CN1303105A - 高频介电陶瓷组合物、介电共振器、介电滤波器、介电双工器和通讯装置 - Google Patents
高频介电陶瓷组合物、介电共振器、介电滤波器、介电双工器和通讯装置 Download PDFInfo
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Abstract
可以获得具有介电常数(εr)为30~50、在1GHz时的Q值为15000或更高以及共振频率的温度系数(ιf)可以任意控制在0(ppm/℃)附近的高频介电陶瓷组合物。该组合物是以钙钛矿型晶体相为主的晶体,并且可以通过表达式为(1-x)MeTiaO1+2a-xLn(Ma1/2Mb1/2)bO(3+3b)/2来表示,其中Ln是一种稀土元素、Ma是选自包括Mg和Zn中的至少一种、Mb是选自包括Sn和Zr中的至少一种、以及Me是选自包括Ca和Sr中的至少一种,X为摩尔分数以及0.950≤a≤1.050、0.900≤b≤1.050和0.300≤x≤0.500。
Description
本发明涉及高频介电陶瓷组合物和使用了所说的组合物的介电共振器、介电滤波器、介电双工器以及通讯装置。
作为介电共振器、介电滤波器和电子设备的基底电路的使用材料的介电陶瓷已被广泛地应用,例如,蜂窝电话、个人收音机和利用高频如微波和毫米波的卫星广播接收器。
这样的高频介电陶瓷组合物所要求的介电性能优选如下:
(1)相对介电常数(εr)较大以便符合由于电磁波长在介质中缩短至1/(εr)1/2而小型化的要求,
(2)介电损耗小,或Q值较大,和
(3)共振频率的温度稳定生好,或共振频率的温度系数(ιf)接近为0(ppm/℃)。
作为这些介电陶瓷组合物的种类有:Ba(Zn,Ta)O3系列(日本审查专利申请公开号58-25068);Ba(SN,Mg,Ta)O3系列(日本审查专利申请公开号3-34164);(Zr,Sn)TiO4系列(日本审查专利申请公开号4-59267);Ba2Ti9O20(日本待审查专利申请公开号61-10806)和其它已公开的介电陶瓷组合物。
但是,虽然Ba(Zn,Ta)O3系列和Ba(SN,Mg,Ta)O3系列的材料在1GHz时具有150000~300000的很大的Q值,而其所具有相对介电常数(εr)24~30的则相对较小。
其间,(Zr,Sn)TiO4系列和Ba2Ti9O20系列的材料在1GHz时具有相对较大的37~40的相对介电常数(εr)和50000~60000的较大的Q值,但是,很难进一步提高其相对介电常数(εr),例如超过40。
在最近几年,增强了对损耗最小化和电子设备的小型化的要求。与此同时,对于介电材料增强了要求开发出具有更优越介电性能的材料,特别是同时具有大的相对介电常数(εr)和大的Q值的材料。但是直到现在这些要求还无法满足。
据此,本发明的目的之一是要提供一种在1GHz时具有30~50的相对介电常数(εr)、Q值为15000或更高以及共振频率的温度系数(ιf)能够任意控制在0(ppm/℃)附近的高频介电陶瓷组合物。本发明的另一个目的是要提供使用了这种组合物的介电共振器、介电滤波器、介电双工器和通讯装置。
为了实现上述目的,本发明的一种高频介电陶瓷组合物,其特征在于含有:一种稀土元素(Ln)、Ma是选自包括Mg和Zn中的至少一种、Mb是选自包括Sn和Zr中的至少一种、和Ti以及Me是选自包括Ca和Sr中的至少一种,介电陶瓷所具有的成分通过分子式(1-x)MeTiaO1+2a-xLn(Ma1/2Mb1/2)bO(3+3b)/2来表示,其中x为摩尔分数以及a、b和x所在的范围为0.950≤a≤1.050、0.900≤b≤1.050、0.300≤x≤0.500,以及该介电陶瓷具有钙钛矿型晶体相的主晶体。
上述的稀土元素(Ln)可以是选自下列一组物质中的至少一种:Y、La、Pr、Nd和Sm。
上述的Me可以是Ca以及上述的Ma可以是Mg。
一种本发明的通过终端输入/输出端电磁连接所激励的介电共振器,以及一种介电陶瓷,其特征在于该介电陶瓷含有本发明的高频介电陶瓷组合物。
一种本发明的介电滤波器,其特征在于包括上述的含有外接元件的介电共振器。
一种本发明的介电双工器,其至少包括至少两个介电滤波器、连接每一个介电滤波器的输入/输出连接元件和共同连接到介电滤波器上的一个天线连接元件,其特征在于上述介电滤波器至少有一个是本发明的一种介电滤波器。
一种本发明的通讯装置,其特征在于包括:一种本发明的介电双工器;一种连接到至少一个介电双工器的输入/输出连接元件上的发射电路;一种接收电路,其连接在至少一个不同于所说的连接发射电路输入/输出连接元件上的输入/输出连接元件;和连接在介电双工器的天线连接元件上的一种天线。
图1是根据本发明的一个实施方案的介电共振器的透视图;
图2是图1所示的介电共振器的沿a-b线的剖面图;
图3是根据本发明的一个实施方案的介电滤波器的透视图;
图4是根据本发明的一个实施方案的介电双工器的透视图;
图5是根据本发明的一个实施方案的通讯装置的方框图。
图1示出了根据本发明的一个实施方案的介电共振器的透视图,以及图2是图1所示的介电共振器1的沿a-b线的剖面图。参考图1和图2,介电共振器1含有具有穿透孔洞的矩形棱柱形的介电陶瓷2。在穿透孔洞里形成了内部导体3a和在介电陶瓷2的外边缘形成了外部导体3b。然后一个输入/输出终端或一个外连接元件通过电磁连接相接在介电陶瓷2上,并且介电陶瓷2激励成为介电共振器。构成这样的介电共振器1的介电陶瓷2含有本发明的高频介电陶瓷组合物。
图1所示的是矩形棱柱形的TEM模型介电共振器的实施方案;但是本发明并不限于这种。本发明的高频介电陶瓷组合物也可以用于其它形状的介电共振器、其它TEM模型、TM模型、TE模型等等。
图3是根据本发明的一个实施方案的介电滤波器的透视图。参考图3,介电滤波器4是通过在具有穿透孔洞的介电陶瓷2上形成了内部导体3a和外部导体3b的介电共振器上所形成外连接元件5而制备的。图3所示是一块形介电滤波器;但是,本发明的介电滤波器也可以是离散型的介电滤波器。
图4是根据本发明的一个实施方案的介电双工器的透视图。参考图4,介电双工器6包括:两个装备有通过在具有穿透孔洞的介电陶瓷2上形成了内部导体3a和外部导体3b的介电滤波器、一个连接在其中的一个介电滤波器上的输入连接元件7、一个连接在另一个介电滤波器上的输出连接元件8、和将这些介电滤波器连接在一起的天线连接元件9。图4所示是一块形介电双工器;但是,本发明的介电双工器也可以是离散型的介电双工器。
图5是根据本发明的一个实施方案的通讯装置的方框图。通讯装置10包括:一个介电双工器12、一个发射电路14、一个接收电路16和一个天线18。发射电路14连接在介电双工器12的一个输入连接元件20上,以及接收电路16连接在介电双工器12的一个输出连接元件22上。天线18连接在介电双工器12的一个天线连接元件24上。介电双工器12包括两个介电滤波器26和28。介电滤波器26和28是通过在本发明的介电共振器上形成外接元件而制备的。例如,在这实施方案中,介电滤波器是通过将外连接元件30与介电共振器1的每一个输入/输出终端连接在一起而制备的。然后将介电滤波器26中的一个连接端连接在输入连接元件20和另一个介电滤波器28之间,以及这样的另一个介电滤波器28连接在另一个介电滤波器26和输出连接元件22之间。
如上所述,本发明的高频介电陶瓷组合物包括:一种稀土元素(Ln);Ma,其中Ma是选自包括Mg和Zn中的至少一种;Mb,其中Mb是选自包括Sn和Zr中的至少一种;和Ti;以及Me,其中Me是选自包括Ca和Sr中的至少一种,并且其成分通过分子式(1-x)MeTiaO1+2a-xLn(Ma1/2Mb1/2)bO(3+3b)/2来表示,其中x为摩尔分数以及a、b和x所在的范围如下。
关于a,其优选的范围为0.950≤a≤1.050。假如a<0.950或a>1.050,Q值可能降低并且可能很难达到本发明的目的。
关于b,其优选的范围为0.900≤b≤1.050。假如b<0.900或b>1.050,Q值可能降低。
关于x,其优选的范围为0.300≤x≤0.500。假如x<0.300,共振频率的温度系数(ιf)可能会增加至高于+50ppm/℃,以及假如x>0.500,共振频率的温度系数(ιf)可能会降低至低于-50ppm/℃。
关于本发明的高频介电陶瓷组合物的成分,作为Mb,优选采用Sn和Zr之中的至少一种。
作为一种稀土元素(Ln),钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)和镥(Lu)是可以使用的,并且在这些当中,为了获得较大的相对介电常数(εr)和Q值,优选钇(Y)、镧(La)、镨(Pr)、钕(Nd)和钐(Sm)中的至少一种。
作为Me,优选Ca和Sr中的至少一种,并且更优选Ca。作为Ma,优选Mg和Zn中的至少一种,并且更优选Mg。当作为Me采用Ca和作为Ma采用Mg时,可以获得较大的相对介电常数(εr)和Q值。
下面将通过具体的实施例以说明本发明。
实施例1
在这实施例中,在本发明的高频介电陶瓷组合物中的Mb采用了Sn。
作为初始材料,制备了高纯的碳酸钙(CaCO3)、碳酸锶(SrCO3)、氧化钛(TiO2)、稀土氧化物(如La2O3)、氧化镁(MgO)、氧化锌(ZnO)和氧化锡(SnO2)。然后对这些初始材料进行适当地混合以获得通过分子式(1-x)MeTiaO1+2a-xLa(Ma1/2Sn1/2)bO(3+3b)/2其中x为摩尔分数,所表示的示于表1的成分。也对这些初始材料进行适当地混合以获得通过分子式0.65CaTiO3-0.35Ln(Mg1/2Sn1/2)O3所表示的如表2所示的成分。
表1(1-x)MeTiaO1+2a-xLa(Ma1/2Sn1/2)bO(3+3b)/2系列
试样号 | Me | Ma | a | b | x | 相对介电常数εr | Q值1GHz | 共振频率的温度系数τf(ppm/℃) |
*1 | Ca | Mg | 1.000 | 1.000 | 0.250 | 51.4 | 15300 | 56 |
2 | Ca | 0.8Mg0.2Zn | 1.000 | 1.000 | 0.300 | 48.2 | 15500 | 32 |
3 | Ca | Mg | 1.000 | 1.000 | 0.300 | 47.3 | 19700 | 38 |
*4 | Ca | Mg | 0.900 | 1.000 | 0.350 | 43.0 | 10300 | 13 |
5 | Ca | Mg | 0.950 | 1.000 | 0.350 | 43.2 | 23900 | 12 |
*6 | Ca | Mg | 1.000 | 0.850 | 0.350 | 43.2 | 10100 | 14 |
7 | Ca | Mg | 1.000 | 0.900 | 0.350 | 43.1 | 28000 | 13 |
8 | Ca | Mg | 1.000 | 1.000 | 0.350 | 43.2 | 28200 | 12 |
9 | Ca | Mg | 1.000 | 1.050 | 0.350 | 43.0 | 26300 | 13 |
*10 | Ca | Mg | 1.000 | 1.100 | 0.350 | 43.1 | 9800 | 12 |
11 | Ca | Mg | 1.050 | 1.000 | 0.350 | 43.2 | 17200 | 12 |
*12 | Ca | Mg | 1.100 | 1.000 | 0.350 | 43.1 | 6500 | 14 |
13 | Ca | 0.8Mg0.2Zn | 1.000 | 1.000 | 0.400 | 39.7 | 33100 | -16 |
14 | Ca | Mg | 1.000 | 1.000 | 0.400 | 39.0 | 39900 | -12 |
15 | Ca | Mg | 1.000 | 1.000 | 0.450 | 35.8 | 35100 | -31 |
16 | Ca | Mg | 1.000 | 1.000 | 0.500 | 30.3 | 36000 | -48 |
*17 | Ca | Mg | 1.000 | 1.000 | 0.550 | 26.4 | 37100 | -63 |
*18 | 0.8Ca0.2Sr | Mg | 0.900 | 1.000 | 0.350 | 40.6 | 9300 | 15 |
19 | 08Ca0.2Sr | Mg | 0.950 | 1.000 | 0.350 | 40.3 | 18300 | 13 |
*20 | 0.8Ca0.2Sr | Mg | 1.000 | 0.850 | 0.350 | 40.1 | 12100 | 14 |
21 | 0.8Ca0.2Sr | Mg | 1.000 | 0.900 | 0.350 | 40.3 | 22900 | 16 |
22 | 0.8Ca0.2Sr | Mg | 1.000 | 1.000 | 0.350 | 40.6 | 23600 | 16 |
23 | 0.8Ca0.2Sr | Mg | 1.000 | 1.050 | 0.350 | 40.2 | 21300 | 15 |
*24 | 0.8Ca0.2Sr | Mg | 1.000 | 1.100 | 0.350 | 40.3 | 11000 | 14 |
25 | 0.8Ca0.2Sr | Mg | 1.050 | 1.000 | 0.350 | 40.1 | 20600 | 15 |
*26 | 0.8Ca0.2Sr | Mg | 1.100 | 1.000 | 0.350 | 40.2 | 7500 | 13 |
表20.65CaTiO3-0.35Ln(Mg1/2Sn1/2)O3系列
试样号 | 稀土元素(Ln) | 相对介电常数εr | Q值1GHz | 共振频率的温度系数τf(ppm/℃) | 备注 |
27 | Y | 41.3 | 27800 | 11 | 与表1中的试样8一致 |
28 | 0.1Y-0.9La | 42.9 | 27800 | 12 | |
29 | 0.3Y-0.7La | 42.3 | 27800 | 12 | |
30 | Pr | 42.9 | 28300 | 13 | |
31 | 0.1Pr-0.9La | 43.1 | 28100 | 14 | |
32 | 0.3Pr-0.7La | 42.7 | 28400 | 13 | |
33 | Nd | 42.5 | 29100 | 13 | |
34 | 0.1Nd-0.9La | 42.8 | 27600 | 14 | |
35 | 0.3Nd-0.7La | 42.1 | 28100 | 13 | |
36 | Sm | 41.3 | 29300 | 16 | |
37 | 0.1Sm-0.9La | 42.6 | 28400 | 15 | |
38 | 0.3Sm-0.7La | 42.1 | 28600 | 14 |
如表2所示的试样27~38采用了不同的稀土元素(如“稀土元素”一列所示)以代替表1所示的成分表达式中的La,而且其它成分与表1中的试样8是一致的。
然后,使用球磨机对这些混合的初始材料的粉末进行湿混合16小时、脱水、干燥,并随后在1100~1300℃下煅烧3小时。然后加入适量的粘结剂,使用球磨机对煅烧粉末进行湿磨16小时以获得制备好的粉末。
将制备好的粉末在1000~2000Kg/cm2的压力下模压成圆盘,在空气中将其在1400~1500℃的温度下烧结4~10小时以获得具有以钙钛矿型晶体相为主晶体的直径为10mm厚度为5mm的陶瓷。
在频率为6~8GHz下测量其相对介电常数(εr),以及通过两个端表面短路型的介电共振器方法确定所获得陶瓷的Q值,并且根据定律Q×f=常数,将此Q值换算为在1GHz下的Q值。根据TE01δ型共振器频率确定其在25℃~55℃之间的共振频率的温度系数(ιf)。这些结果示于表1和表2。在表1中,带星号的试样号表示超出了本发明的范围。
表1和2清楚地表明在本发明范围内的试样在微波段可以获得大的Q值同时相对介电常数(εr)也保持为大的数值。
主要参考表1,下面将给以说明,限制通过分子式(1-x)MeTiaO1+2a-xLn(Ma1/2Sn1/2)bO(3+3b)/2其中Ln是稀土元素、Ma是Mg和Zn中的至少一种、Me是Ca和Sr中的至少一种以及x为摩尔分数所表示本发明的成分的原因。
关于a,其优选的范围为0.950≤a≤1.050。假如a<0.950如试样4和18所示以及假如a>1.050如试样12和26所示,其Q值都较低,并且很难达到本发明的目的。
关于b,其优选的范围为0.900≤b≤1.050。假如b<0.900如试样6和20所示以及假如b>1.050如试样10和24所示,其Q值都较低。
关于x,其优选的范围为0.300≤x≤0.500。假如x<0.300如试样1所示,其共振频率的温度系数(ιf)增加至高于+50ppm/℃,以及假如x>0.500如试样17,其共振频率的温度系数(ιf)变为低于-50ppm/℃。
表2清楚地表明,当采用钇(Y)、镧(La)、镨(Pr)、钕(Nd)和钐(Sm)中的至少一种以替换表1所示的作为稀土元素的单一的镧(La)时,其性能与在单一的镧(La)时所获得的性能是相等的。
实施例2
在这实施例中,在本发明的高频介电陶瓷组合物中的Mb采用了Zr。
作为初始材料,制备了高纯的碳酸钙(CaCO3)、碳酸锶(SrCO3)、氧化钛(TiO2)、稀土氧化物(如La2O3)、氧化镁(MgO)、氧化锌(ZnO)和氧化锆(ZrO2)。然后对这些初始材料进行适当地混合以获得通过分子式(1-x)MeTiaO1+2a-xLa(Ma1/2Zr1/2)bO(3+3b)/2其中x为摩尔分数,所表示的示于表3的成分。也对这些初始材料进行适当地混合以获得通过分子式0.6CaTiO3-0.4Ln(Mg1/2Zr1/2)O3所表示的如表4所示的成分。
表3(1-x)MeTiaO1+2a-xLa(Ma1/2Zr1/2)bO(3+3b)/2系列
试样号 | Me | Ma | a | b | x | 相对介电常εr | Q值1GHz | 共振频率的温度系数τf(pp/℃) |
*39 | Ca | Mg | 1.000 | 1.000 | 0.275 | 57.2 | 14700 | 55 |
40 | Ca | 0.8Mg0.2Zn | 1.000 | 1.000 | 0.300 | 55.0 | 18900 | 41 |
41 | Ca | Mg | 1.000 | 1.000 | 0.300 | 54.3 | 21000 | 46 |
42 | Ca | Mg | 1.000 | 1.000 | 0.325 | 52.0 | 24600 | 37 |
43 | Ca | Mg | 1.000 | 1.000 | 0.350 | 49.4 | 27400 | 29 |
44 | Ca | Mg | 1.000 | 1.000 | 0.375 | 46.7 | 24800 | 14 |
*45 | Ca | Mg | 0.900 | 1.000 | 0.400 | 44.8 | 12100 | 3 |
46 | Ca | Mg | 0.950 | 1.000 | 0.400 | 44.9 | 26900 | 3 |
*47 | Ca | Mg | 1.000 | 0.850 | 0.400 | 44.8 | 14300 | 3 |
48 | Ca | Mg | 1.000 | 0.900 | 0.400 | 44.8 | 30200 | 4 |
49 | Ca | Mg | 1.000 | 1.000 | 0.400 | 44.9 | 29600 | 3 |
50 | Ca | Mg | 1.000 | 1.050 | 0.400 | 44.7 | 27600 | 4 |
*51 | Ca | Mg | 1.000 | 1.100 | 0.400 | 44.8 | 11600 | 2 |
52 | Ca | Mg | 1.050 | 1.000 | 0.400 | 44.8 | 22700 | 3 |
*53 | Ca | Mg | 1.100 | 1.000 | 0.400 | 44.7 | 9800 | 4 |
54 | Ca | Mg | 1.000 | 1.000 | 0.425 | 42.3 | 30800 | -13 |
55 | Ca | 0.8Mg0.2Zn | 1.000 | 1.000 | 0.425 | 43.1 | 27200 | -16 |
56 | Ca | Mg | 1.000 | 1.000 | 0.450 | 40.5 | 31700 | -25 |
57 | Ca | Mg | 1.000 | 1.000 | 0.475 | 38 8 | 33000 | -33 |
58 | Ca | Mg | 1.000 | 1.000 | 0.500 | 36.4 | 34800 | -46 |
*59 | Ca | Mg | 1.000 | 1.000 | 0.550 | 34.3 | 35600 | -57 |
*60 | 0.8Ca0.2Sr | Mg | 0.900 | 1.000 | 0.400 | 42.4 | 12000 | 6 |
61 | 0.8Ca0.2Sr | Mg | 0.950 | 1.000 | 0.400 | 42.5 | 19600 | 6 |
*62 | 0.8Ca0.2Sr | Mg | 1.000 | 0.850 | 0.400 | 42.4 | 7600 | 7 |
63 | 0.8Ca0.2Sr | Mg | 1.000 | 0.900 | 0.400 | 42.4 | 21300 | 6 |
64 | 0.8Ca0.2Sr | Mg | 1.000 | 1.000 | 0.400 | 42.5 | 23900 | 7 |
65 | 0.8Ca0.2Sr | Mg | 1.000 | 1.050 | 0.400 | 42.5 | 22300 | 6 |
66 | 0.8Ca0.2Sr | Mg | 1.000 | 1.100 | 0.400 | 42.4 | 10600 | 7 |
67 | 0.8Ca0.2Sr | Mg | 1.050 | 1.000 | 0.400 | 42.6 | 17000 | 7 |
*68 | 0.8Ca0.2Sr | Mg | 1.100 | 1.000 | 0.400 | 42.5 | 7200 | 8 |
表40.6CaTiO3-0.4Ln(Mg1/2Zr1/2)O3系列
试样号 | 稀土元素(Ln) | 相对介电常数εr | Q值1GHz | 共振频率的温度系数τf(ppm/℃) | 备注 |
69 | Y | 43.8 | 28600 | 3 | 与表3中的试样49一致 |
70 | 0.1Y-0.9La | 44.7 | 28300 | 3 | |
71 | 0.3Y-0.7La | 44.2 | 27900 | 2 | |
72 | Pr | 44.4 | 28900 | 3 | |
73 | 0.1Pr-0.9La | 44.7 | 28600 | 4 | |
74 | 0.3Pr-0.7La | 44.3 | 28300 | 3 | |
75 | Nd | 44.0 | 30100 | 2 | |
76 | 0.1Nd-0.9La | 44.6 | 29600 | 3 | |
77 | 0.3Nd-0.7La | 44.2 | 29500 | 3 | |
78 | Sm | 43.2 | 28900 | 6 | |
79 | 0.1Sm-0.9La | 44.3 | 28600 | 5 | |
80 | 0.3Sm-0.7La | 43.9 | 28400 | 5 |
如表4所示的试样69~80采用了不同的稀土元素(如“稀土元素”一列所示)以代替表3所示的成分表达式中的La,而且其它成分与表3中的试样49是一致的。
然后,使用球磨机对这些混合的初始材料的粉末进行湿混合16小时、脱水、干燥,并随后在1100~1300℃下煅烧3小时。然后加入适量的粘结剂,使用球磨机对煅烧粉末进行湿磨16小时以获得制备好的粉末。
将制备好的粉末在1000~2000Kg/cm2的压力下模压成圆盘,在空气中将其在1300~1400℃的温度下烧结4~10小时以获得具有以钙钛矿型晶体相为主晶体的直径为10mm厚度为5mm的陶瓷。
在频率为6~8GHz下测量其相对介电常数(εr),以及通过两个端表面短路型的介电共振器方法确定所获得陶瓷的Q值,并且根据定律Q×f=常数,将此Q值换算为在1GHz下的Q值。根据TE01δ型共振器频率确定其在25℃~55℃之间的共振频率的温度系数(ιf)。这些结果示于表3和表4。在表3中,带星号的试样号表示超出了本发明的范围。
表3和4清楚地表明在本发明范围内的试样在微波段可以获得大的Q值同时相对介电常数(εr)也保持为大的数值。
主要参考表3,下面将给以说明,限制通过分子式(1-x)MeTiaO1+2a-xLn(Ma1/2Zr1/2)bO(3+3b)/2其中Ln是稀土元素、Ma是Mg和Zn中的至少一种、Me是Ca和Sr中的至少一种以及x为摩尔分数所表示本发明的成分的原因。
关于a,其优选的范围为0.950≤a≤1.050。假如a<0.950如试样45和60所示以及假如a>1.050如试样53和68所示,其Q值都较低,并且很难达到本发明的目的。
关于b,其优选的范围为0.900≤b≤1.050。假如b<0.900如试样47和62所示以及假如b>1.050如试样51和66所示,其Q值都较低。
关于x,其优选的范围为0.300≤x≤0.500。假如x<0.300如试样39所示,其共振频率的温度系数(ιf)增加至高于+50ppm/℃,以及假如x>0.500如试样59,其共振频率的温度系数(ιf)变为低于-50ppm/℃。
表4清楚地表明,当采用钇(Y)、镧(La)、镨(Pr)、钕(Nd)和钐(Sm)中的至少一种以替换表3所示的作为稀土元素的单一的镧(La)时,其性能与在单一的镧(La)时所获得的性能是相等的。
实施例3
在这实施例中,在本发明的高频介电陶瓷组合物中的Mb采用了Sn和Zr。
作为初始材料,制备了高纯的碳酸钙(CaCO3)、碳酸锶(SrCO3)、氧化钛(TiO2)、氧化镧(LaO3)、氧化镁(MgO)、氧化锌(ZnO)、氧化锡(SnO2)和氧化锆(ZrO2)。
然后对这些初始材料进行适当地混合以获得通过分子式(1-x)CaTiO3-xLa(Ma1/2Mb1/2)O3其中x为摩尔分数,所表示的示于表5的成分。
表5(1-x)CaTiO3-xLa(Ma1/2Mb1/2)3系列
试样号 | Ma | Mb | x | 相对介电常数εr | Q值1GHz | 共振频率的温度系数τf(ppm/℃) |
81 | Mg | 0.8Zr0.2Sn | 0.35 | 48.3 | 28200 | 24 |
82 | Mg | 0.5Zr0.5Sn | 0.35 | 45.9 | 27000 | 19 |
83 | Mg | 0.8Zr0.2Sn | 0.40 | 43.7 | 30900 | -1 |
84 | Mg | 0.5Zr0.5Sn | 0.40 | 41.8 | 34100 | -7 |
85 | 0.8Mg0.2Zn | 0.5Zr0.5Sn | 0.40 | 42.0 | 34000 | -9 |
然后,使用球磨机对这些混合的初始材料的粉末进行湿混合16小时、脱水、干燥,并随后在1100~1300℃下煅烧3小时。加入适量的粘结剂后,使用球磨机对煅烧粉末进行湿磨16小时以获得制备好的粉末。
将制备好的粉末在1000~2000Kg/cm2的压力下模压成圆盘,在空气中将其在1300~1400℃的温度下烧结4~10小时以获得具有以钙钛矿型晶体相为主晶体的直径为10mm厚度为5mm的陶瓷。
在频率为6~8GHz下测量其相对介电常数(εr),以及通过两个端表面短路型的介电共振器方法确定所获得陶瓷的Q值,并且根据定律Q×f=常数,将此Q值换算为在1GHz下的Q值。根据TE01δ型共振器频率确定其在25℃~55℃之间的共振频率的温度系数(ιf)。这些结果示于表5。
表5中的试样81~85清楚地表明在本发明的范围内的试样,其中Mb是Sn和Zr,其共振频率的温度系数(ιf)可以保持为0±30ppm/℃之间,同时其Q值和相对介电常数(εr)在微波段内可以保持在大的数值。
只要不防碍达到本发明的目的,本发明的高频介电陶瓷组合物可以加入少量的添加物。例如可加入0.01~1.0重量%的二氧化硅(SiO2)、碳酸锰(MnCO3)、氧化硼(B2O3)、氧化镍(NiO)、氧化铜(CuO)、碳酸锂(Li2CO3)等,烧结温度可以降低20~30℃以防止性能的下降。另外,通过加入1~3重量%的Nb2O5、Ta2O5、V2O5等可以精确地控制相对介电常数(εr)和温度特性,以及可以获得很好的介电陶瓷。
从上述的说明可以清楚地表明,根据本发明可以获得具有介电常数(εr)为30~50、在1GHz时的Q值为15000或更高以及共振频率的温度系数(ιf)可以任意控制在0(ppm/℃)附近的高频介电陶瓷组合物。因此通过使用具有本发明成分的介电陶瓷可以制备具有优越性能的介电共振器、介电滤波器、介电双工器和通讯装置。
Claims (7)
1.一种含有以钙钛矿型晶体相为主晶体的高频介电陶瓷组合物,其结构表达式为(1-x)MeTiaO1+2a-xLn(Ma1/2Mb1/2)bO(3+3b)/2,其中Ln是一种稀土元素、Ma是选自包括Mg和Zn中的至少一种、Mb是选自包括Sn和Zr中的至少一种、和Ti以及Me是选自包括Ca和Sr中的至少一种,并且其中x为摩尔分数以及a、b和x所在的范围为0.950≤a≤1.050、0.900≤b≤1.050、0.300≤x≤0.500。
2.一种根据权利要求1的高频介电陶瓷组合物,其特征在于所说的稀土元素(Ln)是选自下列一组中的至少一种:钇(Y)、镧(La)、镨(Pr)、钕(Nd)和钐(Sm)。
3.一种根据权利要求2的高频介电陶瓷组合物,其特征在于所说的Me是Ca,和所说的Ma是Mg。
4.一种通过输入/输出接线端和一种介电陶瓷的电磁连接而激励的介电共振器,其特征在于所说的介电陶瓷是含有根据权利要求1~3中的任一项的高频介电陶瓷组合物。
5.一种介电滤波器,其特征在于含有一种权利要求4的介电共振器,所说的共振器含有一个外连接元件。
6.一种介电双工器,其包括:至少两个介电滤波器、连接每一个介电滤波器的输入/输出连接元件和一个共同连接所说的介电滤波器的天线连接元件,其特征在于至少有一个所说的介电滤波器是根据权利要求5的介电滤波器。
7.一种通讯装置,其特征在于包括:一个根据权利要求6的介电双工器;一个连接在所说的介电双工器的至少一个输入/输出连接元件上的发射电路;一个连接在至少一个输入/输出连接元件上的接收电路,其不同于所说的连接在所说的发射电路上的输入/输出连接元件;和一个连接在所说的介电双工器的天线连接元件的天线。
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CN102037093A (zh) * | 2008-05-23 | 2011-04-27 | 石原产业株式会社 | 红外反射材料及其制备方法以及含所述材料的油漆和树脂组合物 |
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US6649553B2 (en) * | 2001-04-12 | 2003-11-18 | Murata Manufacturing Co. Ltd. | Dielectric ceramic composition, dielectric ceramic compact and electronic component including the same |
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US3785834A (en) * | 1972-06-09 | 1974-01-15 | Owens Illinois Inc | Glasses,glass-ceramics and process for making same |
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