CN107043252A - 半导体陶瓷组合物以及ptc热敏电阻 - Google Patents

半导体陶瓷组合物以及ptc热敏电阻 Download PDF

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CN107043252A
CN107043252A CN201710067787.7A CN201710067787A CN107043252A CN 107043252 A CN107043252 A CN 107043252A CN 201710067787 A CN201710067787 A CN 201710067787A CN 107043252 A CN107043252 A CN 107043252A
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content
ceramic composition
semiconductive ceramic
resistivity
particle diameter
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伊藤和彦
志村寿
志村寿一
藤田孝
藤田一孝
守越广树
寺田朋广
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TDK Corp
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TDK Corp
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Abstract

本发明的目的在于提供一种使居里点移向高于120℃的高温侧，25℃电阻率小而且耐电压以及机械强度优异的半导体陶瓷组合物、以及PTC热敏电阻。本发明所涉的半导体陶瓷组合物的特征为：在BaTiO3类的半导体陶瓷组合物中，Ba的一部分至少被A(选自Na或K中的至少一种)、Bi以及RE(选自含有Y的稀土元素中的至少一种)取代，并且Ti的一部分至少被TM(选自V、Nb以及Ta中的至少一种)取代，在将(Ti含量+TM含量)设定为1mol时，满足0.7≤[(Bi含量)/(A含量)]≤1.43；0.017≤[(Bi含量)+(A含量)]≤0.25；0＜(RE含量+TM含量)≤0.01，并且在晶体粒径为1.1～4.0μm的范围内具有粒径分布的最大峰值，该峰值的分布频率为20％以上。

Description

半导体陶瓷组合物以及PTC热敏电阻
技术领域
本发明涉及用于加热器元件和过热检测元件等的半导体陶瓷组合物以及PTC热敏电阻。
背景技术
作为热敏电阻之一，已知有一种具有正的电阻温度系数的PTC(PositiveTemperature Coefficient)热敏电阻。该PTC热敏电阻相对于温度上升而电阻增大，因此能够作为自控式加热器元件、过电流保护元件、过热检测元件等使用。一直以来，PTC热敏电阻是一种将微量稀土元素等添加到主成分的钛酸钡(BaTiO3)从而被半导体化的热敏电阻，所以在居里点以下为低电阻，但是在其上会有几个数量级的急剧高电阻化。
BaTiO3的居里点一般为大约120℃，但是由用Sr来取代Ba的一部分或者用Sn来取代Ti的一部分等方法就能够使居里点移向低温侧。但是，对于居里点的向高温侧的移动来说，现在是用Pb来取代Ba的一部分，从降低环境负荷的世界潮流出发，也要求实现不使用Pb的替代材料的实用化。
在下述的专利文献1中，记载有在用Bi、碱金属Al(Na、K、Li中的一种或者两种以上)以及稀土元素Q(La、Dy、Eu、Gd中的一种或者两种以上)来取代BaTiO3的Ba的一部分的半导体陶瓷组合物中，通过将(Bi0.5Al0.5)以及Q的含量控制在规定的范围内，从而不使用Pb就能够将居里点提高到130～183℃，并且能够获得25℃电阻率小的半导体陶瓷组合物。
现有技术文献
专利文献
专利文献1：日本专利第4765258号公报
发明内容
发明所要解决的技术问题
在上述专利文献1中，记载了不使用Pb就能够将居里点提高到130～183℃，并且能够获得25℃电阻率小的半导体陶瓷组合物，但是在考虑了作为PTC热敏电阻特别是作为加热器元件的用途的情况下，存在耐电压或机械强度不够充分的可能性。
例如，被用于汽车室内暖气设备的PTC热敏电阻作为加热器元件是在被夹于铝制散热片的状态下被施加高电压，因此要求优异的机械强度和高耐电压化。
本发明就是鉴于上述实际情况而完成的发明，其目的在于提供一种能使居里点移向高于120℃的高温侧，25℃电阻率小并且耐电压以及机械强度优异的半导体陶瓷组合物、以及具备该半导体陶瓷组合物的PTC热敏电阻。
解决技术问题的手段
本发明所涉及的半导体陶瓷组合物的特征为：在BaTiO3系的半导体陶瓷组合物中，Ba的一部分至少被A(选自Na或K中的至少一种碱金属元素)、Bi以及RE(选自含有Y的稀土元素中的至少一种元素)取代，并且Ti的一部分至少被TM(选自V、Nb以及Ta中的至少一种元素)取代，在将(上述Ti的含量+上述TM的含量)设定为1mol的时候满足0.7≤[(Bi的含量)/(A的含量)]≤1.43；0.017≤[(Bi的含量)+(A的含量)]≤0.25；0＜(RE的含量+TM的含量)≤0.01，并且上述半导体陶瓷组合物由多个晶体颗粒构成，上述多个晶体颗粒的晶体粒径在1.1μm以上且4.0μm以下的范围内具有粒径分布的最大峰值，该峰值的分布频率为20％以上。
另外，本发明所涉及的PTC热敏电阻的特征在于：在使用上述的半导体陶瓷组合物形成的陶瓷素体的表面上形成有一对电极。
发明的效果
根据本发明，能够提供一种使居里点移向高于120℃的高温侧，25℃电阻率小并且耐电压以及机械强度优异的半导体陶瓷组合物以及PTC热敏电阻。
附图说明
图1是表示具备本发明的一个实施方式所涉及的半导体陶瓷组合物的PTC热敏电阻的一个构成例子的立体图。
图2是表示本发明的一个实施方式所涉及的半导体陶瓷组合物的粒度分布的一个例子的图。
符号说明
1：PTC热敏电阻
2：陶瓷素体
3a、3b：电极
具体实施方式
如图1所示，PTC热敏电阻1具备由本申请发明的BaTiO3类半导体陶瓷组合物构成的陶瓷素体2、形成在陶瓷素体的相对的表面上的一对电极3a以及3b。作为电极3a以及3b可以使用由Cu、Ni、Al、Cr、Zn、Ag、Ni-Cr合金、Ni-Cu等导电性材料构成的单层结构或者多层结构来形成。
作为本发明的一个实施方式的半导体陶瓷组合物，只要是包含用Bi、A(选自Na或K中的至少一种碱金属元素)来取代BaTiO3中的Ba的一部分，进一步作为半导体化剂用RE(选自含有Y的稀土元素的至少一种元素)来取代Ba的一部分，并且用TM(选自V、Nb以及Ta中的至少一种元素)来取代Ti的一部分的组成的，可以采用任意组成，例如用下述式(1)表示组成式，
(Ba1-b-c-eBibAcREe)(Ti1-fTMf)O3 (1)
在上述组成式(1)中，优选分别表示用Bi、A、RE来取代Ba位点的一部分的量、用TM来取代Ti位点的一部分的量的b、c、e、f满足下述式(2)～(4)。
0.7≤b/c≤1.43 (2)
0.017≤(b+c)≤0.25 (3)
0＜(e+f)≤0.01 (4)
另外，上述半导体陶瓷组合物由多个晶体颗粒构成，上述多个晶体粒径在1.1μm以上且4.0μm以下的范围内具有粒径分布的最大峰值，该峰值的分布频率为20％以上。
通过满足上述式(2)～(4)，将晶体粒径的粒径分布的最大峰值范围设定为1.1μm以上且4.0μm以下，并且将该峰值的分布频率设定为20％以上，从而25℃电阻率小，并且耐电压以及机械强度高，进一步还能够使居里点移向高于120℃的高温侧。另外，本发明中的居里点是指上述半导体陶瓷组合物的电阻率与25℃的电阻率相比成为2倍时的温度。上述晶体粒径分布的最大峰值的范围以及该峰值的分布频率可以通过在上述组成式(1)中满足上述(2)～(4)，并且适当调整TiO2原料的粒径或煅烧后的球磨粉碎时间来获得。
另外，晶体粒径的粒度分布是从将上述半导体陶瓷组合物(烧结体)的埋入研磨截面进行了蚀刻处理后的样品的扫描电子显微镜照片中，通过图像解析来求得的。具体而言，使用图像处理软件Mac-view在上述扫描电子显微镜照片上测量颗粒的大小和个数，将粒径设定为Heywood径，并在体积分布中计算粒度分布。另外，上述扫描电子显微镜照片的倍率为能够获得颗粒数50个以上的倍率。
在图2中示出了用上述方法获得的晶体粒径的粒度分布的一个例子。在此，最大分布峰值为取得了相对于Heywood直径的体积分布频率时的峰值P，此时的Heywood直径Hp为1.1μm以上且4.0μm以下的范围，并且在频率Fp成为20％以上的情况下，能够获得25℃电阻率小并且在耐电压以及机械强度优异的半导体陶瓷组合物。在图2的例子中，Hp为1.64μm，Fp为33％，两者都处于上述范围内。
另外，关于横轴(Heywood直径)的晶体粒径的范围为默认设置，并且将0.005～6.541μm的范围分割成42点。
在上述组成式(1)中，上述Bi的含量b和上述A的含量c优选为，在将(Ti+TM)设定为1mol时，以摩尔比换算满足0.017≤(b+c)≤0.25并且0.7≤b/c≤1.43。在(b+c)小于0.017的情况下，会有居里点不移向高于120℃的高温侧的情况，因而不优选。另外，如果(b+c)超过0.25，则半导体化变得不充分，并且25℃电阻率上升，因此不优选。另外，在不满足0.7≤b/c≤1.43的情况下，半导体化变得不充分并且25℃电阻率上升，因而不优选。
在上述组成式(1)中，关于作为半导体化剂而作用的RE(选自含有Y的稀土元素中的至少一种元素)和TM(选自V、Nb以及Ta中的至少一种元素)的总量：(e+f)，优选为0＜(e+f)≤0.01的范围。如果(e+f)为0或者大于0.01，则25℃电阻率上升，因而不优选。进一步优选为通过控制为0.001以上且0.006以下，从而25℃电阻率减小效果大。另外，上述半导体化剂不管是单独的RE或者是单独的TM，其优选的添加范围都相同。另外，进一步优选选择La、Sm、Gd作为RE，选择Nb作为TM。进一步，更加优选各以等量添加上述RE(Sm、Gd、Er)和TM(Nb)。通过设定上述半导体化剂以及添加方法从而能够稍稍提高25℃电阻率减小效果。
另外，在上述半导体陶瓷组合物中，进一步优选(Ba、Bi、A、Re的总摩尔数)相对于(Ti和TM的总摩尔数)的摩尔比满足1.001以上且1.06以下。由此，就能够进一步减小25℃电阻率。
另外，在上述半导体陶瓷组合物中，在将(Ti的含量+TM的含量)设定为1mol时，优选以按元素进行换算为0.049以下的比例含有Ca。由此，烧结密度变高，并且能够进一步减小25℃电阻率。
另外，上述半导体陶瓷组合物中，在将(Ti的含量+TM的含量)设定为1mol时，优选以按元素进行换算为0.003mol以下的比例含有Mn。由此，在结晶晶界形成适度的受主能级(acceptor level)，并且会有提高PTC跳跃的效果。但是，如果Mn超过0.003mol，则传导电子的陷阱变得过剩，并且会有25℃电阻率稍稍上升的倾向。另外，PTC突跳成为用于判断PTC热敏电阻的能力的一个指标，并且作为Log10(280℃条件下的电阻率/25℃条件下的电阻率)来计算。
另外，上述半导体陶瓷组合物中，在将(Ti的含量+TM的含量)设定为1mol时，优选以按元素进行换算为0.015mol以下的比例含有Si。由此，就能够进一步减小25℃电阻率。但是，如果Si超过0.015mol，则过剩的Si元素会大量偏析于结晶晶界，并且会有妨碍传导电子的移动而25℃电阻率稍稍变差的倾向。
另外，在上述碱金属元素A为Na的情况和为K的情况下，居里点移向高温侧的移动量不同，但是25℃电阻率或耐电压以及机械强度相同。
本发明的半导体陶瓷组合物可以通过下述工序获得，即，混合并煅烧含有构成上述通式(1)的各元素的化合物，在粉碎了该煅烧粉之后，添加胶粘剂并进行造粉和成型，之后进行脱胶粘剂和烧结。上述烧结可以在大气中或者氮气氛的任一气氛中进行，但在氮气氛中烧结的情况下，需要进一步在800～1000℃的氧化性气氛中进行热处理，所以从简化工序的观点出发优选是在大气中进行烧成。
另外，本发明并不限定于上述实施方式。例如，在上述半导体陶瓷组合物中，Ba的一部分至少被A(选自Na或K中的至少一种碱金属元素)、Bi以及RE(选自含有Y的稀土元素中的至少一种元素)取代，并且Ti的一部分至少被TM(选自V、Nb以及Ta中的至少一种元素)取代，在将(Ti的含量+TM的含量)设定为1mol的时候，满足0.7≤[(Bi的含量)/(A的含量)]≤1.43；0.017≤[(Bi的含量)+(A的含量)]≤0.25；0＜(RE的含量+TM的含量)≤0.01，并且晶体粒径在1.1μm以上且4.0μm以下的范围内具有粒径分布的最大峰值，如果该峰值的分布频率为20％以上，则即使混入不可避免的杂质也不会对特性产生影响。例如，在以湿式进行混合粉碎时使用于粉碎介质的氧化锆球有可能混入整体的0.2～0.3重量％左右，但是不会对特性产生影响。同样，有可能会混入包含于原料中的10重量ppm程度的微量的Fe、Al、Sr等，但是不会对特性产生影响。
另外，本实施方式所涉及的半导体陶瓷组合物也可以含有Pb作为杂质，但是优选其含量为1重量％以下，进一步优选完全不含有Pb。这样能够将烧结时的Pb的挥发或者作为PTC热敏电阻流通于市场并被废弃之后的Pb向环境中的排放抑制到最小限度，因此从低公害化、环境保护性以及生态学的观点出发优选不含Pb。
[实施例]
以下根据实施例以及比较例进一步具体说明本发明，但是本发明完全不限定于以下的实施例。
[实施例1试样号1～65、比较例1～20]
作为起始原料准备了BaCO3、TiO2、Bi2O3、Na2CO3、K2CO3、CaCO3、SiO2、MnCO3、RE的氧化物(例如Y2O3)、TM的氧化物(例如Nb2O5)，以烧结后的组成成为表1～7的形式称量各原料。之后，用球磨机在丙酮中进行湿式混合，之后进行干燥，在900℃下进行煅烧2小时。在此，由于TiO2原料的粒径会对烧结体的晶体粒径产生影响，所以在本实施例中使用了平均粒径D50为0.7μm的TiO2原料。另外，关于TiO2原料的平均粒径D50，使用Microtrac MT3000II来计算。
使用球磨机在纯水中湿式粉碎了上述煅烧物。在此，球磨机粉碎时间会影响到烧结体的晶体粒径分布的最大峰值的分布频率，因此在本实施例中将该粉碎时间设定为17小时。另外，粉碎粉的平均粒径D50为0.5～0.8μm。在此，粉碎粉的平均粒径D50与TiO2原料同样使用Microtrac MT3000II来计算。之后，进行脱水干燥，使用聚乙烯醇等胶粘剂将其造粒并获得造粒粉体。通过单轴压机将该造粒粉体成型为板状(□50mm×厚度2.5mm)，在大气中1200℃下进行2小时烧结，并获得了烧结体。
在研磨了上述烧结体的两面并将厚度加工成1.5mm之后，用湿式切片机切割成35mm×6.5mm的长方形状。按照JIS R 1601在切断了的烧结体上测定了3点弯曲强度。另外，用丝网印刷在切断了的烧结体的两面上涂布了Ag-Zn膏，在大气中以500～700℃进行烧附，之后从25℃到280℃测定了电阻率的温度特性。进一步测定了耐电压。另外，以上述方法从烧结体的截面求得晶体粒径分布的最大峰值以及该峰值的分布频率。将本发明中的实施例1的结果示于表1～表7。
[实施例2试样号66～69、比较例21～24]
作为起始原料准备了BaCO3、TiO2、Bi2O3、Na2CO3、Sm2O3，并以烧结后的组成成为表8的形式称量各原料。之后，用球磨机在丙酮中进行了湿式混合，之后进行干燥，在900℃下煅烧了2小时。另外，对于TiO2原料，如表8所示，使用了几种平均粒径D50不同的原料粉末。
用球磨机在纯水中湿式粉碎了上述煅烧体。在此，球磨机粉碎时间在表8所示的范围内变更了。另外，粉碎粉末的平均粒径D50为0.35～3.2μm。之后，使用与实施例1相同的制作方法并进行了同样的评价。将本发明中的实施例2的结果示于表8中。
另外，在本发明中，25℃电阻率小是指为103Ωcm以下。同样，耐电压高是指300V/mm以上，进一步，机械强度高是指3点弯曲强度为100MPa以上。
由表1可知，Bi的成分范围b和A的成分范围c的含量的合计(b+c)与居里点以及25℃电阻率相关。另外，A为选自Na或K中的至少一种元素。根据试样号1～8，如果(b+c)为0.017以上且0.25以下，则居里点移向高于钛酸钡的居里点120℃的高温侧，并且25℃电阻率成为103Ωcm以下。(b+c)的成分范围小于0.017的比较例1和比较例3的25℃电阻率小，但是居里点没有移向高于120℃的高温侧。另外，可知(b+c)的成分范围超过0.25的比较例2和比较例4的25℃电阻率远远超过了103Ωcm。另外，可知在A为Na的情况下和A为K的情况下居里点移向高温侧的位移量有若干不同，但是25℃电阻率基本上相同。
[表1]
另外，从表2可知Bi的成分范围b和A的成分范围c满足0.7≤b/c≤1.43的试样号4以及9～11的25℃电阻率成为103Ωcm以下，但是小于0.07的比较例5以及大于1.43的比较例6的25℃电阻率远远超过103Ωcm。
[表2]
从表3可知，(Ba、Bi、A、RE的总mol数)相对于(Ti和TM的总mol数)之比(A/B)会对25℃电阻率产生影响。还可知A/B的范围为1.001以上且1.06以下的试样号12～14的25℃电阻率稍稍变小。但是，如果超过1.06，则可发现25℃电阻率增大的倾向。
[表3]
从表4可知Ca元素的成分范围与25℃电阻率相关。还可知在Ca的含量为0.049mol以下的试样号15～17中，25℃电阻率稍稍变小。但是，如果超过0.049mol，则可发现25℃电阻率减小效果增大的倾向。
[表4]
由表5的试样号18～20可知，如果副成分Si的成分范围为0.015mol以下，则有25℃电阻率减小的效果。但是，如果Si的成分范围超过0.015，则可发现25℃电阻率增大的倾向。
[表5]
由表6的试样号21～23可知，如果Mn的成分范围为0.003mol以下，则其成分量越多PTC突跳越提高。但是，如果超过0.003mol，则可发现25℃电阻率增大的倾向。
[表6]
从表7的试样号24～65可知如果RE以及TM的总量(e+f)为0.01以下，则有25℃电阻率减小的效果。进一步，更加优选为0.001mol以上且0.006mol以下。另外，进一步优选La、Sm、Gd作为RE；Nb作为TM的情况。另外，对于(e+f)大于0.01的比较例7～20，可知其25℃电阻率超过103Ωcm。进一步，由试样号60～65可知即使(e+f)为相同值，但是各以等量添加了RE和TM的试样的25℃电阻率小。
[表7]
从表8可知试样号66～69通过适当调整TiO2原料的粒径以及球磨粉碎时间从而晶体粒径分布的最大峰值为1.1μm以上且4.0μm以下，并且该峰值的分布频率成为20％以上，耐电压为300Vmm以上并且3点弯曲强度成为100MPa以上。相对于此，比较例21以及24由于没有适当调整TiO2原料的粒径以及球磨粉碎时间，因而晶体粒径分布的最大峰值成为上述最适当范围之外，并且全部的3点弯曲强度都小于100MPa。另外，TiO2原料的粒径以及球磨粉碎时间没有适当调整的比较例22以及23的晶体粒径分布的最大峰值在1.1μm以上且4.0μm以下的范围内，但是该峰值的分布频率小于20％，并且所有都是耐电压小于300V/mm并且3点弯曲强度小于100MPa。这被认为是由于通过晶体粒径分布变得宽广从而存在有部分粗大的晶体颗粒，并且该处成为降低耐电压或3点弯曲强度的起点。另外，在晶体粒径分布的最大峰值在1.1μm以上且4.0μm以下的范围内的情况下，25℃电阻率基本相同。
[表8]

Claims (2)

1.一种半导体陶瓷组合物，其特征在于：
在BaTiO3类的半导体陶瓷组合物中，Ba的一部分至少被A、Bi以及RE取代，并且Ti的一部分至少被TM取代，其中，A为选自Na或K中的至少一种碱金属元素，RE为选自含有Y的稀土元素中的至少一种元素，TM为选自V、Nb以及Ta中的至少一种元素，
在将所述Ti的含量与所述TM的含量的总和设定为1mol时，满足：
0.7≤Bi的含量/A的含量≤1.43；
0.017≤Bi的含量+A的含量≤0.25；
0＜RE的含量+TM的含量≤0.01，
并且所述半导体陶瓷组合物由多个晶体颗粒构成，
所述多个晶体颗粒的晶体粒径在1.1μm以上且4.0μm以下的范围内具有粒径分布的最大峰值，且该峰值的分布频率为20％以上。
2.一种PTC热敏电阻，其特征在于：
具备使用权利要求1所述的半导体陶瓷组合物所形成的陶瓷素体和形成于所述陶瓷素体表面上的一对电极。
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CN101516802A (zh) * 2006-09-28 2009-08-26 株式会社村田制作所 钛酸钡系半导体瓷组合物和使用其的ptc元件
CN104513061A (zh) * 2013-10-03 2015-04-15 Tdk株式会社 半导体陶瓷组合物以及ptc热敏电阻

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