CN113292327B - 一种具有宽温性质的软磁铁氧体材料及其生产工艺 - Google Patents

一种具有宽温性质的软磁铁氧体材料及其生产工艺 Download PDF

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CN113292327B
CN113292327B CN202110569843.3A CN202110569843A CN113292327B CN 113292327 B CN113292327 B CN 113292327B CN 202110569843 A CN202110569843 A CN 202110569843A CN 113292327 B CN113292327 B CN 113292327B
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CN113292327A (zh
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李崇华
汪竞阳
廖继红
黄刚
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China Magnetic Electronic Technology Co ltd
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Abstract

本发明涉及软磁铁氧体技术领域,公开了一种具有宽温性质的软磁铁氧体材料,包括主体料和辅助料;所述主体料按摩尔份数计,包括有:53‑56molFe2O3;7‑10molMnO;10‑13molZnO;1‑3molNiO;相对于所述主体料的质量,所述辅助料按质量添加为:400‑700ppmCuO;400‑800ppmBi2O3;600‑900ppmCo3O4;300‑500ppmCaCO3;100‑200ppmSiO2。本发明能够减小低温环境下功率损耗。

Description

一种具有宽温性质的软磁铁氧体材料及其生产工艺
技术领域
本发明涉及软磁铁氧体技术领域,特别涉及一种具有宽温性质的软磁铁氧体材料及其生产工艺。
背景技术
软磁铁氧体是以Fe2O3为主成分的亚铁磁性氧化物,采用粉末冶金方法生产。有Mn-Zn、Cu-Zn、Ni-Zn等几类,其中Mn-Zn铁氧体的产量和用量最大,Mn-Zn铁氧体的电阻率低,为1~10 欧姆/米,一般在100kHZ以下的频率使用。Cu-Zn、Ni-Zn铁氧体的电阻率为102~104欧姆/米,在100kHz~10兆赫的无线电频段的损耗小,多用在无线电用天线线圈、无线电中频变压器。
发明内容
本发明的目的是提供一种具有宽温性质的软磁铁氧体材料及其生产工艺,旨在达到减小低温环境下功率损耗的目的。
本发明的上述技术目的是通过以下技术方案得以实现的:一种软磁铁氧体材料,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 53-56mol;
MnO 7-10mol;
ZnO 10-13mol;
NiO 1-3mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 400-700ppm;
Bi2O3 400-800ppm;
Co3O4 600-900ppm;
CaCO3 300-500ppm;
SiO2 100-200ppm。
本发明的进一步设置为:相对于所述主体料的质量,所述辅助料按质量还包括有200-500ppm的CdO。
本发明的进一步设置为:相对于所述主体料的质量,所述辅助料按质量还包括有100-300ppm的Li2CO3
本发明的进一步设置为:相对于所述主体料的质量,所述辅助料按质量还包括有200-400ppm的Ta2O5
本发明还提供了一种制备如上任一项所述的宽温高效软磁铁氧体材料的方法,包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为1-2h;
S2,对一次球磨完成的物料进行预烧;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为4-6h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
本发明的进一步设置为:相对于所述主体料的质量,所述PVA溶液的浓度为8-12wt%,按质量添加量为10-15wt%。
本发明的进一步设置为:所述S2中预烧温度为900-1000℃。
本发明的进一步设置为:所述S7中的烧结方法包括:
S71,从室温开始以2-2.5℃/min的速度升至900-1000℃,保持1.5-3h;
S72,以1.5-2℃/min的速度升至1350-1370℃,保持5-6h。
本发明的进一步设置为:所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为20-30。
本发明的有益效果是:在实际软磁铁氧体使用的过程中,总的功率损耗通常主要是包括磁滞损耗、涡流损耗和剩余损耗,但是同时在工作频率低于500kHz时的剩余损耗非常少,几乎可以忽略不计,因此在实践中通常情况下都可以将剩余损耗不计入考虑,即通常会把磁滞损耗和涡流损耗之和考虑为总的功率损耗;不仅如此,在较低的温度(例如零下20℃至零下40℃)的情况下,总的功率损耗通常是以磁滞损耗为主。
在主体料中加入的各个辅助料在生产的过程中,由于Bi2O3的熔点为825℃,因此在逐步加热的过程中,首先温度升高到Bi2O3能够熔化的状态,即高于825℃并保持一定的时间;在保持高温的时间段内,呈现为液态的Bi2O3能够在物料间隙之间流动,并作用于各个主体料和辅助料上,同时可以将材料中的气隙进行填充,且为晶粒的生长提供一个预备液相环境;在后续继续升温的过程中,由于CdO的熔点为900℃,因此在后续继续加热的过程中,CdO也相继液化,并进一步的将物料中的气隙进行充盈以及填满,同时也形成了更为优质的液相环境,不仅能够减少材料气孔率,同时也能够提升烧结密度,使得晶粒的均匀性也更佳。其中在升温过程中,通过逐步加热的方式,可以使得Bi2O3和CdO能够逐步液化,并分布充盈物料之间的间隙,液相的全面性更佳。不仅如此,由于Bi2O3和CdO的润湿角度不同,因此在二者分步融化之后,能够更好的将其他所有组分润湿,从而提高产品的整体性,并减小产品的气隙;同时由于Bi2O3是先形成的液相,而CdO是后形成的液相,所以二者在润湿其他组分的时候,能够分别润湿可以润湿的组份或成分,从而使得两段加热完成后,可以最大程度上将可以被润湿的组分润湿,整体润湿效果更好。
同时加入的CaCO3和SiO2(优选尺寸选择为50-100nm,下同)在烧结的过程中,能够很有效的改善晶界处的电阻,即可以很好的提高晶界处的电阻,从而可以明显的改善材料的涡流损耗,从而在较高温度的使用环境中,也可以使得材料具有较低的功率损耗。同时Bi2O3和CdO在烧结前期升温的过程中,能够与CaCO3和SiO2之间形成相互的作用,并促成CaCO3和SiO2覆盖或包裹在初步生成的晶粒表面,使得后续晶粒成型后,能够更好的提高晶粒晶界处的电阻,并保证了具有较低的涡流损耗,使得材料能够在较高的温度中进行使用。
其中,将SiO2的尺寸选择为50-100nm,能够保证SiO2具有较好的分散度,并且在晶粒形成时,可以较好的覆盖于晶粒的表面,同时也可以使得其能够与CaCO3之间较好的发生接触,从而更好的进行反应。
不仅如此,由于Li2CO3的熔点是720℃,则在逐步升温的过程中,Li2CO3会优先熔化,并提供更前期的液相,同时在润湿各相组分的时候,其单独具有的润湿角,也能够使得对全组分的润湿效果更佳。而Ta2O5的熔点较高,则在成型后的过程中,其能够较好的防止晶粒过度生长,保持了晶粒的质量。
将物料压制的密度为为2.92-2.98g/cm3时,能够使得成品材料的烧结密度在4.869-4.98g/cm3之间,而在该密度下能够较好的保证材料具有较高的饱和磁通密度。
具体实施方式
下面将结合具体实施例对本发明的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种具有宽温性质的软磁铁氧体材料,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 53mol;
MnO 10mol;
ZnO 10mol;
NiO 3mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 400ppm;
Bi2O3 800ppm;
Co3O4 600ppm;
CaCO3 500ppm;
SiO2 100ppm。
一种制备如上所述的具有宽温性质的软磁铁氧体材料的方法,包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为2h;
S2,对一次球磨完成的物料进行预烧,预烧温度为900℃;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为6h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
相对于所述主体料的质量,所述PVA溶液的浓度为8wt%,按质量添加量为15wt%。
所述S7中的烧结方法包括:
S71,从室温开始以2℃/min的速度升至1000℃,保持1.5h;
S72,以2℃/min的速度升至1350℃,保持6h。
所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为20。
所述S6中压制成型的物料的密度为2.93g/cm3,材料的烧制密度为4.871g/cm3
经检测,最终产品晶粒尺寸为3-5μm,起始磁导率ui为2400(±25%),-40℃、100kHz、200mT Bs值下功率损耗为310 kW/m3,100℃Bs值为440mT。
实施例2
一种具有宽温性质的软磁铁氧体材料,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 56mol;
MnO 7mol;
ZnO 13mol;
NiO 1mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 700ppm;
Bi2O3 400ppm;
Co3O4 900ppm;
CaCO3 300ppm;
SiO2 200ppm;
CdO 200ppm。
一种制备如上所述的具有宽温性质的软磁铁氧体材料的方法,包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为1h;
S2,对一次球磨完成的物料进行预烧,预烧温度为1000℃;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为5h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
相对于所述主体料的质量,所述PVA溶液的浓度为12wt%,按质量添加量为10wt%。
所述S7中的烧结方法包括:
S71,从室温开始以2.5℃/min的速度升至900℃,保持3h;
S72,以1.5℃/min的速度升至1370℃,保持5h。
所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为30。
所述S6中压制成型的物料的密度为2.95g/cm3,材料的烧制密度为4.874g/cm3
经检测,最终产品晶粒尺寸为3-5μm,起始磁导率ui为2400(±25%),-35℃、100kHz、200mT Bs值下功率损耗为300kW/m3,100℃Bs值为450mT。
实施例3
一种具有宽温性质的软磁铁氧体材料,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 54mol;
MnO 9mol;
ZnO 11mol;
NiO 2mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 500ppm;
Bi2O3 600ppm;
Co3O4 400ppm;
CaCO3 400ppm;
SiO2 150ppm;
CdO 500ppm;
Li2CO3 100ppm。
一种制备如上所述的具有宽温性质的软磁铁氧体材料的方法,包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为1.5h;
S2,对一次球磨完成的物料进行预烧,预烧温度为950℃;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为4.5h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
相对于所述主体料的质量,所述PVA溶液的浓度为10wt%,按质量添加量为12wt%。
所述S7中的烧结方法包括:
S71,从室温开始以2.5℃/min的速度升至950℃,保持2h;
S72,以1.8℃/min的速度升至1360℃,保持5.5h。
所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为25。
所述S6中压制成型的物料的密度为2.98g/cm3,材料的烧制密度为4.883g/cm3
经检测,最终产品晶粒尺寸为3-5μm,起始磁导率ui为2600(±25%),-45℃、100kHz、200mT Bs值下功率损耗为290kW/m3,100℃Bs值为470mT。
实施例4
一种具有宽温性质的软磁铁氧体材料,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 54mol;
MnO 8mol;
ZnO 12mol;
NiO 2.5mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 650ppm;
Bi2O3 700ppm;
Co3O4 500ppm;
CaCO3 450ppm;
SiO2 120ppm;
CdO 350ppm;
Li2CO3 300ppm;
Ta2O5 300ppm。
一种制备如上所述的具有宽温性质的软磁铁氧体材料的方法,包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为1.2h;
S2,对一次球磨完成的物料进行预烧,预烧温度为980℃;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为4.5h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
相对于所述主体料的质量,所述PVA溶液的浓度为11wt%,按质量添加量为11wt%。
所述S7中的烧结方法包括:
S71,从室温开始以2℃/min的速度升至980℃,保持2.5h;
S72,以1.8℃/min的速度升至1370℃,保持5.8h。
所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为22。
所述S6中压制成型的物料的密度为2.976g/cm3,材料的烧制密度为4.882g/cm3
经检测,最终产品晶粒尺寸为3-5μm,起始磁导率ui为2700(±25%),-40℃、100kHz、200mT Bs值下功率损耗为270kW/m3,100℃Bs值为470mT。
需要说明的是,本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。
上述描述仅是对本发明较佳实施例的描述,并非对本发明范围的任何限定,本发明领域的普通技术人员根据上述揭示内容做的任何变更、修饰,均属于权利要求书的保护范围。

Claims (7)

1.一种具有宽温性质的软磁铁氧体材料,其特征在于,包括主体料和辅助料;
所述主体料按摩尔份数计,包括有:
Fe2O3 53-56mol;
MnO 7-10mol;
ZnO 10-13mol;
NiO 1-3mol;
相对于所述主体料的质量,所述辅助料按质量添加为:
CuO 400-700ppm;
Bi2O3 400-800ppm;
Co3O4 600-900ppm;
CaCO3 300-500ppm;
SiO2 100-200ppm;
相对于所述主体料的质量,所述辅助料按质量还包括有200-500ppm的CdO;
相对于所述主体料的质量,所述辅助料按质量还包括有200-400ppm的Ta2O5
2.根据权利要求1所述的一种具有宽温性质的软磁铁氧体材料,其特征在于:相对于所述主体料的质量,所述辅助料按质量还包括有100-300ppm的Li2CO3
3.一种制备如权利要求1至2任一项所述的具有宽温性质的软磁铁氧体材料的方法,其特征在于:包括以下步骤:
S1,按摩尔份取主体料的各个组分,并将主体料混合后进行一次球磨,时间为1-2h;
S2,对一次球磨完成的物料进行预烧;
S3,向预烧完成的物料中按照质量加入各个辅助料;
S4,对S3中的物料进行二次球磨,时间为4-6h;
S5,向二次球磨中的物料中加入PVA溶液后混匀,然后对物料进行喷雾制粒;
S6,将S5中的物料进行压制成型;
S7,对成型的材料进行烧结,冷却得到产品。
4.根据权利要求3所述的一种具有宽温性质的软磁铁氧体材料的生产工艺,其特征在于:相对于所述主体料的质量,所述PVA溶液的浓度为8-12wt%,按质量添加量为10-15wt%。
5.根据权利要求3所述的一种具有宽温性质的软磁铁氧体材料的生产工艺,其特征在于:所述S2中预烧温度为900-1000℃。
6.根据权利要求3所述的一种具有宽温性质的软磁铁氧体材料的生产工艺,其特征在于:所述S7中的烧结方法包括:
S71,从室温开始以2-2.5℃/min的速度升至900-1000℃,保持1.5-3h;
S72,以1.5-2℃/min的速度升至1350-1370℃,保持5-6h。
7.根据权利要求6所述的一种具有宽温性质的软磁铁氧体材料的生产工艺,其特征在于:所述S7中的气氛为O2和N2的混合,其中N2和O2体积比为20-30。
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