4×10-41.3×10-3 0.010    ＞105*号表示本发明范围外的样品(比较例样品)
由表1所示的结果可知本发明的效果。
请特别注意样品№2、样品№9、样品№10、样品№13和样品№14的数据。这些半导体陶瓷样品的组成全都一样，仅仅是主组合物的焙烧条件的温度条件和焙烧气氛不同。即它们是预定实际的工序的变动，使主组合物的焙烧条件变动来获取数据的样品。可知这些用本发明的制造方法得到的产品样品，尽管工序变动但电阻率ρ25的值几乎不发生变动，得到了无偏差的均一的质量。
同样，在样品№13和样品№14这一组(对)以及样品№15和样品№16这一组(对)中，主组合物的组成和主组合物的焙烧条件，对每一组都是相同的。但是，样品№15和样品№16这一组(对)，其添加组合物的含有比率处于非优选范围内，故电阻率ρ25的值取稍低的值，而且，得知随着主组合物的焙烧条件的变动(焙烧气氛的变动)，电阻率ρ25的值方面也产生了离散。
[实施例2]
对于上述实施例1的半导体陶瓷样品№1的制作，不分别进行主组合物和添加组合物的热处理，在一次混合搅拌这些原料后，进行焙烧，然后进行正式烧结(比较实验)。其结果是，在焙烧温度1130℃下得到的样品，电阻率ρ25为73Ω·cm，在焙烧温度1150℃下得到的样品，电阻率ρ25为85Ω·cm，在焙烧温度1170℃下得到的样品，电阻率ρ25=110Ω·cm，随着主组合物的焙烧条件的变动(焙烧气氛的变动)，电阻率ρ25的值方面地产生了离散。
在图1的曲线图中示出了由该比较实验得到的3个比较例样品的电阻率ρ25数据，和在上述表1中示出的本发明的样品№2、样品№9和样品№10的电阻率ρ25数据，并进行了比较。由图1示出的曲线图可知，本发明的样品随着主组合物的焙烧条件的变动(焙烧气氛的变动)的电阻率ρ25数据的值的离散极其之少。
由上述的结果可知本发明的效果。就是说，本发明的正特性半导体陶瓷的制造方法，由于其构成为准备以实质上不含有Si的BaTiO3为主成分的钛酸钡系半导体的主组合物的焙烧物，分别准备Ba2TiSi2O8和BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的添加组合物，在使上述主组合物的焙烧物和上述添加组合物进行配比混合后，进行正式烧结，故所得到的产品不仅的电学特性优良，而且电学特性不易受制造条件的变动的影响，可以保证稳定的质量这样的极其卓越的效果。
工业上利用的可能性
用本发明制造方法得到的正特性半导体陶瓷，可以在自控型加热器(恒温发热体)、温度传感器、彩电的自动消磁装置或过电流防止等领域中使用。

Claims (10)

  1. 一种正特性半导体陶瓷的制造方法，其特征是：准备以实质上不含有Si的BaTiO3为主成分的钛酸钡系半导体的主组合物的焙烧物，
    分别准备Ba2TiSi2O8和BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的添加组合物，
    在使上述主组合物的焙烧物和上述添加组合物进行配比混合后，进行正式烧结。
  2. 2、权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：上述添加组合物是分别通过热处理使之反应后的反应物。
  3. 3、权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：对于100摩尔上述钛酸钡系半导体的主组合物，上述Ba2TiSi2O8的含有量为0.25～3摩尔，上述BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的含有量为0.03～6.5摩尔。
  4. 4、权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：对于100摩尔上述钛酸钡系半导体的主组合物，上述Ba2TiSi2O8的含有量为0.35～2摩尔，上述BanTimOn+2m(1≤n≤4,2≤m≤13,n＜m)的含有量为0.1～4摩尔。
  5. 5、权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：在上述主组合物中含有用于半导体化的半导体化剂。
  6. 6．权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：在上述主组合物中含有Mn作为特性改性剂。
  7. 7．权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：上述主组合物的焙烧，在焙烧温度1000～1400℃下进行。
  8. 8．权利要求2所述的正特性半导体陶瓷的制造方法，其特征是：利用上述添加组合物的热处理的反应，在反应温度1000～1400℃下进行处理。
  9. 9．权利要求2所述的正特性半导体陶瓷的制造方法，其特征是：上述添加组合物在平均粒径0.1～3.0微米的颗粒状态下进行配合。
  10. 10．权利要求1所述的正特性半导体陶瓷的制造方法，其特征是：上述正式烧结在大气中，在烧结温度1300～1400℃下进行处理。
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CN102674831A (zh) * 2005-04-28 2012-09-19 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN102674831B (zh) * 2005-04-28 2016-01-20 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN101909199B (zh) * 2006-09-19 2013-01-02 株式会社东芝 广播接收终端装置
CN104302599A (zh) * 2012-04-20 2015-01-21 日立金属株式会社 半导体陶瓷组合物的制造方法
CN106431390A (zh) * 2015-08-04 2017-02-22 Tdk株式会社 半导体陶瓷组合物和ptc热敏电阻
CN106431390B (zh) * 2015-08-04 2019-03-15 Tdk株式会社 半导体陶瓷组合物和ptc热敏电阻
CN114560694A (zh) * 2022-03-30 2022-05-31 深圳市金科特种材料股份有限公司 一种陶瓷ptc热敏电阻材料的制备方法
CN114560694B (zh) * 2022-03-30 2022-12-09 深圳市金科特种材料股份有限公司 一种陶瓷ptc热敏电阻材料的制备方法

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JP4080576B2 (ja) 2008-04-23
EP0961299B1 (en) 2006-01-11
EP0961299A4 (en) 2000-07-05
US6221800B1 (en) 2001-04-24
DE69833203D1 (de) 2006-04-06
KR20000068888A (ko) 2000-11-25
EP0961299A1 (en) 1999-12-01
TW393652B (en) 2000-06-11
DE69833203T2 (de) 2006-09-21

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