CN115806431A - 瓷器组合物和绕组型线圈部件 - Google Patents

瓷器组合物和绕组型线圈部件 Download PDF

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CN115806431A
CN115806431A CN202211102145.3A CN202211102145A CN115806431A CN 115806431 A CN115806431 A CN 115806431A CN 202211102145 A CN202211102145 A CN 202211102145A CN 115806431 A CN115806431 A CN 115806431A
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zno
cuo
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岛村笃
喜多代裕树
铃木崇规
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Abstract

本发明提供具有充分的导磁率、抗折强度以及韧性且居里温度高的瓷器组合物。本发明提供一种瓷器组合物，含有Fe、Cu、Ni、Zn、Co以及Cr，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100摩尔份时，含有换算成Fe2O3为48.20摩尔份～49.85摩尔份的Fe，换算成CuO为2.00摩尔份～8.00摩尔份的Cu，换算成NiO为11.90摩尔份～18.70摩尔份的Ni，换算成ZnO为27.00摩尔份～33.50摩尔份的Zn，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，含有换算成CoO为5ppm～100ppm的Co，换算成Cr2O3为10ppm～400ppm的Cr。

Description

瓷器组合物和绕组型线圈部件
技术领域
本发明涉及瓷器组合物和绕组型线圈部件。
背景技术
专利文献1公开了使用具有卷芯部和凸缘部的鼓芯的绕组型的线圈装置。根据专利文献1记载的线圈装置，形成于卷芯部的一端的凸缘部的安装用第1凸部与形成于卷芯部的另一端的凸缘部的安装用第2凸部错位地配置，因此耐热冲击特性优异。
专利文献1：日本特开2018－125397号公报
发明内容
专利文献1中记载了鼓芯例如通过将Ni－Zn系铁氧体或Mn－Zn系铁氧体等铁氧体材料成型和烧结而制作。然而，鼓芯使用的铁氧体材料不具备充分的坯体强度(例如抗折强度和韧性)时，有安装于基板等的线圈装置的强度降低的顾虑。进而，鼓芯使用的铁氧体材料不具有充分的抗折强度和韧性时，线圈装置的制造过程中，也有鼓芯容易碎裂的顾虑。
另外，从提供高温条件下也发挥作用的线圈部件的观点考虑，也希望铁氧体材料的居里温度高。
本发明是为了解决上述的问题而作出的，其目的在于提供具有充分的导磁率、抗折强度和韧性且居里温度高的瓷器组合物。本发明的目的还在于提供具备上述瓷器组合物的烧结体作为陶瓷芯的绕组型线圈部件。
本发明的瓷器组合物是含有Fe、Cu、Ni、Zn、Co以及Cr的瓷器组合物，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100摩尔份时，含有换算成Fe2O3为48.20摩尔份～49.85摩尔份的Fe，换算成CuO为2.00摩尔份～8.00摩尔份的Cu，换算成NiO为11.90摩尔份～18.70摩尔份的Ni，换算成ZnO为27.00摩尔份～33.50摩尔份的Zn，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，含有换算成CoO为5ppm～100ppm的Co，换算成Cr2O3为10ppm～400ppm的Cr。
本发明的绕组型线圈部件具备：由本发明的瓷器组合物的烧结体构成且具有轴芯部和设置于在上述轴芯部的长度方向相对的两端部的一对凸缘部的陶瓷芯，设置于上述凸缘部的高度方向的一个端面的电极，以及卷绕于上述轴芯部且端部与上述电极电连接的绕组。
根据本发明，能够提供具有充分的导磁率、抗折强度和韧性且居里温度高的瓷器组合物。
附图说明
图1是示意地表示本发明的绕组型线圈部件的一个例子的主视图。
图2是示意地表示构成图1所示的绕组型线圈部件的陶瓷芯的一个例子的立体图。
符号说明
10 绕组型线圈部件
20 陶瓷芯
30 轴芯部
31，32 轴芯部的主面
33，34 轴芯部的侧面
40 凸缘部
41，42 凸缘部的主面
43，44 凸缘部的侧面
45，46 凸缘部的端面
50 电极
55 绕组
Ld 长度方向
Td 高度方向
Wd 宽度方向
具体实施方式
以下，对本发明的瓷器组合物和绕组型线圈部件进行说明。
然而，本发明不限于以下构成，可以在不变更本发明的主旨的范围内适当地变更而应用。应予说明，将2个以上以下记载的本发明的各优选的构成组合而得的方案也是本发明。
[瓷器组合物]
本发明的瓷器组合物含有Fe、Cu、Ni、Zn、Co以及Cr。本发明的瓷器组合物例如包含铁氧体、优选尖晶石型的铁氧体作为主成分。
本发明的瓷器组合物中，将Fe、Cu、Ni以及Zn分别换算成Fe2O3，CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100摩尔份时，含有换算成Fe2O3为48.20摩尔份～49.85摩尔份的Fe，换算成CuO为2.00摩尔份～8.00摩尔份的Cu，换算成NiO为11.90摩尔份～18.70摩尔份的Ni，换算成ZnO为27.00摩尔份～33.50摩尔份的Zn。
本发明的瓷器组合物中，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，含有换算成CoO为5ppm～100ppm的Co，换算成Cr2O3为10ppm～400ppm的Cr。
本发明的瓷器组合物中，通过使Fe、Cu、Ni、Zn、Co以及Cr的含量为上述的范围，能够提高导磁率、抗折强度、韧性以及居里温度。例如，能够得到导磁率μ为900以上、居里温度Tc为140℃以上、抗折强度为165.0MPa以上、韧性值Kc为1.00Pa·m1/2以上的瓷器组合物。
各元素的含量可以通过使用电感耦合等离子体发光/质谱法(ICP－AES/MS)分析瓷器组合物的烧结体的组成而求出。
本发明的瓷器组合物中，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，优选进一步含有换算成Mn2O3为500ppm～3800ppm的Mn。如果瓷器组合物在上述的范围含有Mn，则能够进一步提高导磁率。应予说明，本发明的瓷器组合物可以不含有Mn。
本发明的瓷器组合物中，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，优选进一步含有换算成MgO为5ppm～50ppm的Mg。如果瓷器组合物在上述的范围含有Mg，则能够进一步提高居里温度。应予说明，本发明的瓷器组合物可以不含有Mg。
本发明的瓷器组合物中，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，优选进一步含有换算成BaO为0.6ppm～30ppm的Ba。如果瓷器组合物在上述的范围含有Ba，则与不含有Ba的瓷器组合物相比，能够提高抗折强度和韧性这两者。应予说明，本发明的瓷器组合物可以不含有Ba。
本发明的瓷器组合物中，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，优选进一步含有换算成GeO2为0.6ppm～80ppm的Ge。如果瓷器组合物在上述的范围含有Ge，则能够进一步提高抗折强度。应予说明，本发明的瓷器组合物可以不含有Ge。
本发明的瓷器组合物优选如下制造。
首先，以煅烧后的组成成为规定的组成的方式称量Fe2O3、CuO、NiO、ZnO、CoO以及Cr2O3，将该配合原料与纯水和PSZ(部分稳定化氧化锆)球一起放入球磨机，以湿式混合粉碎规定的时间(例如，4小时～8小时)。使其蒸发干燥后，以规定的温度(例如，700℃～800℃)预烧规定的时间(例如，2小时～5小时)，制成预烧物(预烧粉)。
将得到的预烧物(预烧粉)与纯水、作为粘合剂的聚乙烯醇、分散剂、增塑剂以及PSZ球一起放入球磨机中，以湿式进行混合粉碎。将该混合粉碎而得的浆料用喷雾干燥机干燥、造粒，制成颗粒粉末。
准备金属模，将制作的颗粒粉末加压成型而形成成型体。
接下来，将成型体用煅烧炉以规定的温度(例如，1100℃～1200℃)保持规定的时间(例如，2小时～5小时)进行煅烧。通过以上的制造工序得到瓷器组合物。
以下，示出更具体地公开了本发明的瓷器组合物的实施例。应予说明，本发明不仅限于这些实施例。
(实施例1)
以煅烧后的组成成为表1所示的组成的方式称量Fe2O3、CuO、NiO、ZnO、CoO以及Cr2O3，将该配合原料与纯水以及PSZ球一起放入球磨机中，以湿式混合粉碎4小时。使其蒸发干燥后，在800℃预烧2小时，由此制作预烧物。应予说明，作为配合原料，除上述原料之外，还将Mn2O3、MgO、BaO以及GeO2放入上述球磨机中。
将制作的预烧物与纯水、作为粘合剂的聚乙烯醇、分散剂、增塑剂以及PSZ球一起放入球磨机中，混合粉碎。将该混合粉碎而得的浆料用喷雾干燥机进行干燥、造粒，制作颗粒粉末。
将制作的颗粒粉末压制成型，制作煅烧后的尺寸为·外径20mm、内径12mm、厚度1.5mm的环状的试样，或者·4mm×2mm×1.5mm的单板状的试样的成型体。
将制作的成型体在1100℃煅烧2小时。通过以上操作制作试样1～21。
对于单板状的各试样，使用ICP－AES/MS分析烧结体的组成，由此测定各元素的含量。将结果示于表1。对于Fe、Cu、Ni、Zn、Co以及Cr，将换算成氧化物而得的值示于表1。
对于环状的各试样，收容于导磁率测定夹具Agilent Technologies公司制，16454A－s)，使用阻抗分析仪(Agilent Technologies公司制，E4991A)，测定25±2℃、测定频率1MHz下的初导磁率作为导磁率μ。另外，测定导磁率μ的温度特性，求出居里温度Tc。将结果示于表1。
对于单板状的各试样，通过3点弯曲试验测定抗折强度。抗折强度的测定使用煅烧后的试样。抗折强度进行10个试样的测定，采用其平均值。将结果示于表1。
对于单板状的各试样，通过维氏试验测定韧性值Kc。
将煅烧后的试样用树脂固定，将成为测定面的剖面研磨后测定韧性值Kc。韧性值Kc进行10个试样的测定，采用其平均值。将结果示于表1。
将韧性值Kc的测定方法的详情示于以下。
使用Tegramin－25(STRUERS公司制)进行剖面的粗研磨后，通过3μm和1μm的金刚石磨粒进行磨光，使用于形成压痕的剖面作为测定面露出。
压痕和裂纹的形成使用Micro Vickers硬度计(三丰公司制，HM220)以载荷1.0N、负荷时间1sec、保持时间4sec、接近速度60μm/1sec实施。
应予说明，韧性值Kc按照JIS R 1607由以下的公式计算。
Kc＝0.018×(E/HV)1/2×(P/C3/2)＝0.026×E1/2×P1/2×a/C3/2
Kc：断裂韧性值[Pa·m1/2]
E：弹性模量[Pa]*使用按照JIS R 1602测定的值
HV：维氏硬度[Pa]
P：压入载荷[N]
C：裂纹的长度的平均值的一半[m]
a：压痕的对角线的长度的平均值的一半[m]
[表1]
Figure BDA0003841021580000071
表1中，带*标记的试样是在本发明范围外的比较例。
根据表1，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3、上述CuO、上述NiO以及上述ZnO的合计量设为100摩尔份时，含有换算成Fe2O3为48.20摩尔份～49.85摩尔份的Fe，换算成CuO为2.00摩尔份～8.00摩尔份的Cu，换算成NiO为11.90摩尔份～18.70摩尔份的Ni，换算成ZnO为27.00摩尔份～33.50摩尔份的Zn，将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将上述Fe2O3，将上述CuO、上述NiO以及上述ZnO的合计量设为100重量份时，含有换算成CoO为5ppm～100ppm的Co，换算成Cr2O3为10ppm～400ppm的Cr的试样2～4、7、8、11、12、15、16、19以及20中，得到了导磁率μ为900以上、居里温度Tc为140℃以上、抗折强度为165.0MPa以上、韧性值Kc为1.00Pa·m1/2以上的瓷器组合物。
(实施例2)
表1的试样3在煅烧后的组成中含有换算成Mn2O3为2500ppm的Mn。制作表1的试样3的组成中换算成Mn2O3在煅烧后的组成中含有100ppm、500ppm、3800ppm或4500ppm的Mn的试样22～25，进行与实施例1同样的评价。测定Mn的含量的方法与实施例1同样。将结果示于表2。
[表2]
Figure BDA0003841021580000081
根据表2，含有换算成Mn2O3为500ppm～3800ppm的Mn的试样23、3以及24与试样22以及25相比，能够提高导磁率μ。
(实施例3)
表1的试样3在煅烧后的组成中含有换算成MgO为20ppm的Mg。制作表1的试样3的组成中换算成MgO在煅烧后的组成中含有2ppm、5ppm、50ppm或80ppm的Mg的试样26～29，进行与实施例1同样的评价。测定Mg的含量的方法与实施例1同样。将结果示于表3。
[表3]
Figure BDA0003841021580000091
根据表3，含有换算成MgO为5ppm～50ppm的Mg的试样27、3以及28与试样26以及29相比，能够提高居里温度Tc。
(实施例4)
表1的试样3在煅烧后的组成中含有换算成BaO为5ppm的Ba。制作表1的试样3的组成中换算成BaO在煅烧后的组成中含有0ppm、0.6ppm、30ppm或50ppm的Ba的试样30～33，进行与实施例1同样的评价。测定Ba的含量的方法与实施例1同样。将结果示于表4。
[表4]
Figure BDA0003841021580000092
根据表4，含有换算成BaO为0.6ppm～30ppm的Ba的试样31、3以及32与试样33不同，与试样30相比，能够提高抗折强度和韧性值Kc这两者。
(实施例5)
表1的试样3在煅烧后的组成中含有换算成GeO2为20ppm的Ge。制作表1的试样3的组成中换算成GeO2在煅烧后的组成中含有0ppm、0.6ppm、80ppm或130ppm的Ge的试样34～37，进行与实施例1同样的评价。测定Ge的含量的方法与实施例1同样。将结果示于表5。
[表5]
Figure BDA0003841021580000101
根据表5，含有换算成GeO2为0.6ppm～80ppm的Ge的试样35、3以及36与试样34和37相比，能够提高抗折强度。
应予说明，虽然实施例1的表1中未示出，但试样1、2和4～21分别含有与试样3相同程度的组成的Mn2O3、MgO、BaO以及GeO2。
[绕组型线圈部件]
本发明的绕组型线圈部件具备本发明的瓷器组合物的烧结体作为陶瓷芯。如上所述，本发明的瓷器组合物具有充分的导磁率、抗折强度和韧性，因此能够适用作在车载用途等要求对冲击的耐性的环境中使用的绕组型线圈部件。进而，本发明的瓷器组合物具有高的居里温度，因此也能够适用作在车载用途等高温环境下使用的绕组型线圈部件。
图1是示意地表示本发明的绕组型线圈部件的一个例子的主视图。图2是示意地表示构成图1所示的绕组型线圈部件的陶瓷芯的一个例子的立体图。
图1和图2是示意性的图，其尺寸、纵横比的比例尺等有时与实际的制品不同。
图1所示的绕组型线圈部件10具备陶瓷芯20、电极50和绕组(线圈)55。陶瓷芯20由本发明的瓷器组合物的烧结体构成。
如图2所示，陶瓷芯20具有轴芯部30和设置于在该轴芯部30的长度方向相对的两端部的一对凸缘部40。轴芯部30与凸缘部40一体地形成。
本说明书中，如图1和图2所示，将一对凸缘部40排列的方向定义为长度方向Ld，将与长度方向Ld正交的方向中图1和图2的上下方向定义为高度方向(厚度方向)Td，将与长度方向Ld和高度方向Td均正交的方向定义为宽度方向Wd。
轴芯部30例如形成为在长度方向Ld延伸的长方体状。轴芯部30的中心轴与长度方向Ld大致平行地延伸。轴芯部30具有在高度方向Td相对的一对主面31和32以及在宽度方向Wd相对的一对侧面33和34。
本说明书中，长方体状包括角部和棱线部被倒角的长方体、角部和棱线部被磨圆的长方体等。另外，可以在主面和侧面的一部分或全部形成凹凸等。
一对凸缘部40设置于轴芯部30的长度方向Ld的两端部。各凸缘部40形成为在长度方向Ld薄的长方体状。各凸缘部40形成为朝向高度方向Td和宽度方向Wd在轴芯部30的周围伸出。具体而言，从长度方向Ld观察时的各凸缘部40的平面形状形成为相对于轴芯部30在高度方向Td和宽度方向Wd伸出。
各凸缘部40具有在长度方向Ld相对的一对主面41和42、在宽度方向Wd相对的一对侧面43以及44以及在高度方向Td相对的一对端面45和46。一个凸缘部40的主面41与另一个凸缘部40的主面41对置地配置。
各凸缘部40的主面41形成为例如其整面与轴芯部30的中心轴延伸的方向(简言之，长度方向Ld)大致垂直地延伸。即，各凸缘部40的主面41的整面形成为与高度方向Td大致平行地延伸。其中，可以在各凸缘部40的主面41形成倾斜面。
如图1所示，电极50设置于各凸缘部40的高度方向Td的一个端面46。电极50例如在电路基板安装绕组型线圈部件10时与电路基板的电极电连接。电极50例如由镍(Ni)－铬(Cr)、Ni－铜(Cu)等Ni系合金、银(Ag)、Cu、锡(Sn)等构成。
绕组55卷绕于轴芯部30。绕组55例如具有以Cu等导电性材料为主成分的芯线被聚氨酯、聚酰亚胺或酰亚胺改性聚氨酯等绝缘材料被覆的结构。绕组55的两端部分别与电极50电连接。
本发明的绕组型线圈部件例如如下制造。
如上述的[瓷器组合物]中说明所示，将颗粒粉末加压成型而形成成型体。接下来，将成型体用煅烧炉在规定的温度(例如，1100℃～1200℃)保持规定的时间(例如，2小时～5小时)进行煅烧。将得到的烧结体投入滚筒内利用研磨件进行研磨。通过该滚筒研磨从烧结体除去毛刺，对烧结体的外表面(特别是角部和棱线部)赋予曲线状的圆度。通过以上的制造工序，得到如图2所示的陶瓷芯。
接着，在陶瓷芯的凸缘部的端面形成电极。例如，在凸缘部的端面涂布包含Ag和玻璃粉等的导电性糊料，在规定的温度(例如，800℃～820℃)进行烘烤处理而形成基底金属层后，通过电镀在基底金属层上依次形成镀Ni膜和镀Sn膜，由此形成电极。另外，作为形成电极的其它方法，可以通过在凸缘部的端面安装金属端子而作为电极使用。
接着，将绕组卷绕于陶瓷芯的轴芯部后，将绕组的端部与电极通过热压接等公知的方法接合。通过以上的工序，能够制造如图1所示的绕组型线圈部品。
本发明的绕组型线圈部件不仅限于上述的实施方式，可以在本发明的范围内施加各种应用、变更。作为其它形状，例如可以具备在长度方向Ld方向延伸并将凸缘部与凸缘部之间连接的顶板。另外，绕组的周围可以被树脂被覆。芯的形状不限于鼓芯，也可以为环状芯。
本发明的绕组型线圈部件中，陶瓷芯的轴芯部的形状和尺寸、陶瓷芯的凸缘部的形状和尺寸、绕组的粗细(线径)、卷数(匝数)、绕组的剖面形状和绕组的根数没有特别限定，可以根据期望的特性、安装场所而适当地变更。另外，电极的位置和数量也可以根据绕组的根数和用途而适当地设定。

Claims (6)

1.一种瓷器组合物，含有Fe、Cu、Ni、Zn、Co以及Cr，
将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100摩尔份时，含有：
换算成Fe2O3为48.20摩尔份～49.85摩尔份的Fe，
换算成CuO为2.00摩尔份～8.00摩尔份的Cu，
换算成NiO为11.90摩尔份～18.70摩尔份的Ni，
换算成ZnO为27.00摩尔份～33.50摩尔份的Zn；
将Fe、Cu、Ni以及Zn分别换算成Fe2O3、CuO、NiO以及ZnO，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100重量份时，含有：
换算成CoO为5ppm～100ppm的Co，
换算成Cr2O3为10ppm～400ppm的Cr。
2.根据权利要求1所述的瓷器组合物，其中，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100重量份时，进一步含有换算成Mn2O3为500ppm～3800ppm的Mn。
3.根据权利要求1或2所述的瓷器组合物，其中，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100重量份时，进一步含有换算成MgO为5ppm～50ppm的Mg。
4.根据权利要求1～3中任一项所述的瓷器组合物，其中，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100重量份时，进一步含有换算成BaO为0.6ppm～30ppm的Ba。
5.根据权利要求1～4中任一项所述的瓷器组合物，其中，将所述Fe2O3、所述CuO、所述NiO以及所述ZnO的合计量设为100重量份时，进一步含有换算成GeO2为0.6ppm～80ppm的Ge。
6.一种绕组型线圈部件，具备：
陶瓷芯，由权利要求1～5中任一项所述的瓷器组合物的烧结体构成且具有轴芯部和设置于在所述轴芯部的长度方向相对的两端部的一对凸缘部；
电极，设置于所述凸缘部的高度方向的一个端面；以及
绕组，卷绕于所述轴芯部且端部与所述电极电连接。
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Publication number Priority date Publication date Assignee Title
CN103717551A (zh) * 2011-07-28 2014-04-09 京瓷株式会社 铁氧体烧结体及具备它的铁氧体磁芯

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CN103717551A (zh) * 2011-07-28 2014-04-09 京瓷株式会社 铁氧体烧结体及具备它的铁氧体磁芯

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殷景华 等主编， 哈尔滨工业大学出版社: "《冶金炉料处理工艺》", vol. 1, pages: 167 - 77 *

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