CN101160270B - 制造半导体瓷组合物的方法 - Google Patents
制造半导体瓷组合物的方法 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 235000021438 curry Nutrition 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
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- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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Abstract
课题：本发明的目的是提供一种制造方法，该方法可提供半导体瓷组合物，其可在不使用Pb的情况下在正方向上改变居里温度，并具有显著降低的室温下电阻系数，本发明还提供了一种制造半导体瓷组合物的方法，其即使在具有相对大和厚的形状的材料中仍可提供直到材料内部的均匀性质。解决手段：一种制造由具有组成式[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3的半导体瓷组合物的方法，其中R是La、Dy、Eu、Gd、Y中的至少一种，并且x和y各自满足0＜x≤0.14和0.002≤y≤0.02，该方法包括在氧气浓度等于或小于1％的惰性气氛中进行烧结。
Description
技术领域
本发明涉及用于PTC热敏电阻、PTC加热器、PTC开关、温度检测器等的半导体瓷组合物的制造方法，所述半导体瓷组合物具有正的电阻温度，具有显著降低的室温电阻系数，并能够提供直到材料内部的均匀性质。
背景技术
通常地，作为显示出正PCTR的材料，已经有人提出了通过向BaTiO3中加入多种半导体形成成分而构成组合物。这些组合物具有约120℃的居里温度，并因此需要根据应用改变该居里温度。
例如，尽管已经有人提出通过向BaTiO3中加入SrTiO3改变居里温度，但在这种情况下，所述居里温度仅在负方向上改变并且不在正方向上改变。目前，已知仅有PbTiO3作为用于在正方向上改变居里温度的添加剂成分。然而PbTiO3包括引起环境污染的成分，并且因此近年来，希望得到其中不采用PbTiO3的材料。
在BaTiO3半导体瓷中，为了防止由Pb的替代导致的电阻温度系数降低，以及降低电压依赖性和提高生产率和可靠性的目的，已经有人提出如下制造BaTiO3半导体瓷的方法，其中将通过向如下组合物中加入一种或多种Nb、Ta和稀土元素中的任一种而获得的组合物在氮气中烧结，和之后在氧化气氛中进行热处理，所述组合物中其中BaTiO3 的一部分Ba被Ba-Na替代的Ba1-2x(BiNa)xTiO3中的x被控制在0＜x≤0.15的范围内(参见专利文献1)。
专利文献1：JP-A-56-169301
在其中所述组合物的化合价控制在其中一部分Ba被Bi-Na替代的体系中进行的情况下，当将三价正离子作为半导体形成成分加入时，由于存在一价Na离子而降低了半导体形成的效果，并且增加了室温下电阻系数。尽管在专利文献1中，作为实施方式，已经公开了通过向作为半导成分的Ba1-2x(BiNa)xTiO3(0＜x≤0.15)中加入0.1mo1％的Nd2O3构成的组合物，Nd2O3的添加剂的量不能实现充分用于PTC应用的半导体形成。
在上述材料中，其电阻值被认为是由晶界的Schottky势垒导致的。作为控制所述Schottky势垒的手段，已经有人提出了晶界的氧化/还原处理，并且有报道称可通过通常经历过在氧气中的氧化处理的材料而获得高的PTC性质(参见非专利文献1)。另外，还有人报道了在所述热处理中的处理速度也影响性质(参见非专利文献2)，这样造成的问题是所述材料的热处理变得非常复杂。
非专利文献1：Titabari kenkyukai Shiryo XVII-95-659(1968)
非专利文献2：J.Am.Ceram.Soc.48，81(1965)
另外，根据所述热处理，造成的问题是，尽管当所述材料的形状相对小时，通过所述热处理的作用可均匀作用于所述材料的内部，但在例如PTC加热器的应用中应用相对大的形状(厚的形状)的情况下，难以提供直到所述材料内部的均匀的PTC性质。
发明内容
本发明的目的是解决上述传统问题并提供一种制造方法，该方法提供一种半导体瓷组合物，其可在不使用Pb的情况下在正方向上改变居里温度，并具有显著降低的室温下电阻系数。
另外，本发明的另一个目的是提供制造半导体瓷组合物的方法，其即使在材料具有相对大和厚的形状的情况下无需进行复杂的热处理仍可提供直到材料内部的均匀性质。
本发明的发明人注意到当在BaTiO3半导体瓷组合物中用Bi-Na替代Ba时的化合价控制，并且由于深入研究了用于进行最优化化合价控制的添加剂成分的含量，本发明的发明人发现，用特定量的R元素替代Ba可获得最佳的化合价控制并且室温下电阻系数可被显著降低。
另外，作为对制造所述半导体瓷组合物的方法的研究结果，本发明的发明人发现，通过在氧气浓度等于或小于1％的惰性气氛中进行所述组合物的烧结，可提供直到所述组合物内部的均匀的PTC性质，并且可提供具有优异性质的半导体瓷组合物，而无需进行对气氛、处理速度等的复杂控制。因此完成了本发明。
根据本发明的制造半导体瓷组合物的方法是制造由组成式[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3表示的半导体瓷组合物的方法，其中R是La、Dy、Eu、Gd和Y中的至少一种元素，并且x和y各自满足0＜x≤0.14和0.002≤y≤0.02，该方法包括在氧气浓度等于或小于1％的惰性气氛中进行烧结。
本发明还提出了根据上述制造半导体瓷组合物的方法的组成，其中氧气浓度等于或小于10ppm，和如下组成，其中Si氧化物的含量为3.0mol％或更小，和Ca氧化物的含量为3.0mol％或更小。
根据本发明，可以提供一种半导体瓷组合物，其可在不使用引起环境污染的Pb的情况下提高其居里温度，并具有显著降低的室温下电阻系数。
根据本发明，还可赋予相对大和厚的形状的半导体瓷组合物直到所述材料内部的均匀性质。
根据本发明，由于不必进行复杂的热处理，可以低成本提供具有优异性能的半导体瓷组合物。
附图说明
图1是表示根据本发明的半导体瓷组合物的电阻系数的温度变化的图。
具体实施方式
本发明的一个特征在于通过用Bi-Na替代一部分Ba，在正方向上改变居里温度，以及在于为了最佳控制受所述Bi-Na的替代干扰的化合价，将一部分Ba用特定量的R元素(La、Dy、Eu、Gd和Y中的至少一种元素)替代以得到[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组合物。限制各组成的原因描述如下。
在[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组合物中，R是La、Dy、Eu、Gd和Y中的至少一种元素。在优选的实施方案中，R是La。在所述组成式中，x指Bi+Na的含量，并且其优选的范围是0＜x≤0.14。当x是0时，所述居里温度不能移动到高温侧，而当其超过0.14时，室温下电阻系数变得接近于104Ωcm，并且其变得难于应用到PTC加热器等中，这不是优选的。
另外，y表示R的含量范围，并优选0.002≤y≤0.02。当y小于0.02时，所述组合物的化合价控制变得不充分并且增大了室温下电阻系数。另外，当y超出0.02时，增大了室温下电阻系数，并且因此这不是优选的。y的优选范围是0.005≤y≤0.02，并且室温下电阻系数可被进一步降低。上述的范围0.002≤y≤0.02以mol％表达是0.2mol％至2.0mol％。
在[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组合物中，优选加入3.0mol％或更少的Si的氧化物，和加入4.0mol％的或更少的Ca的氧化物。所述Si的氧化物的加入抑制了晶粒的不正常生长并可容易地控制所述电阻系数，和Ca的氧化物的加入可提高低温下的烧结性能。在任何所述氧化物中，当以超过所述限定量的量加入时，所述组合物不显示出半导体形成，并且因此其不是优选的。
本发明的另一个特征在于，在制造所述[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组合物的方法中，在氧气浓度等于或小于1％的惰性气氛中进行烧结。进一步优选氧气浓度等于或小于10ppm。从而，常规在氧气气氛中进行的复杂的热处理不再是必须的，并且在可赋予具有相对大和厚的形状的材料中直到所述材料内部的均匀性质。
当所述氧气浓度超出1％时，不能赋予直到所述材料内部的均匀性质，并且因此其不是优选的。作为惰性气体，可以使用氮气、氩气、氦气、二氧化碳气体等。在烧结过程中，优选使用具有气密性结构的烧结炉。
将在下文中说明根据本发明的制造半导体瓷组合物的方法的例子。关于除烧结步骤以外的步骤，其不限于如下说明，而是可采用公知的方法。
(1)分别制备：BaCO3和TiO2的粉末作为主要原料；La2O3、Dy2O3、Eu2O3、Gd2O3和Y2O3的至少一种作为半导体形成成分和化合价控制成分；SiO2和CaO作为烧结助剂；和(Na2CO3·Bi2O3·TiO2)作为居里温度的改变剂。
(2)以湿法将各粉末混合并然后干燥。在这种情况下，取决于所述原料粉末的粒径，混合过程的同时可进行粉碎。作为在所述混合过程的媒介，优选纯水或乙醇。优选在混合或粉碎后的混合粉末的平均粒径为0.6μm至1.5μm。
(3)将混合的粉末烧结。优选烧结温度是900℃至1100℃。优选烧结时间是2小时至6小时。优选烧结气氛是在大气中或在氧气中。
(4)将烧结的产物在烧结后精细粉碎并然后干燥。优选以湿法进行精细粉碎。优选在所述粉碎过程中的媒介是纯水或乙醇。优选被粉碎的粉末在精细粉碎后的平均粒径为0.6μm至1.5μm。
(5)将被粉碎的粉末在精细粉碎后通过希望的成形装置成形。在成形过程前，可任选将所述粉碎的粉末通过造粒设备造粒。优选成形的产物在成形后的密度是2至3g/cm3。
(6)烧结成形的产物。关于烧结气氛，如上所述的那样，当所述惰性气体是例如氮气时，在氧气浓度为1％或更低，优选10ppm或更低的包含99％或更高氮气的气氛中进行烧结。优选烧结温度是1200℃至1400℃，并且优选烧结时间是2小时至4小时。当将所述粉末造粒时，优选在300℃至700℃下进行除去粘合剂的处理。
通过包含上述烧结步骤作为必须的步骤，可提供具有[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组成的半导体瓷组合物，并且显著降低室温下的电阻系数。
实施例
分别制备：BaCO3和TiO2的粉末作为主要原料；La2O3、Dy2O3、Eu2O3、Ga2O3和Y2O3作为半导体形成成分和化合价控制成分；SiO2 和CaO作为烧结助剂；和(Na2CO3·Bi2O3·TiO2)作为居里温度的改变剂。将各粉末如表1所示那样掺混以得到[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 的组合物，将其与乙醇混合，并然后干燥以得到具有约9.0μm的平均粒径的混合粉末。
将所述混合粉末在大气中在1000℃下烧结4小时，将形成的烧结过粉末通过湿法粉碎过程进行粉碎至平均粒径为0.9μm，并然后干燥形成的经粉碎的粉末。随后，将PVA加入到所述干燥的粉末中，并将形成的混合物混合，然后通过造粒设备进行造粒。将形成的粒化粉末通过单轴压制设备成形，以得到尺寸为28.5mm×28.5mm，厚度为0.7mm至18mm，和成形密度为2.5至3.5g/cm3的成形产物。
将所述成形产物在300℃至700℃下进行粘合剂除去处理，之后在具有表1所示的氧气浓度的氮气气氛中，根据各个组成将所述成形产物在1280℃至1380℃下烧结4小时，得到尺寸为23.0mm×23.0mm，厚度为0.5mm至15mm，和烧结密度为5.5g/cm3的烧结产物。将形成的烧结产物加工成10mm×10mm×1mm的板状(前提为排除所述烧结产物的厚度等于或小于1mm的情况)以得到测试片。
各测试片的电阻值的热变化通过电阻测量仪在室温至270℃的范围内进行测量。测量结果示于表1中。在表1中，第52号样品是利用Dy作为R的例子，第53号样品是利用Eu作为R的例子，第54号样品是利用Gd作为R的例子，第55号样品是利用Y作为R的例子。
另外，在表1中，对比例在样品编号侧带有*号。图1是显示在各情况下电阻系数的热变化的图，所述情况为在[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3组合物中，y的值被设定在0.006，和x的值被设定在0.02(黑圈a)，0.075(黑圈b)，0.875(黑菱形c)，0.1(黑正方形d)，0.1375(黑三角形e)，或0.2(白圈f)。
如从表1和图1中可知，根据通过本发明的实施例提供的半导体瓷组合物，可在不使用Pb的情况下提高居里温度，并且可显著降低室温下电阻系数。
另外，如从表1和图1中可知，在x满足0＜x≤0.14和y满足0.002≤y≤0.02的范围内提供了优异的性能。
另外，如从表1中可知，应理解的是，当在氧气浓度等于或小于1％的气氛中烧结时，获得了优异的性能，并且进一步地，甚至在厚度为15mm的相对大的材料中获得了优异的性能。这是因为可通过在氧气浓度等于或小于1％的惰性气氛中进行烧结而赋予直到所述材料内部的均匀性质。
表1
| No. | x | y | SiO2 (mol％) | CaO (mol％) | ρ30(Ωcm) | Tc (℃) | 烧结体厚度(mm) | 氧气浓度(ppm，％) |
| 1* | 0 | 0 | 1 | 1.9 | 绝缘物 | - | 4.0 | 9ppm |
| 2* | 0 | 0.005 | 1 | 1.9 | 10127 | 110 | 4.0 | 9ppm |
| 3 | 0.02 | 0.002 | 1 | 1.9 | 320 | 132 | 4.0 | 9ppm |
| 4 | 0.02 | 0.005 | 1 | 1.9 | 288 | 132 | 4.0 | 9ppm |
| 5 | 0.02 | 0.008 | 1 | 1.9 | 246 | 132 | 4.0 | 9ppm |
| 6 | 0.02 | 0.02 | 1 | 1.9 | 228 | 134 | 4.0 | 9ppm |
| 7 | 0.075 | 0.002 | 1 | 1.9 | 666 | 161 | 4.0 | 9ppm |
| 8 | 0.075 | 0.005 | 1 | 1.9 | 545 | 162 | 4.0 | 9ppm |
| 9 | 0.075 | 0.008 | 1 | 1.9 | 439 | 161 | 4.0 | 9ppm |
| 10 | 0.075 | 0.02 | 1 | 1.9 | 387 | 162 | 4.0 | 9ppm |
| 11 | 0.0875 | 0.002 | 1 | 1.9 | 2601 | 170 | 4.0 | 9ppm |
| 12 | 0.0875 | 0.005 | 1 | 1.9 | 2556 | 170 | 4.0 | 9ppm |
| 13 | 0.0875 | 0.008 | 1 | 1.9 | 2421 | 171 | 4.0 | 9ppm |
| 14 | 0.0875 | 0.02 | 1 | 1.9 | 2132 | 173 | 4.0 | 9ppm |
| 15 | 0.1 | 0.002 | 1 | 1.9 | 3109 | 170 | 4.0 | 9ppm |
| 16 | 0.1 | 0.005 | 1 | 1.9 | 3003 | 170 | 4.0 | 9ppm |
| 17 | 0.1 | 0.008 | 1 | 1.9 | 2985 | 171 | 4.0 | 9ppm |
| 18 | 0.1 | 0.02 | 1 | 1.9 | 2867 | 173 | 4.0 | 9ppm |
| 19 | 0.1375 | 0.002 | 1 | 1.9 | 5006 | 170 | 4.0 | 9ppm |
| 20 | 0.1375 | 0.005 | 1 | 1.9 | 4911 | 170 | 4.0 | 9ppm |
| 21 | 0.1375 | 0.008 | 1 | 1.9 | 4827 | 171 | 4.0 | 9ppm |
| 22 | 0.1375 | 0.02 | 1 | 1.9 | 4695 | 173 | 4.0 | 9ppm |
| 23* | 0.2 | 0.002 | 1 | 1.9 | 8323 | 230 | 4.0 | 9ppm |
| 24* | 0.2 | 0.005 | 1 | 1.9 | 8122 | 231 | 4.0 | 9ppm |
| 25* | 0.2 | 0.008 | 1 | 1.9 | 7834 | 234 | 4.0 | 9ppm |
| 26* | 0.2 | 0.02 | 1 | 1.9 | 7619 | 236 | 4.0 | 9ppm |
| 27 | 0.0875 | 0.002 | 1 | 1.9 | 1532 | 173 | 0.5 | 9ppm |
| 28 | 0.0875 | 0.002 | 1 | 1.9 | 2285 | 173 | 8.0 | 9ppm |
| 29 | 0.0875 | 0.002 | 1 | 1.9 | 2331 | 173 | 12.0 | 9ppm |
| 30 | 0.0875 | 0.002 | 1 | 1.9 | 2894 | 173 | 15.0 | 9ppm |
| 31 | 0.0875 | 0.002 | 1 | 1.9 | 2761 | 171 | 4.0 | 100ppm |
| 32 | 0.0876 | 0.002 | 1 | 1.9 | 2947 | 171 | 4.0 | 1％ |
| 33* | 0.0875 | 0.002 | 1 | 1.9 | 72 | 156 | 0.5 | 3％ |
| 34* | 0.02 | 0.002 | 1 | 1.9 | 7134 | 142 | 4.0 | 3％ |
| 35* | 0.02 | 0.02 | 1 | 1.9 | 4309 | 144 | 4.0 | 3％ |
| 36* | 0.075 | 0.002 | 1 | 1.9 | 10023 | 159 | 4.0 | 3％ |
| 37* | 0.075 | 0.02 | 1 | 1.9 | 8209 | 159 | 4.0 | 3％ |
| 38* | 0.0875 | 0.002 | 1 | 1.9 | 34297 | 171 | 4.0 | 3％ |
| 39* | 0.0875 | 0.02 | 1 | 1.9 | 12224 | 170 | 4.0 | 3％ |
| 40* | 0.1 | 0.002 | 1 | 1.9 | 不能测定 | 170 | 4.0 | 3％ |
| 41* | 0.1 | 0.02 | 1 | 1.9 | 198563 | 不能确定 | 4.0 | 3％ |
| 42* | 0.1375 | 0.002 | 1 | 1.9 | 不能测定 | 4.0 | 3％ | |
| 43* | 0.1375 | 0.02 | 1 | 1.9 | 不能测定 | 4.0 | 3％ | |
| 44* | 0.2 | 0.002 | 1 | 1.9 | 不能测定 | 4.0 | 3％ | |
| 45* | 0.2 | 0.02 | 1 | 1.9 | 不能测定 | 4.0 | 3％ | |
| 46* | 0.25 | 0.002 | 1 | 1.9 | 不能测定 | 4.0 | 9ppm | |
| 47* | 0.0875 | 0.025 | 1 | 1.9 | 43285 | 160 | 4.0 | 9ppm |
| 48 | 0.0875 | 0.005 | 0 | 0 | 61 | 161 | 4.0 | 9ppm |
| 49 | 0.0875 | 0.005 | 0 | 1 | 102 | 159 | 4.0 | 9ppm |
| 50 | 0.0875 | 0.005 | 1 | 0 | 92 | 161 | 4.0 | 9ppm |
| 51 | 0.0875 | 0.005 | 0.5 | 1.9 | 84 | 160 | 4.0 | 9ppm |
| 52 | 0.0875 | 0.005 | 1 | 1.9 | 108 | 156 | 4.0 | 9ppm |
| 53 | 0.0875 | 0.005 | 1 | 1.9 | 62 | 166 | 4.0 | 9ppm |
| 54 | 0.0875 | 0.005 | 1 | 1.9 | 82 | 155 | 4.0 | 9ppm |
| 55 | 0.0875 | 0.005 | 1 | 1.9 | 76 | 161 | 4.0 | 9ppm |
工业实用性
通过本发明提供的半导体瓷组合物最适合作为用于PTC热敏电阻、PTC加热器、PTC开关、温度检测器等的材料。
Claims (3)
1.一种制造具有组成式[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3的半导体瓷组合物的方法，其中R是La、Dy、Eu、Gd和Y中的至少一种元素，并且x和y各自满足0＜x≤0.14和0.002≤y≤0.02，
所述方法包括在氧气浓度等于或小于1％的惰性气氛中进行烧结，并且不进行在氧气气氛中的热处理。
2.根据权利要求1的制造半导体瓷组合物的方法，其中所述的氧气浓度等于或小于10ppm。
3.根据权利要求1的制造半导体瓷组合物的方法，其中所述的组合物包含3.0mol％或更少的Si的氧化物和4.0mol％或更少的Ca的氧化物。
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| PCT/JP2006/306816 WO2006106910A1 (ja) | 2005-03-31 | 2006-03-31 | 半導体磁器組成物の製造方法 |
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| CN101160270A CN101160270A (zh) | 2008-04-09 |
| CN101160270B true CN101160270B (zh) | 2012-04-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006800110486A Expired - Fee Related CN101160270B (zh) | 2005-03-31 | 2006-03-31 | 制造半导体瓷组合物的方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7700509B2 (zh) |
| EP (2) | EP1873130A4 (zh) |
| JP (2) | JP5163118B2 (zh) |
| KR (1) | KR101039951B1 (zh) |
| CN (1) | CN101160270B (zh) |
| WO (1) | WO2006106910A1 (zh) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007097462A1 (ja) * | 2006-02-27 | 2007-08-30 | Hitachi Metals, Ltd. | 半導体磁器組成物 |
| EP2077256B1 (en) * | 2006-10-27 | 2013-09-04 | Hitachi Metals, Ltd. | Semiconductor ceramic composition and method for producing the same |
| EP2077257A4 (en) * | 2006-10-27 | 2011-05-18 | Hitachi Metals Ltd | SEMICONDUCTOR CERAMIC COMPOSITION AND MANUFACTURING METHOD THEREFOR |
| JP5228917B2 (ja) * | 2006-10-27 | 2013-07-03 | 日立金属株式会社 | 半導体磁器組成物とその製造方法 |
| CN101395100B (zh) * | 2006-10-27 | 2013-03-27 | 日立金属株式会社 | 半导体陶瓷组合物及其制备方法 |
| KR20090082198A (ko) * | 2006-11-01 | 2009-07-29 | 히다찌긴조꾸가부시끼가이사 | 반도체 자기 조성물과 그 제조 방법 |
| WO2008152976A1 (ja) * | 2007-06-14 | 2008-12-18 | Murata Manufacturing Co., Ltd. | 半導体セラミック材料 |
| JP5251119B2 (ja) * | 2007-12-26 | 2013-07-31 | 日立金属株式会社 | 半導体磁器組成物 |
| KR100941522B1 (ko) | 2008-01-17 | 2010-02-10 | 한국세라믹기술원 | 납성분을 포함하지 않는 ｐｔｃ 써미스터용 세라믹 조성물및 이에 의해 제조되는 ｐｔｃ 세라믹 써미스터 |
| JP5844507B2 (ja) | 2008-03-19 | 2016-01-20 | 日立金属株式会社 | 半導体磁器組成物の製造方法及び半導体磁器組成物を用いたヒータ |
| JP5263668B2 (ja) * | 2008-10-02 | 2013-08-14 | 日立金属株式会社 | 半導体磁器組成物 |
| KR20120093834A (ko) * | 2009-10-06 | 2012-08-23 | 히다찌긴조꾸가부시끼가이사 | 반도체 자기 조성물 및 그 제조 방법, ｐｔｃ 소자 및 발열 모듈 |
| DE102010045597B4 (de) * | 2010-09-16 | 2021-11-04 | Tdk Electronics Ag | Keramischer Werkstoff, piezoelektrischer Aktor enthaltend den keramischen Werkstoff und Verfahren zur Herstellung des keramischen Werkstoffs |
| WO2013157649A1 (ja) * | 2012-04-20 | 2013-10-24 | 日立金属株式会社 | 半導体磁器組成物、その製造方法、およびptc素子 |
| JP6337689B2 (ja) * | 2013-10-03 | 2018-06-06 | Tdk株式会社 | 半導体磁器組成物およびｐｔｃサーミスタ |
| JP6424728B2 (ja) * | 2014-07-03 | 2018-11-21 | Tdk株式会社 | 半導体磁器組成物およびｐｔｃサーミスタ |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5444797A (en) * | 1977-09-16 | 1979-04-09 | Murata Manufacturing Co | Barium titanate semiconductor porcelain |
| JPS56169301A (en) | 1980-06-02 | 1981-12-26 | Tohoku Metal Ind Ltd | Method of producing barium titanate semiconductor porcelain |
| US4384989A (en) * | 1981-05-06 | 1983-05-24 | Kabushiki Kaisha Toyota Chuo Kenyusho | Semiconductive barium titanate |
| JPS5916303A (ja) * | 1982-07-19 | 1984-01-27 | 松下冷機株式会社 | 半導体磁器材料の製造方法 |
| JPH06251903A (ja) * | 1993-02-26 | 1994-09-09 | Murata Mfg Co Ltd | 正の抵抗温度特性を有する積層型半導体磁器 |
| JP2000003802A (ja) * | 1998-06-16 | 2000-01-07 | Matsushita Electric Ind Co Ltd | 正特性サーミスタの製造方法 |
| JP3482394B2 (ja) | 2000-11-20 | 2003-12-22 | 松下電器産業株式会社 | 圧電磁器組成物 |
| JP2004323315A (ja) * | 2003-04-25 | 2004-11-18 | Nec Tokin Corp | 誘電体磁器組成物及びその製造方法並びにそれを用いた積層セラミックコンデンサ |
| JP4765258B2 (ja) | 2004-03-12 | 2011-09-07 | 日立金属株式会社 | 半導体磁器組成物 |
-
2006
- 2006-03-31 KR KR1020077022192A patent/KR101039951B1/ko not_active IP Right Cessation
- 2006-03-31 US US11/910,222 patent/US7700509B2/en not_active Expired - Fee Related
- 2006-03-31 JP JP2007511158A patent/JP5163118B2/ja not_active Expired - Fee Related
- 2006-03-31 EP EP06730764A patent/EP1873130A4/en not_active Withdrawn
- 2006-03-31 CN CN2006800110486A patent/CN101160270B/zh not_active Expired - Fee Related
- 2006-03-31 WO PCT/JP2006/306816 patent/WO2006106910A1/ja active Application Filing
- 2006-03-31 EP EP12173237.4A patent/EP2502893B1/en not_active Not-in-force
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2012
- 2012-08-06 JP JP2012173673A patent/JP5445640B2/ja not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US20080286185A1 (en) | 2008-11-20 |
| EP2502893B1 (en) | 2014-07-30 |
| EP1873130A1 (en) | 2008-01-02 |
| KR20080010388A (ko) | 2008-01-30 |
| EP2502893A3 (en) | 2013-04-03 |
| EP1873130A9 (en) | 2012-06-27 |
| JP5445640B2 (ja) | 2014-03-19 |
| JP5163118B2 (ja) | 2013-03-13 |
| WO2006106910A1 (ja) | 2006-10-12 |
| JP2013014508A (ja) | 2013-01-24 |
| JPWO2006106910A1 (ja) | 2008-09-11 |
| CN101160270A (zh) | 2008-04-09 |
| EP2502893A2 (en) | 2012-09-26 |
| EP1873130A4 (en) | 2012-01-04 |
| US7700509B2 (en) | 2010-04-20 |
| KR101039951B1 (ko) | 2011-06-09 |
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