CN114031393A - 一种谐振频率温度系数近零的微波介电材料及其制备方法 - Google Patents
一种谐振频率温度系数近零的微波介电材料及其制备方法 Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910003080 TiO4 Inorganic materials 0.000 claims abstract description 40
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 27
- 239000011777 magnesium Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 238000004891 communication Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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Abstract
本发明公开了一种谐振频率温度系数近零的微波介电材料,由Mg2TiO4和Li2TiO3按照(1‑x)Li2TiO3‑xMg2TiO4质量比复合,最终形成Mg2TiO4、Li2MgTi3O8和Li2TiO3三相复合体系,其中,所述Mg2TiO4的质量百分数x为:0<x<100%;本发明通过将Mg2TiO4与Li2TiO3进行复合,一方面改善了Mg2TiO4较差的烧结性能,使其能够烧结成型;另一方面通过具有正τf值的Li2TiO3进行τf补偿,使整个体系具有近零的τf值,且Li2TiO3较低的烧结温度也能改善体系的烧结温度。
Description
技术领域
本发明涉及微波电子陶瓷材料技术领域,更具体的说是涉及一种谐振频率温度系数近零的微波介电材料及其制备方法。
背景技术
随着新一代无线通讯网络技术的革新,对微波元器件小型化和高稳定性提出了更高的要求,相比传统材料,中介电常数(10<εr<50)的微波介质陶瓷使用频率高,而且更容易满足微波元器件小型化的需求和低损耗的要求,因而成为微波通信的重要基础材料。
在中介电常数的微波陶瓷中,钛酸盐因其优越的性能而受到广泛关注。Mg2TiO4作为MgO-TiO2体系的一员,具有较好的介电性能:介电常数(εr)=14.51,品质因数(Q×f)=161570GHz,谐振频率温度系数(τf)=-49.3ppm/℃(H.Li,R.Xiang,X.Chen,H.Hua,S.Yu,B.Tang,G.Chen,S.Zhang,Intrinsic dielectric behavior of Mg2TiO4 spinel ceramic,Ceram.Int.46(2020)4235–4239.);而Li2TiO3作为具有正τf值的材料而常被作为τf补偿剂(εr=17.5,Q×f=51000GHz,τf=28.2ppm/℃)(J.Ma,Z.Fu,Y.Li,X.Li,Effects ofpreparation methods on synthesis,microstructures and microwave dielectricproperties ofLi2TiO3 ceramics,Ferroelectrics.504(2016)116–122.);因此,以Mg2TiO4为基体制作的微波介质陶瓷器件能降低微波器件的介电损耗。
然而,Mg2TiO4微波陶瓷较大的负的τf值和较差的烧结性能限制了它在微波通信系统中的广泛应用,因此,如何在保证εr和Q×f符合要求的同时,实现Mg2TiO4基微波陶瓷的近零τf值和提高其烧结性能是亟待解决的问题。Cheng等(L.Cheng,P.Liu,S.X.Qu,L.Cheng,H.Zhang,Microwave dielectric properties ofMg2TiO4 ceramics synthesized viahigh energyball milling method,J.Alloys Compd.623(2015)238–242.)通过高能球磨法获得了Mg2TiO4纳米粉末,且在1175℃下烧结获得了最佳介电性能:εr=13.9,Q×f=98600GHz,τf=-50.9ppm/℃,虽然纳米粉末降低了烧结温度,但τf值没有得到改善。Li等(H.Li,P.Zhang,S.Yu,H.Yang,B.Tang,F.Li,S.Zhang,Structural dependence ofmicrowave dielectric properties of spinel structured Mg2(Ti1-xSnx)O4 solidsolutions:Crystal structure refinement,Raman spectra study and complexchemical bond theory,Ceram.Int.45(2019)11639–11647.)用Sn4+取代Ti4+以期改善系统的介电性能,Mg2(Ti0.8Sn0.2)O4在1510℃下烧结获得了最佳介电性能(εr=12.18,Q×f=170130GHz,τf=-53.1ppm/℃),但τf值同样没有得到改善。此外,Bleous等(A.Belous,O.Ovchar,D.Durilin,M.M.Krzmanc,M.Valant,D.Suvorov,High-Q microwave dielectricmaterials based on the spinel Mg2TiO4,J.Am.Ceram.Soc.89(2006)3441–3445.)通过将Co2TiO4和CaTiO3分别与Mg2TiO4复合,获得了0.95Mg2TiO4-0.05Co2TiO4(εr=14,Q×f=86000GHz,τf=-54ppm/℃)、0.8Mg2TiO4-0.2Co2TiO4(εr=13,Q×f=75000GHz,τf=-60ppm/℃)和0.93Mg2TiO4-0.07CaTiO3(εr=15,Q×f=35000GHz,τf=-2ppm/℃)微波陶瓷,通过对比发现,CaTiO3比Co2TiO4对τf值的改善效果较好,但Q×f都被恶化,且εr没有明显变化。
因此,如何提供一种成本低廉、制备过程简单易操作且具有近零τf值的微波介电材料及其制备方法是本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明的目的在于提供一种谐振频率温度系数近零的微波介电材料。本发明通过将Mg2TiO4与Li2TiO3进行复合,一方面改善了Mg2TiO4较差的烧结性能,使其能够烧结成型;另一方面通过具有正τf值的Li2TiO3进行τf补偿,使整个体系具有近零的τf值,且Li2TiO3较低的烧结温度也能改善体系的烧结温度。
为了实现上述目的,本发明采用如下技术方案:
一种谐振频率温度系数近零的微波介电材料,由Mg2TiO4和Li2TiO3按照(1-x)Li2TiO3和xMg2TiO4质量比复合,最终形成Mg2TiO4、Li2MgTi3O8和Li2TiO3三相复合体系,其中,所述质量百分数x为:0≤x<100%。
本发明通过将Mg2TiO4与Li2TiO3进行复合,一方面改善了Mg2TiO4较差的烧结性能,使其能够烧结成型;另一方面通过具有正τf值的Li2TiO3进行τf补偿,使整个体系具有近零的τf值,且Li2TiO3较低的烧结温度也能改善系统的烧结温度;本发明展示的近零τf的微波介电材料:τf值可达-0.3ppm/℃,εr=15~19,Q×f=21920~30310GHz,近零的τf值能够提高制成的微波元器件的稳定性,可广泛应用于新一代无线移动通信及微波通信中。
优选地,所述质量百分数x为38%。
采用上述百分比所得微波介电材料的介电性能为:τf=-0.3ppm/℃、Q×f=29900GHz、εr=17。
优选地,所述微波介电材料通过固相反应法制备,该制备方法工艺路线简单成熟,易于大规模生产。
上述所述一种谐振频率温度系数近零的微波介电材料的制备方法,具体包括以下步骤:
(1)称取原材料MgO和TiO2进行球磨、烘干后,加热到800~1100℃保温2~6h,反应完成后冷却至室温即得Mg2TiO4预烧料;
(2)称取原材料Li2CO3和TiO2进行球磨、烘干后,加热至600~900℃保温2~6h,反应完成后冷却至室温即得Li2TiO3预烧料;
(3)将所述Mg2TiO4预烧料和所述Li2TiO3预烧料按比例混合后,依次进行球磨、烘干、造粒和压片,然后加热至400~600℃保温2~6h进行排胶处理,冷却至室温,得到生坯样品;
(4)将所述生胚样品加热至1250~1550℃保温2~6h后,冷却至室温即得一种谐振频率温度系数近零的微波介电材料。
优选地,步骤(1)-(3)所述球磨的磨球为化锆球,介质为去离子水。
优选地,所述粉料与去离子水的质量比按1:1.2~1.5。
优选地,步骤(1)-(3)所述球磨的转速为200-400rpm,球磨时间为2-8h。
优选地,步骤(1)和(2)中所述原材料的质量根据Mg2TiO4和Li2TiO3的质量进行称量。
优选地,步骤(1)-(4)中所述加热的升温速率为2~10℃/min。
优选地,步骤(3)中所述造粒的粘结剂为PVA溶液,PVA溶液的浓度为8~10%,添加量为5~20wt%。
优选地,步骤(3)中所述压片的压力为10~20MPa,压片压制成的圆柱样品尺寸为:直径12mm×厚度4~6mm。
经由上述的技术方案可知,与现有技术相比,本发明公开了一种谐振频率温度系数近零的微波介电材料及其制备方法,具有以下技术效果:
本发明通过将Mg2TiO4与Li2TiO3进行复合,一方面改善了Mg2TiO4较差的烧结性能,使其能够烧结成型;另一方面通过具有正τf值的Li2TiO3进行τf补偿,使整个系统具有近零的τf值,且Li2TiO3较低的烧结温度也能改善系统的烧结温度。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。
图1是实施例1制备微波介电材料在1400℃下烧结的XRD图;
图2是实施例2制备微波介电材料在1400℃下烧结的微波介电性能图;
图3是实施例2制备微波介电材料在1350℃下烧结的微波介电性能图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中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一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做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
一种谐振频率温度系数近零的微波介电材料的制备方法,具体包括以下步骤:
(1)按照摩尔比MgO:TiO2=1:1进行原料的称取,然后将配好的原料分别放置于装有锆球的球磨罐内,以去离子水作为球磨介质,粉料与去离子水质量比按1:1.2,球磨机转速设置为250rpm,球磨时间设置为4h,球磨结束后将料浆放置于100℃的恒温干燥箱内,烘干至恒重,得到MgO和TiO2均匀混合的烘干粉料;将MgO和TiO2均匀混合的烘干粉料在研钵中捣碎,放入坩埚中压实,先按照5℃/min的升温速率升至100℃,然后以10℃/min的升温速率升至1000℃,最后以5℃/min的升温速率升至1100℃并保温4h,再以5℃/min降至500℃后随炉冷却至室温,即得Mg2TiO4预烧料;
(2)按照摩尔比Li2CO3:TiO2=1:1进行原料的称取,然后将配好的原料分别放置于装有锆球的球磨罐内,以去离子水作为球磨介质,粉料与去离子水质量比按1:1.2,球磨机转速设置为250rpm,球磨时间设置为4h,球磨结束后将料浆放置于100℃的恒温干燥箱内,烘干至恒重,得到Li2CO3和TiO2均匀混合的烘干粉料;将Li2CO3和TiO2均匀混合的烘干粉料在研钵中捣碎,放入坩埚中压实,首先按照先按照5℃/min的升温速率升至100℃,然后以10℃/min的升温速率升至850℃并保温4h,再以5℃/min降至500℃后随炉冷却至室温,得到Li2TiO3预烧料;
(3)将38wt%Mg2TiO4预烧料和62wt%Li2TiO3预烧料均匀混合后,在装有锆球的球磨罐内,以去离子水作为球磨介质,粉料与去离子水质量比按1:1.2,球磨机转速设置为250rpm,球磨时间设置为4h,球磨结束后将料浆放置于100℃恒温干燥箱内,烘干至恒重。然后加入20wt%的PVA溶液作为粘结剂,进行造粒,并在20MPa下单轴干压成12mm(直径)×6mm(厚度)的圆柱,PVA溶液的浓度为8%;然后将圆柱放入高温烧结炉中,按5℃/min的升温速率升至100℃,再以10℃/min的升温速率升至600℃并保温4h,最后以5℃/min降至500℃后随炉冷却至室温,获得排胶后的生坯样品;
(4)将排胶后的生坯样品再次放入高温烧结炉中,按5℃/min的升温速率升至100℃,再以10℃/min的升温速率升至1000℃,然后以5℃/min升至1400℃进行烧结,并保温4h,保温结束后以5℃/min降至500℃再随炉冷却至室温,获得近零τf的复合钛酸盐微波介电材料;
同时,如图1,是本实施例微波介电材料在1400℃下烧结的XRD图,由图可知:实施例1所制备的样品含Mg2TiO4、Li2TiO3和Li2MgTi3O8三相。
实施例2
一种谐振频率温度系数近零的微波介电材料的制备方法,其与实施例1的区别点在于Li2TiO3预烧料的质量百分数为53-66(除62)%;
其中,如图2,为不同质量百分数Li2TiO3预烧料的物相组成及在1400℃下烧结微波介电性能图,从图中可以看出,x=53~66时,τf和εr随着Li2TiO3含量的增加而逐渐变大,τf=-17.4~8.6ppm/℃,Q×f=25270~29900GHz,εr=15.8~17.9,且当x=62时,τf=-0.3ppm/℃、Q×f=29900GHz、εr=17;
其中,如图3,为不同质量百分数Li2TiO3预烧料的物相组成及在1350℃下烧结微波介电性能图,从图中可以看出,x=53~66时,τf和εr随着Li2TiO3含量的增加而逐渐变大,τf=-21.7~17.7ppm/℃,Q×f=21920~26100GHz,εr=15.7~17.5,且当x=62时,τf=7.4ppm/℃、Q×f=25350GHz、εr=16.9。
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。对于实施例公开的装置而言,由于其与实施例公开的方法相对应,所以描述的比较简单,相关之处参见方法部分说明即可。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种谐振频率温度系数近零的微波介电材料,其特征在于,由Mg2TiO4和Li2TiO3按照(1-x)Li2TiO3-xMg2TiO4质量比复合,最终形成Mg2TiO4、Li2MgTi3O8和Li2TiO3三相复合体系,其中,所述质量百分数x为:0<x<100%。
2.根据权利要求1所述的一种谐振频率温度系数近零的微波介电材料,其特征在于,所述质量百分数x为38%。
3.根据权利要求1所述的一种谐振频率温度系数近零的微波介电材料,其特征在于,所述微波介电材料通过固相反应法制备。
4.一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,具体包括以下步骤:
(1)称取原材料MgO和TiO2进行球磨、烘干后,加热到800~1100℃保温2~6h,反应完成后冷却至室温即得Mg2TiO4预烧料;
(2)称取原材料Li2CO3和TiO2进行球磨、烘干后,加热至600~900℃保温2~6h,反应完成后冷却至室温即得Li2TiO3预烧料;
(3)将所述Mg2TiO4预烧料和所述Li2TiO3预烧料按比例混合后,依次进行球磨、烘干、造粒和压片,然后在400~600℃保温2~6h,冷却至室温,得到生坯样品;
(4)将所述生胚样品在1250~1550℃保温2~6h后,冷却至室温即得一种谐振频率温度系数近零的微波介电材料。
5.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,步骤(1)-(3)所述球磨的磨球为化锆球,介质为去离子水。
6.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,步骤(1)-(3)中所述球磨的转速为200-400rpm,球磨时间为2-8h。
7.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,步骤(1)和(2)中所述原材料根据Mg2TiO4和Li2TiO3的质量进行称量。
8.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料,其特征在于,步骤(1)-(4)中所述加热的升温速率为2~10℃/min。
9.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,步骤(3)中所述造粒的粘结剂为PVA溶液,PVA溶液的浓度为8~10%,添加量为5~20wt%。
10.根据权利要求4所述的一种谐振频率温度系数近零的微波介电材料的制备方法,其特征在于,步骤(3)中所述压片的压力为10~20MPa,压片压制成的圆柱样品尺寸为:直径12mm×厚度4~6mm。
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