CN113548888B - 一种频率温度系数改善的微波介质材料及其制备方法 - Google Patents
一种频率温度系数改善的微波介质材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种频率温度系数改善的微波介质陶瓷材料及其制备方法,属于微波介质材料技术领域。该微波介质陶瓷材料的组成表达式为:(1‑x)Mg2TiO4‑x[CaTiO3‑yMO],其中:0≤x≤0.3,0.1≤y≤0.2,MO为助剂。该材料制备时,首先合成CaTiO3‑yMO,使其频率温度系数相比于单相CaTiO3得到改善;然后再与Mg2TiO4进行两相复合。本发明微波介质陶瓷材料的介电常数为18.5~24,Q×f值为40000~70000GHz,频率温度系数|τf(‑40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
Description
技术领域
本发明涉及微波介质材料技术领域,具体涉及一种频率温度系数改善的微波介质材料及其制备方法。
背景技术
谐振频率温度系数τf是用来衡量材料元件谐振频率随温度漂移程度的参数,单位ppm/℃。谐振频率温度系数的正负值并不代表元件性能好坏,但是谐振频率温度系数接近零才是元件的稳定关键。τf=[f(T2)-f(T1)]/f(T0)/(T2-T1),其中,f(T2)为T2温度点的谐振峰频率,f(T1)为T1温度点的谐振峰频率,f(T0)为室温时的谐振峰频率。大多数情况下,大部分微波介质材料的谐振频率随温度呈线性变化,研究人员一般选取T1=-40℃、T2=80℃、T0=20℃作为测试温度点,即用τf(-40℃→80℃)来评价微波介质材料的谐振频率随温度的变化。
(1-x)Mg2TiO4-xCaTiO3系微波介质材料是应用最广的微波介质材料之一,但其谐振频率随温度变化却是呈抛物线状(非线性),τf(-40℃→80℃)并不能代表其真正的温漂特性,需要引入更多温度点变化下的频率温度系数τf来进行更全面的评价。对于谐振频率随温度呈抛物线变化的材料来说,|τf(T1℃→20℃)|+|τf(20℃→T2℃)|来评价其温漂特性更为合适。随着5G通讯技术的发展,特别是微波介质陶瓷在介质波导滤波器领域内的应用,高功率带来的放热问题,也使得元件需要适应更高使用环境温度的变化。传统的(1-x)Mg2TiO4-xCaTiO3系微波介质材料的频率温度系数(τf(-40℃→80℃)≤±10ppm/℃,|τf(-40℃→20℃)|+|τf(20℃→80℃)|≥15ppm/℃)已不能满足介质波导滤波器等新型射频元器件在-40℃~135℃温度区间内正负两端同时近零的设计要求。
发明内容
针对现有(1-x)Mg2TiO4-xCaTiO3系微波介质材料的频率温度系数|τf(T1℃→20℃)|+|τf(20℃→T2℃)|值过大的缺点,本发明提供一种频率温度系数改善的微波介质陶瓷材料,该材料频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
为实现上述目的,本发明所采用的技术方案如下:
一种频率温度系数改善的微波介质陶瓷材料,其特征在于:该微波介质陶瓷材料的组成表达式为:(1-x)Mg2TiO4-x[CaTiO3-yMO],其中:0≤x≤0.3,0.1≤y≤0.2,MO为助剂。
所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种。
该微波介质陶瓷材料的介电常数为18.5~24,Q×f值为40000~70000GHz,Q×f用于衡量微波介质陶瓷损耗的大小,其中Q=1/tanδ表示材料的品质因数,f代表谐振频率;频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
所述频率温度系数改善的微波介质陶瓷材料的制备方法为:首先合成CaTiO3-yMO,使其频率温度系数相比于单相CaTiO3的得到改善;然后再与Mg2TiO4进行两相复合。该方法具体包括如下步骤:
(1)配料:以氧化镁、二氧化钛、碳酸钙和MO助剂为原料,首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ,再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ;
(2)混合:将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理并干燥后,得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料;
(3)预烧:将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中,在碳棒炉中预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉;
(4)二次配料:将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合,得到二次原料粉;
(5)造浆:将二次原料粉球磨粉碎20~26小时,球磨介质为锆球与去离子水,得到粘稠状的浆料;
(6)成型:在步骤(5)所得浆料中添加占浆料5~20wt%的粘结剂,然后依次进行喷雾造粒和压制成型,最后在碳棒炉中烧结成型,即得到所述频率温度系数改善的微波介质陶瓷材料。
上述步骤(2)中,所述球磨过程中,球磨介质为锆球与去离子水;球磨后置于150℃烘箱中经12小时干燥处理。
上述步骤(3)中,在碳棒炉中预烧温度1000℃~1150℃,预烧时间2~4小时。
上述步骤(6)中,在碳棒炉中烧结温度1250℃~1350℃烧结时间3小时。
本发明的优点和有益效果如下:
1、本发明配方设计中CaTiO3-yMO进行了单独预合成,使得单相CaTiO3的频率温度系数得到改善后,再与Mg2TiO4进行两相复合。
2、本发明的频率温度系数改善的微波介质材料,其介电常数为18.5~24,品质因数Q×f值为40000~70000GHz,频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃,可广泛应用在基带天线、导航天线、介质波导滤波器等领域。
具体实施方式
为了使本发明的目的及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。
实施例1-4和对比例1:
本发明中微波介质陶瓷材料组成表达式为:(1-x)Mg2TiO4-x[CaTiO3-yMO],其中:0≤x≤0.3,0.1≤y≤0.2,MO为助剂。所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种。
实施例1-4及对比例1的具体组成见表1。对比例1中未加入助剂MO。
所述微波介质陶瓷材料的制备方法具体如下:
(1)配料:以氧化镁、二氧化钛、碳酸钙和MO助剂为原料,首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ,再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ;
(2)混合:将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理,球磨介质为锆球与去离子水;球磨后置于150℃烘箱中经12小时干燥处理,得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料;
(3)预烧:将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中,在碳棒炉中进行1100℃、3小时的预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉;
(4)二次配料:将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合,得到二次原料粉;
(5)造浆:将二次原料粉球磨粉碎20~26小时,球磨介质为锆球与去离子水,得到粘稠状的浆料;
(6)成型:在步骤(5)所得浆料中添加占浆料10wt%的聚乙烯醇粘结剂,然后依次进行喷雾造粒和压制成型,最后在碳棒炉中进行1300℃、3小时的烧结成型,即得到微波介质陶瓷材料。
表1~2示出了实施例1-4及对比例1各组成材料的微波介电性能。
表1(1-x)Mg2TiO4-x[CaTiO3-yMO]的微波介电性能
编号 | x | y | ε<sub>r</sub> | Q×f | |τ<sub>f(-40℃→20℃)</sub>|+|τ<sub>f(20℃→135℃)</sub>| |
对比例1 | 0.07 | 0 | 19.5 | 65000 | 16.7 |
实施例1 | 0.135 | 0.1 | 18.6 | 64129 | 9.7 |
实施例2 | 0.205 | 0.15 | 20.9 | 62005 | 9.9 |
实施例3 | 0.13 | 0.05 | 22.8 | 57473 | 9.8 |
实施例4 | 0.135 | 0.1 | 23.2 | 56540 | 9.9 |
表2(1-x)Mg2TiO4-x[CaTiO3-yMO]的各温度区间段的频率温度系数
编号 | τ<sub>f(-40℃→20℃)</sub> | τ<sub>f(-10℃→20℃)</sub> | τ<sub>f(20℃→80℃)</sub> | τ<sub>f(20℃→110℃)</sub> | τ<sub>f(20℃→135℃)</sub> |
对比例1 | 12.9 | 8.5 | 0.8 | -1.5 | -3.8 |
实施例1 | 4.8 | 1.9 | -3.3 | -4.1 | -4.9 |
实施例2 | 8.5 | 5.6 | 1.5 | 0.1 | -1.4 |
实施例3 | 3.1 | 0.0 | -3.7 | -5.5 | -6.7 |
实施例4 | 7.5 | 7.4 | 0.8 | -1.1 | -2.4 |
由表1~2可知,未经本发明改善的对比例1的|τf(-40℃→20℃)|+|τf(20℃→135℃)|值高达16.7,而引入适量MO后的实施例1-4的|τf(-40℃→20℃)|+|τf(20℃→135℃)|值都小于10。其中,频率温度系数最为优异的是实施例3,其介电常数为22.8,Q×f值为57473GHz,τf(-40℃→20℃)为3.1ppm/℃,τf(20℃→80℃)为-3.7ppm/℃,|τf(-40℃→20℃)|+|τf(20℃→135℃)|为9.8ppm/℃。为使本发明的(1-x)Mg2TiO4-x[CaTiO3-yMO]微波介质材料的各温度区间段的频率温度系数都尽可能的近零,达到|τf(-40℃→20℃)|+|τf(20℃→135℃)|值减小的目的,配方设计中的x值应随y值的变化而进行微调。因此,本发明设计的组分比例为0≤x≤0.3,0.1≤y≤0.2。
Claims (6)
1.一种频率温度系数改善的微波介质陶瓷材料,其特征在于:该微波介质陶瓷材料的组成表达式为:(1-x)Mg2TiO4-x[CaTiO3-yMO],其中:0.13≤x≤0.3,0.1≤y≤0.2,MO为助剂;所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种;
所述频率温度系数改善的微波介质陶瓷材料在制备时,首先合成CaTiO3-yMO,使其频率温度系数相比于单相CaTiO3的得到改善;然后再与Mg2TiO4进行两相复合。
2.根据权利要求1所述的频率温度系数改善的微波介质陶瓷材料,其特征在于:该微波介质陶瓷材料的介电常数为18.5~24,Q×f值为40000~70000GHz,Q×f用于衡量微波介质陶瓷损耗的大小,其中Q=1/tanδ表示材料的品质因数,f代表谐振频率;频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
3.根据权利要求1所述的频率温度系数改善的微波介质陶瓷材料的制备方法,其特征在于:该方法包括如下步骤:
(1)配料:以氧化镁、二氧化钛、碳酸钙和MO助剂为原料,首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ,再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ;
(2)混合:将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理并干燥后,得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料;
(3)预烧:将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中,在碳棒炉中预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉;
(4)二次配料:将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合,得到二次原料粉;
(5)造浆:将二次原料粉球磨粉碎20~26小时,球磨介质为锆球与去离子水,得到粘稠状的浆料;
(6)成型:在步骤(5)所得浆料中添加占浆料5~20wt%的粘结剂,然后依次进行喷雾造粒和压制成型,最后在碳棒炉中烧结成型,即得到所述频率温度系数改善的微波介质陶瓷材料。
4.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法,其特征在于:步骤(2)中,所述球磨过程中,球磨介质为锆球与去离子水;球磨后置于150℃烘箱中经12小时干燥处理。
5.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法,其特征在于:步骤(3)中,在碳棒炉中预烧温度1000℃~1150℃,预烧时间2~4小时。
6.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法,其特征在于:步骤(6)中,在碳棒炉中烧结温度1250℃~1350℃烧结时间3小时。
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