CN115246736A - 用于vuhf天线应用的镍锌铜铁氧体 - Google Patents
用于vuhf天线应用的镍锌铜铁氧体 Download PDFInfo
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- 229910000859 α-Fe Inorganic materials 0.000 title abstract description 23
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011343 solid material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 58
- 230000035699 permeability Effects 0.000 claims description 28
- 230000005291 magnetic effect Effects 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 11
- 239000003989 dielectric material Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 58
- 239000010949 copper Substances 0.000 abstract description 43
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 44
- 229910017052 cobalt Inorganic materials 0.000 description 14
- 239000010941 cobalt Substances 0.000 description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000002759 woven fabric Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005350 ferromagnetic resonance Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910007564 Zn—Co Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005293 ferrimagnetic effect Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 102000052584 Anaphase-Promoting Complex-Cyclosome Apc7 Subunit Human genes 0.000 description 1
- 101000693970 Homo sapiens Scavenger receptor class A member 3 Proteins 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- -1 cobalt-substituted nickel zinc Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Abstract
本发明涉及一种用于VUHF天线应用的镍锌铜铁氧体。具体涉及一种特别适用于制造天线的组合物和固体材料,该天线适于非常高频(VHF)带以及超高频(UHF)带或V/UHF中操作,以及制造方法及其用途。该组合物具有式NiaZnbCucCodFe2‑δO4,其中:2(a+b+c+d)+3(2‑δ)=80.05<b<0.5,例如0.1<b<0.5,例如0.1<b<0.4,例如0.15<b<0.350.10<c<0.25,优选0.15<c<0.25,或者c为0.20,0.04<d<0.25,优选0.06<d<0.25,更优选为0.07<d<0.25,和δ<0.05。
Description
技术领域
本发明涉及一种特别适用于制造天线的组合物和固体材料,该天线适于在30MHz和300MHz之间的非常高频(VHF)带,以及在300MHz和3GHz之间的超高频(UHF)带,或V/UHF中操作,以及涉及制造方法及其用途。
现有技术
天线的微型性质是一个主要问题,特别是对于低于GHz工作的天线。实际上,天线的尺寸与发送/接收信号的波长成正比,这是VHF/UHF频率的仪表的顺序(VHF:30MHz至300MHz;UHF:300MHz至3000MHz)。如今,通常用于减小天线几何尺寸的策略之一是使用具有高介电常数(ε')的介电材料。然而,使用这种材料导致天线性能的降低(增益,带宽)。
可以通过使用诸如铁氧体的磁性-介电材料来克服这种限制。实际上,使用具有高磁导率(μ')的材料将使减小天线的尺寸成为可能,同时最大化其效率。实际上,尽管ε'对介电损耗和储存能量量具有积极影响,但已经证明:(i)ε'对带宽以及天线效率具有负面影响,以及(ii)μ'具有相反的效果,因此对两个参数产生积极影响。此外,如果天线保持等尺度(iso-dimensional),则这种材料将提高其性能(M.A.C Niamien,S.Collardey,A.Sharaiha,K.Mahdjoubi,"Compact Expressions for Efficiency and Bandwidth ofPatch Antennas Over Lossy Magneto-Dielectric Materials,"IEEE antennas andwireless propaga.letters,10(2011)63-66)。
久已周知,向铁氧体特别是镍-锌铁氧体添加低浓度的钴,可以对化合物的磁损耗具有积极影响。一例子是Lau和Stuijts的研究(J.G.MLau和A.L.Stuijts,ChemicalComposition and High-Frequency Properties of Ni-Zn-Co Ferrites,PhilipsRes.Repts,21(1966)104-112)104-112),其介绍了在(Ni0.8Zn0.2)0.97-XCo0.03Fe2O4+γ晶体结构中的钴离子行为的机理。有大量研究专注于钴替代的镍锌铁氧体。然而,所讨论的组合物不含铜,并且在高频(频率F>100MHz)下的磁损耗方面的表现比本发明中规定低得多。一些组合物在磁导率方面设法表现出稳定的行为。然而,它们具有在太低频率下发生的亚铁磁共振的问题,并且导致磁损耗从约10MHz增加。
有一些实验室级镍-锌的铁氧体材料,具有与本发明类似的性能。例如,Mathur等人的团队在2010年发布的铁氧体组成允许高频使用(P.Mathur,A.Thakur,J.H.Lee,M.Singh,Sustained electromagnetic properties of Ni-Zn-Co nanoferrites for thehigh-frequency applications,Materials Letters,64(2010)2738-2741)。实际上,在10至200MHz的频率范围和约9磁导率μ'下,产生的材料具有低磁损耗(约0.05的损耗正切)。介绍的材料的组成如下:Ni0.49Zn0.49Co0.02Fe2O4。由于钴含量低(0.02mol),作者使用了另一种方法推动共振超过200MHz。它们使用共沉淀方法将化合物合成为约50nm的颗粒,并在较低温度下烧结它们的材料,以避免过量的晶体生长。因此,该材料具有精细的微结构,其允许将磁畴壁的运动动力学改变为排斥共振。共沉淀合成方法与传统的合成方法非常不同。从工业角度来看,它也是昂贵和难以实施的。
Saini等人的团队(A.Saini,A.Thakur,P.Thakur,Matching permeability andpermittivity of Ni0.5Zn0.3Co0.2In0.1Fe1.9O4 ferrite for substrate of largebandwidth miniaturized antenna,J Mater Sci:Mater Electron,27(2016)2816-2823)显示了对组合物Ni0.5Zn0.3Co0.2In0.1Fe1.9O4的兴趣,用于UHF天线的小型化,如果与装载有简单介电材料的天线相比,在带宽中具有增益。该材料通过共沉淀合成,并具有高钴含量(0.2mol)。它具有约5-6的磁导率和直至至少500-600MHz的低磁损耗。
最后,我们还可以提及Brest(法国)的Lab-STICC实验室中进行的工作,该工作专注于通过共沉淀制造磁性-介电材料,其可以满足V/UHF频带的天线要求。已经公布了几种结果,证明了使用共沉淀方法在诸如Ni0.5Zn0.3Co0.2Fe1.98O4-δ的化合物上使用的兴趣,以在高频率下实现低磁损耗,同时保持相对高的磁导率。
镍-锌-铜铁氧体广泛用于电感器。制造商利用了该化合物(<1000℃)的低烧结温度,这是由大程度的铜(通常在0.2和0.25mol)所提供的,以直接与电极或绕组共烧结铁氧体。据报道,当将铜添加到诸如Ni0.8-xZn0.2CuxFe2O4的化合物中时,铜添加存在0.2mol的最佳值(J.J.Shrotri,S.D.Kulkarni,C.E.Deshpande,A.Mitra,S.R.Sainkar,P.S.Anil Kumar,S.K.Date,Effect of Cu substitution on the magnetic and electrical propertiesof Ni-Zn ferrite synthesised by soft chemical method,Materials Chemistry andPhysics,59(1999)1-5)。对于过高(x≥0.3mol)的值,铜形成第二CuO/CuFeO4相,并且材料的性质劣化。
许多研究显示了Ni-Zn-Cu铁氧体具有有趣的高频行为。然而,对于本发明涵盖的应用,所考虑的频率通常太低。这种类型的材料通常具有1至100MHz之间的亚铁磁性共振。另外,共振的发生伴随着磁损耗的增加(由值μ”或tanδμ表示),使得材料不能在超过该共振的频带上用于天线材料。
发明目标
本发明旨在解决提供可用作VHF或V/UHF天线的组合物的技术问题。
特别地,本发明旨在解决提供可用作小型VHF或V/UHF天线的组合物的技术问题。
特别地,本发明旨在解决提供适合在VHF和/或UHF频带上用作(优选小型化的)天线材料的镍-锌-铜铁氧体组合物的技术问题。
特别地,本发明旨在解决提供可用作(优选小型化的)天线的组合物的技术问题,就此共振发生在高于50MHz,优选高于70MHz,优选高于100MHz,或甚至更优选更高的频率下。
特别地,本发明旨在解决提供优选具有磁导率μ'≥5和介电常数ε'≥10的磁性-介电组合物的技术问题,该组合物优选地具有接近介电常数的磁导率。
本发明还旨在解决提供制造这种组合物的方法的技术问题,优选通过研磨/锤击(hammering)制备陶瓷材料的常规工业方法进行制造。
发明内容
发明人已经发现,使用在镍-锌铁氧体组合物中具有高水平钴和高水平铜的本发明组合物解决了上述技术问题中的至少一个,优选所有。
发明人发现,通过增加Ni/Zn之比,使用根据本发明的组合物提供了有利解决上述技术问题的至少一个,优选所有的组合物。
有利地,这种组合物可以通过在式NiaZnbCucCodFe2-δO4合金的铁氧体组合物中引入钴部分替代镍来获得。
本发明涉及式NiaZnbCucCodFe2-δO4的组合物,其中:
2(a+b+c+d)+3(2-δ)=8
0.05<b<0.5,例如0.1<b<0.5,例如0.1<b<0.4。
0.10<c<0.25,优选0.15<c<0.25,或者c为0.20,
0.04<d<0.25,优选0.06<d<0.25,更优选为0.07<d<0.25,和
δ<0.05。
有利地,该组合物是镍锌铜铁氧体,优选具有1至15的Ni/Zn之比。
有利地,该组合物具有尖晶石结构。
本发明涉及一种具有尖晶石结构的镍-锌-铜铁氧体材料,其可用作VUHF频带中的天线材料。
在一个实施方案中,“b”大于或等于0.05。
在一个实施方案中,“b”大于或等于0.1。
在一个实施方案中,“b”小于或等于0.5。
在一个实施方案中,“b”小于或等于0.4。
在一个实施方案中,“b”小于或等于0.35。
有利地,任何所述的下限可以与任何所述的上限组合。
在一个实施方案中,0.05<b<0.5。
在一个实施方案中,0.1<b<0.5。
在一个实施方案中,0.1<b<0.4。
在一个实施方案中,0.15<b<0.35。
在一个实施方案中,“c”大于或等于0.10。
在一个实施方案中,“c”大于或等于0.15。
在一个实施方案中,“c”小于或等于0.25。
有利地,任何所述的下限可以与任何所述的上限组合。
根据一个实施方案,0.10<c<0.25,优选0.15<c<0.25,根据变体c为0.20。
在一个实施方案中,“d”大于或等于0.04。
在一个实施方案中,“d”大于或等于0.05。
在一个实施方案中,“d”大于或等于0.06。
在一个实施方案中,“d”大于或等于0.07。
在一个实施方案中,“d”为0.10。
在一个实施方案中,“d”小于或等于0.25。
有利地,任何所述的下限可以与任何所述的上限组合。
在一个实施方案中,0.04<b<0.25。
优选地,0.06<d<0.25。
有利地,0.07<d<0.25。
有利地,0.09<d<0.25。
在一个实施方案中,“a”大于或等于0.3。
在一个实施方案中,“a”大于或等于0.35。
在一个实施方案中,“a”大于或等于0.4。
在一个实施方案中,“a”小于或等于0.8。
在一个实施方案中,“a”小于或等于0.7。
在一个实施方案中,“a”小于或等于0.6。
有利地,任何所述的下限可以与任何所述的上限组合。
在一个实施方案中,0.3<a<0.7。
在一个实施方案中,0.4<a<0.7。
有利地,该组合物选自以下式的组合物:
Ni0.5005Zn0.3195Cu0.20Co0.04Fe1.96O4,
Ni0.4805Zn0.3195Cu0.20Co0.06Fe1.96O4,
Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4,
Ni0.4347Zn0.3153Cu0.20Co0.11Fe1.96O4,
Ni0.4231Zn0.3069Cu0.20Co0.13Fe1.96O4,
Ni0.4115Zn0.2985Cu0.20Co0.15Fe1.96O4,和
Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4,
在一个实施方案中,Ni/Zn之比为1至15,优选1至10,甚至更优选为1.2至7。
有利地,Ni/Zn之比大于2。
在一种变体中,该比率为1.38,在另一个变体中,该比率为3。
本发明还涉及具有根据本发明定义的组合物的固体材料。
根据一个实施方案,根据本发明的材料形成优选具有磁导率μ'>1和介电常数ε'>1,且优选μ'≥5和ε'≥10的磁性-介电材料。
根据一个实施方案,根据本发明的材料对于VHF范围(1MHz至300MHz)范围具有10至20的磁导率μ',或对于V/UHF范围(200MHz至600MHz)5至15的μ'。
根据一个实施方案,根据本发明的材料具有磁损耗tan(δμ)<0.06,并且优选地在100到200MHz之间的频带上的介电损耗tan(δε)<0.02。
根据一个实施方案,tan(δε)<0.006。
本发明还涉及具有根据本发明所定义的组合物或固体材料的VHF或V/UHF天线。
根据一个实施方案,天线是印刷天线或微带或“贴片”型的VHF或V/UHF天线,其包含一个或多个粘附到辐射元件的基板层,其中一个或多个基板层包括根据本发明的组合物或根据本发明的固体材料,或由该组合物或固体材料组成。
在一个实施方案中,天线是小型化的。通常,天线具有小于300mm的较大尺寸。
本发明还涉及将根据本发明的组合物或根据本发明的固体材料用作VHF或V/UHF天线。
有利地,本发明涉及用于航空的天线。
在一个实施方案中,天线适于在118MHz和156MHz之间,并且优选在118和137MHz之间的操作。
本发明还涉及制造根据本发明所定义的组合物的方法。
特别地,本发明涉及制造根据本发明的组合物或根据本发明的固体材料的方法,所述方法包括:
研磨原料,该原料提供Ni、Zn、Cu、Co、Fe和O,通常为NiO;ZnO;CuO;Co3O4和Fe2O3,
研磨后,干燥粉末,然后筛分,优选用400μm筛,
筛分后,将粉末热处理,优选在至少600℃,例如800℃的温度下,例如1至10小时,通常为2小时,
热处理后,使粉末经历第二研磨,例如用水溶液,
然后将粉末成形为固体材料。
在一个实施方案中,在成形之前,该方法包括用粘合剂涂覆粉末以提供成形的材料。
在一个实施方案中,在成形之后,该方法包括烧结成形的材料。
有利地,该材料根据制备陶瓷材料的方法合成。
在一个实施方案中,研磨原料的步骤包括如下或由如下组成:称量不同氧化物以制备组成:NiO;ZnO;CuO;Co3O4和Fe2O3。考虑到在研磨过程中引入的铁杂质,在该称量引入氧化铁缺陷。根据一个实施方案,然后将原料混合,然后在水性过程中用研磨设备例如球磨机,磨碎机,罐子搅动器等研磨(通常为罐研磨20小时)。
在一个实施方案中,研磨后,干燥该粉末,然后筛分至400μm。然后将其在800℃下在窑中进行热处理(“熟料化”)2小时。
在一个实施方案中,使粉末经受第二研磨。例如,筛分该粉末,然后放入水性浆料中,即在水性溶液(通常是水)中稀释,用于再研磨(通常对罐研磨持续36小时)。
在一个实施方案中,将粉末用粘合剂涂覆,然后通过压制成形。
有利地,使粉末接收涂层以允许粉末的成形。可以通过在第二研磨期间将粘合剂添加到粉浆或一旦干燥并筛分该粉末就在研磨后,完成粘合剂的添加。在每种情况下,优选将粉末干燥,然后在成形之前在200至400μm之间筛分。
有利地,根据需要通过(通常是单轴)压制成片、盘或芯的形式来执行成形。
有利地,烧结成形的材料。
烧结通常高于800℃的温度下进行,优选在850至1000℃之间进行。
通常,烧结在氧化气氛例如空气中进行。
在一个实施方案中,将压制的材料在950℃下在空气中烧结2小时。优选地,在窑温升高到例如950℃之前,在500℃下用缓慢升温将所述材料脱胶(debonded)。脱胶的持续时间取决于部件的尺寸及其质量,并且可以是例如1h至48h。在低于1200℃,有利地在950℃的温度下根据本发明的烧结具有显著的技术优势。通常,在1200-1400℃之间烧结具有尖晶石结构的铁氧体4至12小时。因此,本发明节省了在窑上(温度<1000℃的尺寸)的时间和成本和加热所需的功率。
有利地,根据本发明的组合物或材料构成具有的磁导率接近(例如+/-10个单元,优选+/-5个单位)其介电常数(磁性-介电材料:ε'>1和μ'>1)的磁性-介电材料。
有利地,根据本发明的组合物或材料表现出高于50MHz,优选高于70MHz,最优选高于100MHz的铁磁共振。
高于一定值的铁磁共振意味着在高于该值的频率下出现磁导率峰。
有利地,根据本发明的组合物或材料表现出高于120MHz,优选高于140MHz,最优选高于150MHz的铁磁共振。
甚至更有利地,根据本发明的组合物或材料具有高于200MHz的铁磁共振。
这种优点特别与根据本发明的合金配方的组合物相关。
有利地,对于VHF范围(1MHz至300MHz),根据本发明的组合物和材料具有大于10,优选大于15,甚至更优选大于20的磁导率μ'。
有利地,对于V/UHF范围(200MHz至600MHz),根据本发明的组合物和材料具有大于5,优选大于10,甚至更优选大于15的磁导率μ'。
有利地,根据本发明的组合物和材料在VHF/UHF下具有低磁损耗,在1至50MHz,优选1至70MHz,更优选为1至100MHz的频带中tanδμ低于0.05。
有利地,根据一个实施方案,根据本发明的组合物和材料在VHF/UHF下具有低磁损耗,在100至200MHz的频带中tanδμ低于0.06,优选低于0.05,甚至更优选低于0.04。
有利地,根据本发明的组合物和材料具有中等磁导率(通常μ'为5至20,优选10至20),并且在100到200MHz的频带中在VHF/UHF中具有低磁损耗(tanδμ<0.05)。
在图中:
图1是显示常规镍锌铁氧体(NZ50其中Ni/Zn为1.77和Co为0.008)和镍锌铜铁氧体(Ni0.5005Zn0.3195Cu0.20Co0.04Fe1.96O4其中Ni/Zn为1.57,Co为0.04)相对于频率的磁导率和磁损耗的图。
图2是显示NZC铁氧体相对于频率的磁导率和磁损耗的图。Ni0.5005Zn0.3195Cu0.20Co0.04Fe1.96O4(Ni/Zn为1.57和Co为0.04)和Ni0.4805Zn0.3195Cu0.20Co0.06Fe1.96O4(Ni/Zn为1.50和Co为0.06)。
图3是显示作为频率函数的NZC铁氧体的磁导率和磁损耗的图,其中Ni0.4805Zn0.319 5Cu0.20Co0.06Fe1.96O4(Ni/Zn为1.50和Co为0.06);Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4(Ni/Zn为1.38和Co为0.1)和Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4(Ni/Zn为3和Co为0.06)。
图4是显示作为频率函数的NZC铁氧体的磁导率和磁损耗的图,其中Ni0.4347Zn0.315 3Cu0.20Co0.11Fe1.96O4(Ni/Zn为1.38和Co为0.11);Ni0.4231Zn0.3069Cu0.20Co0.13Fe1.96O4(Ni/Zn为1.38和Co为0.13)和Ni0.4115Zn0.2985Cu0.20Co0.15Fe1.96O4(Ni/Zn为1.38和Co为0.15)。
图5是显示作为频率函数的材料Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4的磁性磁导率和磁损耗的图。
图6是显示作为频率函数的材料Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4磁导率和磁损耗的图。
图7是显示作为频率函数的材料Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4的介电常数和介电损耗的图。
图8是显示作为频率函数的材料Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4的材料的介电常数和介电损耗的图。
实施例
为了评估根据本发明的材料的潜力,我们主要对作为频率函数的磁导率与磁损耗的变化感兴趣。这意味着监视当损耗增加时(这与铁磁共振的开始一致)的时刻和共振前的磁导率的值。
使用HP4291A阻抗分析仪在1MHz和1GHz之间进行磁导率、介电常数、磁和介电损耗的测量。
为了测量磁导率和磁损耗,制造柱形烧结态的托型APC7形式的样品(厚度≤3mm)。测量是在Keysight 16454A MagneticMaterial Test Fixture中进行的。该测试的参考资料可以在制造商的网站上找到(参考文件:16454A Magnetic Material Test Fixture Operation and Service Manual andMaterials Measurement:Magnetic Materials-Application Brief at https://www.keysight.com/en/pd-1000000509%3Aepsg%3Apro-pn-16454A/magnetic-material-test-fixture?pm=PL&nid=-536902475.536879639&cc=FR&lc=fre)。
为了测量介电常数和介电损耗,制造了厚度不等(1;0.5;0.3mm)的10mm见方板形式的样品。然后使用HP Agilent Keysight 16092A Spring Clip Test Fixture(允许在1和500MHz之间测量)在阻抗分析器(HP4291A)中测量电容和损耗因子。
图1显示了这种曲线。虚线显示了经典的尖晶石铁氧体(NZ50,由EXXELIA销售),并且可以在50MHz之前观察到共振的外观(磁导率峰在约20MHz)。损耗增加并使材料不可用作VHF和/或UHF天线材料。如图1所示的铜含量为0.2的镍-锌-铜铁氧体(Ni0.5005Zn0.3195Cu0.20Co0.04Fe1.96O4)的使用允许将共振移至更高的频率,高于50MHz(峰在约100MHz)。
图2显示了组合物Ni0.4805Zn0.3195Cu0.20Co0.06Fe1.96O4。对于1.5的Ni/Zn之比和0.06的增加钴含量,共振被推到较高频率,允许直至100MHz的低损耗(tanδμ<0.04)。这给出了一种可以用作1至100MHz之间的天线材料的材料,而μ’约29。
图3将两种新材料与图2已以薄实线/灰色显示的材料(Ni0.4805Zn0.3195Cu0.20Co0.06Fe1.96O4)进行比较。以厚实线/黑色所示的第一材料具有以下组成:Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4。相比之下,Ni/Zn之比略微降低(由于通过替代镍进行的钴的强加入),但钴的比例大大增加到0.1摩尔。这表明钴在200MHz后推回共振的直接效果。在图3以虚线所示的材料:Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4上观察到类似的效果。与薄/灰色实线所示的材料相比,钴含量保持不变,但Ni/Zn之比加倍。可以看出,在200MHz之后,共振也被推回。
图4显示了三种组合物(Ni0.4347Zn0.3153Cu0.20Co0.11Fe1.96O4;Ni0.4231Zn0.3069Cu0.20Co0.13Fe1.96O4;和Ni0.4115Zn0.2985Cu0.20Co0.15Fe1.96O4),每个都有设定为1.38的Ni/Zn比率。这些组合物的钴含量分别设定为0.11、0.13和0.15。可以清楚地看到钴的效果,允许在较高的频率(对于钴含量为0.15的组合物高于300MHz)下使用材料。
图5和6专注于100到200MHz之间的频率范围。由于在该范围内运行的许多VHF应用,对该频段具有很大的兴趣,特别是用于航空应用(118到156MHz之间的使用带,更特别是在118到137MHz之间用于航空业务)。在这些特定的频带中,在图4和5中观察到,材料Ni0.440 5Zn0.3195Cu0.20Co0.10Fe1.96O4和Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4显示出具有磁损耗tan(δμ)<0.02和磁导率μ'≈15的有利性能。
图7和8显示了频率范围100-200MHz内的Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4和Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4的相对介电常数和介电损耗。它们显示出具有介电损耗tan(δε)<0.006和介电常数ε'≈13-14的有利性能。
这些结果以其一般性支持本发明的范围。特别地,实施例支持了根据本发明定义的Ni/Zn之比,且根据本发明定义的钴含量使得可以适应目标行为成为可能。从根据本发明的实施例的组合物之一开始并在一个方向上改变一个参数,且在相反方向上改变另一个,这在磁导率μ'、介电常数ε'和磁性-介电损耗tan(δμ)+tan(δε)方面实现了类似结果。因此,存在大量可能的组成变体,其具有与实施例中所示的类似性能。
Claims (15)
1.式NiaZnbCucCodFe2-δO4的组合物,其中:
2(a+b+c+d)+3(2-δ)=8
0.05<b<0.5,
0.10<c<0.25,
0.04<d<0.25,和
δ<0.05。
2.根据权利要求1所述的组合物,具有1至15的Ni/Zn之比。
3.根据权利要求1所述的组合物,其特征在于,所述组合物具有尖晶石结构。
4.根据权利要求1所述的组合物,其特征在于,所述组合物选自以下式的组合物:
Ni0.4805Zn0.3195Cu0.20Co0.06Fe1.96O4,
Ni0.4405Zn0.3195Cu0.20Co0.10Fe1.96O4,
Ni0.4347Zn0.3153Cu0.20Co0.11Fe1.96O4,
Ni0.4231Zn0.3069Cu0.20Co0.13Fe1.96O4,
Ni0.4115Zn0.2985Cu0.20Co0.15Fe1.96O4;和
Ni0.6Zn0.2Cu0.20Co0.06Fe1.96O4。
5.一种固体材料,其特征在于它具有如权利要求1所定义的组合物。
6.根据权利要求5所述的固体材料,其特征在于,它形成磁性-介电材料。
7.如权利要求5所述的固体材料,其特征在于,对于VHF范围(1MHz到300MHz),它具有10-20的磁导率μ',对于V/UHF范围(200MHz到600MHz)具有5-15的μ'。
8.根据权利要求5所述的固体材料,其特征在于它具有磁损耗tan(δμ)<0.06。
9.一种VHF或V/UHF天线,其特征在于它包含如下或由如下组成:根据权利要求1的组合物或根据权利要求5的固体材料。
10.印刷或微带型的VHF或V/UHF天线,其特征在于它包括粘附到辐射元件的一个或多个基板层,其中一个或多个基板层由如下组成或包含如下:根据权利要求1的组合物或根据权利要求5的固体材料。
11.根据权利要求9所述的VHF或V/UHF天线,其特征在于它具有小于300mm的较大尺寸。
12.根据权利要求1所述的组合物或根据权利要求5所述的固体材料用作VHF或V/UHF天线的用途。
13.制备根据权利要求1所述的组合物或根据权利要求5所述的固体材料的方法,其特征在于,所述方法包括:
研磨原料,该原料提供Ni,Zn,Cu,Co,Fe和O,通常为NiO;ZnO;CuO;Co3O4和Fe2O3,
研磨后,干燥该粉末,然后筛分,
筛分后,将粉末热处理,
热处理后,使粉末经历第二研磨,
然后将粉末成形为固体材料。
14.根据权利要求13所述的方法,其特征在于,在成形之前,该方法包括用粘合剂涂覆该粉末以提供成形材料。
15.根据权利要求13所述的方法,其特征在于,在成形之后,所述方法包括烧结成形的材料。
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FR2104412A FR3122422A1 (fr) | 2021-04-28 | 2021-04-28 | Ferrite de nickel zinc cuivre pour application antenne VUHF |
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US2995517A (en) * | 1956-02-16 | 1961-08-08 | Plessey Co Ltd | Ferrites containing niobium |
FR2747228B1 (fr) * | 1996-04-05 | 1998-07-17 | Thomson Csf | Ferrite a faibles pertes entre 1 mhz et 100 mhz et procede de realisation |
FR2795855B1 (fr) * | 1999-06-29 | 2001-10-05 | Thomson Csf | Ferrites a faibles pertes |
EP2982651B1 (en) * | 2014-08-05 | 2021-11-17 | Skyworks Solutions, Inc. | Rf device incorporating nickel zinc ferrite doped with cobalt |
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