CN108569903A - 一种低温烧结ltcc微波介质陶瓷及制备方法 - Google Patents

一种低温烧结ltcc微波介质陶瓷及制备方法 Download PDF

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CN108569903A
CN108569903A CN201810618048.7A CN201810618048A CN108569903A CN 108569903 A CN108569903 A CN 108569903A CN 201810618048 A CN201810618048 A CN 201810618048A CN 108569903 A CN108569903 A CN 108569903A
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张赟慧
吴海涛
杨长红
杨耀康
邢春芳
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Abstract

本发明公开了一种满足LTCC应用需求的微波介质陶瓷及制备方法，该陶瓷材料组成表达式为：La2Zr3‑3xTi3xMo9O36。其中0.02≤x≤0.1。本发明先将La2O3，ZrO2，TiO2和MoO3等原材料按照表达式进行配料，经球磨、干燥和过筛后于600℃的温度下进行预烧处理；再经二次球磨、干燥后添加10%重量百分比粘合剂进行炒蜡造粒，压制成型为直径为10mm的圆柱坯体，于700~750℃烧结温度下对陶瓷坯体进行烧结得到致密的陶瓷体。本发明微波介质陶瓷材料具有以下特点：较低的烧结温度（700~750℃），制备工艺较为简单，制备过程环保，成本较低，是一种很有发展前途的低介电微波介质材料。

Description

一种低温烧结LTCC微波介质陶瓷及制备方法
本发明属于微波通信领域核心元器件的技术领域，具体涉及一种满足LTCC应用需求的微波介质陶瓷及其制备方法。
微波介质陶瓷(MWDC)是指在微波频段电路中作为介质材料完成微波信号处理的一种陶瓷，是一种新型的电子功能陶瓷。随着微波通信事业的迅猛发展，移动通讯、汽车电话、电视卫星、军用雷达、全球定位系统等领域对高性能化的微波电路和微波器件的需求日益增加，信息容量呈指数性增长，应用频率朝着更高的频段发展，便携式终端和移动通信进一步向着小型化、高集成化和高可稳定性等方向发展。同时，介质谐振器、滤波器、电容器等器件在电磁波的接受与发送、能量与信号耦合及筛选频率方面有待进一步的提高，这就对微波电路中的元器件提出了更高要求，开发小型化、高稳定、廉价及高集成化的新型微波介质陶瓷已成为当今研究开发的焦点所在。微波介质陶瓷作为制造微波元器件的关键部分，应满足如下性能要求：（1）相对介电常数ε r 要尽量的高，这可以让器件更加小型化；（2）谐振频率温度系数τ f 要尽可能的接近0，这样才能使器件工作时有较好的稳定性；（3）品质因数Q·f值要高，这样才能有优良的选频特性。
近年来，一种新型的三角晶系的Ln2Zr3(MoO4)9（Ln=Sm, Nd, La）陶瓷由于具有良好的微波介电性能而逐渐进入研究人员视线；在2017年，Liu等人首次报道了应用传统固相法分别在875 ℃和850 ℃烧结的Sm2Zr3(MoO4)9和Nd2Zr3(MoO4)9陶瓷具有优异的微波介电性能，即ε r =11，Q·f=74,012 GHz，τ f =-45.3 ppm/℃和ε r =10.8，Q·f=58,942 GHz，τ f =-40.9ppm/℃；在2018年，Liu等人报道了通过传统的固相法制备的La2Zr3(MoO4)9陶瓷在775 ℃的烧结温度下具有ε r =10.8，Q·f=50,628 GHz和τ f =-38.8 ppm/℃的微波介电性能。基于上述研究可以发现Ln2Zr3(MoO4)9（Ln=Sm, Nd, La）陶瓷是比较有应用潜力的一种低温烧结的微波介质陶瓷体系。
本发明的目的是开发一种满足LTCC应用需求的微波介质陶瓷体系。该类陶瓷体系的组成表达式为：La2Zr3-3xTi3xMo9O36，其中0.02≤x≤0.1；在700~750 ℃的温度范围烧结的陶瓷介电常数ε r 为10.13~10.33，品质因数Q·f为77,351 GHz~80,713 GHz，谐振频率温度系数τ f 为-13.56 ppm/℃~-16.08 ppm/℃，能够满足实际生产环节对于微波介电性能的要求。
上述的一种满足LTCC应用需求的微波介质陶瓷及制备方法由下述步骤组成:
（1）混料：将纯度大于99.9%的La2O3、ZrO2、TiO2和MoO3原料粉末按照La2Zr3-3xTi3xMo9O36（0.02≤x≤0.1）的化学通式进行配料，将粉料、氧化锆磨球和无水乙醇加入混料瓶中，在混料机中混料24小时；将混料后的浆料置于设定温度为80 ℃的烘箱中进行烘干。
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料混合物装入氧化铝坩埚后置于马弗炉中，在600 ℃的温度下预烧2小时（升温降温速率为3℃/min），得到预烧粉体。
（3）二次混料：将步骤（2）预烧后的粉料、氧化锆磨球和无水乙醇加入混料瓶，在混料机中混料24小时；将第二次混料后的浆料再次置于设定温度为80 ℃的烘箱中进行烘干。
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末与质量分数为10 %的高纯石蜡进行加热混合，制成微米级的球形颗粒；将造粒后的粉体过60目筛网，并使用粉末压片机以200 MPa的压力将粉体压成直径为10 mm，高度为6 mm的圆柱形生坯。
（5）排胶：将生坯置于马弗炉中，在500 ℃下保温（排胶）4小时，设定工艺为“室温—180 min—200 ℃—180 min—350 ℃—120 min—500 ℃—240 min—500 ℃—100min—室温”，排出石蜡成分。
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于700~750 ℃保温4小时的条件下进行烧结（升温与降温速率均为5 ℃/min）。
本发明的有益效果是：本发明制备工艺过程化学计量比控制精确，工艺较简单，制备设备成本较低，重复性好，能满足未来元器件制备的各方面要求；所制备陶瓷合成物相稳定单一，无杂相干扰，烧结制备温度较低，节约生产能源并满足LTCC生产的要求。
附图说明
图1为本发明实施例1-4的X射线衍射分析图。
图2为本发明实施例1-4的扫描电子显微图。
图3为本发明实施例工艺参数及微波介电性能图表。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明。
实施例1
（1）混料：根据La2Zr3-3xTi3xMo9O36（x=0.02）微波介质陶瓷物相的化学计量比，使用精密天平称取纯度为99.99 %的氧化镧（La2O3）4.9169 g，纯度为99.99 %的氧化锆（ZrO2）5.4666g，纯度为99.9 %的氧化钛（TiO2）0.0724 g和纯度为99.9 %的氧化钼（MoO3）19.5660 g；将称量后的粉料倒入混料瓶中，并加入60 g无水乙醇和450 g氧化锆磨球。其中直径为1 cm与直径为0.5 cm磨球按质量比例为2:1装入；将粉料、磨球及无水乙醇的混料瓶放置于混料机上连续混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料置于马弗炉中于600 ℃下预烧2小时（升温降温速率为3 ℃/min），即可获得预烧后的La2Zr3-3xTi3xMo9O36（x=0.02）粉体。
（3）二次混料：将步骤（2）预烧后的粉料、450 g氧化锆磨球和60 g无水乙醇再次加入混料瓶，在混料机中混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末加入质量百分比为10 %的石蜡作为粘合剂进行加热混合；之后将造粒后粉末过80目标准筛网后，使用粉末压片机以200 MPa的压力压成直径为10 mm，高度为6 mm的圆柱形生坯。
（5）排胶：将生坯置于高温炉中，在500 ℃下排胶4小时，排出石蜡成分。
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于750 ℃保温4小时的条件下进行烧结。
（7）分析测试：通过网络分析仪测试获得在750 ℃烧结的La2Zr3-3xTi3xMo9O36（x=0.02）陶瓷具备ε r =10.13，Q·f=79,658 GHz和τ f =-13.56 ppm/℃的微波介电性能。
实施例2
（1）混料：根据La2Zr3-3xTi3xMo9O36（x=0.08）微波介质陶瓷物相的化学计量比，使用精密天平称取纯度为99.99 %的氧化镧（La2O3）4.9363 g，纯度为99.99 %的氧化锆（ZrO2）5.1521g，纯度为99.9 %的氧化钛（TiO2）0.2907 g和纯度为99.9 %的氧化钼（MoO3）19.6431 g；将称量后的粉料倒入混料瓶中，并加入60 g无水乙醇和450 g氧化锆磨球。其中直径为1 cm与直径为0.5 cm磨球按质量比例为2:1装入；将粉料、磨球及无水乙醇的混料瓶放置于混料机上连续混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料置于马弗炉中于600 ℃下预烧2小时（升温降温速率为3 ℃/min），即可获得预烧后的La2Zr3-3xTi3xMo9O36（x=0.08）粉体。
（3）二次混料：将步骤（2）预烧后的粉料、450 g氧化锆磨球和60 g无水乙醇再次加入混料瓶，在混料机中混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末加入质量百分比为10 %的石蜡作为粘合剂进行加热混合；之后将造粒后粉末过80目标准筛网后，使用粉末压片机以200 MPa的压力压成直径为10 mm，高度为6 mm的圆柱形生坯。
（5）排胶：将生坯置于高温炉中，在500 ℃下排胶4小时，排出石蜡成分。
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于750 ℃保温4小时的条件下进行烧结。
（7）分析测试：通过网络分析仪测试获得在750 ℃烧结的La2Zr3-3xTi3xMo9O36（x=0.08）陶瓷具备ε r =10.33，Q·f=80,713 GHz和τ f =-15.66 ppm/℃的微波介电性能。
实施例3
（1）混料：根据La2Zr3-3xTi3xMo9O36（x=0.08）微波介质陶瓷物相的化学计量比，使用精密天平称取纯度为99.99 %的氧化镧（La2O3）4.9363 g，纯度为99.99 %的氧化锆（ZrO2）5.1521g，纯度为99.9 %的氧化钛（TiO2）0.2907 g和纯度为99.9 %的氧化钼（MoO3）19.6431 g；将称量后的粉料倒入混料瓶中，并加入60 g无水乙醇和450 g氧化锆磨球。其中直径为1 cm与直径为0.5 cm磨球按质量比例为2:1装入；将粉料、磨球及无水乙醇的混料瓶放置于混料机上连续混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料置于马弗炉中于600 ℃下预烧2小时（升温降温速率为3 ℃/min），即可获得预烧后的La2Zr3-3xTi3xMo9O36（x=0.08）粉体。
（3）二次混料：将步骤（2）预烧后的粉料、450 g氧化锆磨球和60 g无水乙醇再次加入混料瓶，在混料机中混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末加入质量百分比为10 %的石蜡作为粘合剂进行加热混合；之后将造粒后粉末过80目标准筛网后，使用粉末压片机以200 MPa的压力压成直径为10 mm，高度为6 mm的圆柱形生坯。
（5）排胶：将生坯置于高温炉中，在500 ℃下排胶4小时，排出石蜡成分。
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于700 ℃保温4小时的条件下进行烧结。
（7）分析测试：通过网络分析仪测试获得在700 ℃烧结的La2Zr3-3xTi3xMo9O36（x=0.08）陶瓷具备ε r =10.25，Q·f=78,621 GHz和τ f =-16.08 ppm/℃的微波介电性能。
实施例4
（1）混料：根据La2Zr3-3xTi3xMo9O36（x=0.1）微波介质陶瓷物相的化学计量比，使用精密天平称取纯度为99.99 %的氧化镧（La2O3）4.9428 g，纯度为99.99 %的氧化锆（ZrO2）5.0467g，纯度为99.9 %的氧化钛（TiO2）0.3638 g和纯度为99.9 %的氧化钼（MoO3）19.6689 g；将称量后的粉料倒入混料瓶中，并加入60 g无水乙醇和450 g氧化锆磨球。其中直径为1 cm与直径为0.5 cm磨球按质量比例为2:1装入；将粉料、磨球及无水乙醇的混料瓶放置于混料机上连续混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料置于马弗炉中于600 ℃下预烧2小时（升温降温速率为3 ℃/min），即可获得预烧后的La2Zr3-3xTi3xMo9O36（x=0.1）粉体。
（3）二次混料：将步骤（2）预烧后的粉料、450 g氧化锆磨球和60 g无水乙醇再次加入混料瓶，在混料机中混料24小时，混料机转速为200 r/min；用粗孔筛将混料后的浆料和磨球分离，将分离后的浆料置于80 ℃下的烘箱中烘干。
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末加入质量百分比为10 %的石蜡作为粘合剂进行加热混合；之后将造粒后粉末过80目标准筛网后，使用粉末压片机以200 MPa的压力压成直径为10 mm，高度为6 mm的圆柱形生坯。
（5）排胶：将生坯置于高温炉中，在500 ℃下排胶4小时，排出石蜡成分。
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于750 ℃保温4小时的条件下进行烧结。
（7）分析测试：通过网络分析仪测试获得在750 ℃烧结的La2Zr3-3xTi3xMo9O36（x=0.1）陶瓷具备ε r =10.14，Q·f=77,351 GHz和τ f =-15.89 ppm/℃的微波介电性能。

Claims (6)

1.一种满足LTCC应用需求的微波介质陶瓷，其特征在于，该陶瓷材料的组成表达式为：La2Zr3-3xTi3xMo9O36，其中0.02≤x≤0.1；在700~750 ℃的温度范围烧结的陶瓷介电常数ε r 为10.13~10.33，品质因数Q·f为77,351 GHz~80,713 GHz，谐振频率温度系数τ f 为-13.56ppm/℃~-16.08 ppm/℃。
2.一种满足LTCC应用需求的微波介质陶瓷及制备方法，其特征在于，包括以下步骤：
（1）混料：将纯度大于99.9 %的原料粉末按照La2Zr3-3xTi3xMo9O36（0.02≤x≤0.1）的化学通式进行配料，将粉料、氧化锆磨球和无水乙醇加入混料瓶中，在混料机中混料24小时；将混料后的浆料置于设定温度为80 ℃的烘箱中进行烘干；
（2）预烧：将步骤（1）中烘干后的粉料在研钵中研磨后过60目的筛网；得到的粉料混合物装入氧化铝坩埚后置于马弗炉中，在600 ℃的温度下预烧2小时（升温降温速率为3 ℃/min），得到预烧粉体；
（3）二次混料：将步骤（2）预烧后的粉料、干净的氧化锆磨球和无水乙醇加入混料瓶，在混料机中混料24小时；将第二次混料后的浆料再次置于设定温度为80 ℃的烘箱中进行烘干；
（4）造粒、成型：将步骤（3）中烘干好的粉料在研钵中研磨后过60目的筛网，所得粉末与质量分数为10 %的高纯石蜡进行加热混合，制成微米级的球形颗粒；将造粒后粉体过60目筛网，并使用粉末压片机以200 MPa的压力将粉体压成圆柱形生坯；
（5）排胶：将生坯置于马弗炉中，在500 ℃下保温（排胶）4小时，按照设定程序排出石蜡成分；
（6）烧结：将排胶后的生坯至于高温烧结炉中，对坯体于700~750 ℃保温4小时的条件下进行烧结（升温与降温速率均为5 ℃/min）。
3.根据权利要求2所述的一种满足LTCC应用需求的微波介质陶瓷及制备方法，其特征在于，所述步骤（1），（3）的料、磨球和无水乙醇的质量比例为1:15:2；直径为1 cm与直径为0.5 cm磨球质量比例为2:1，混料机转速为200 r/min。
4.根据权利要求2所述的一种超低温烧结微波介质陶瓷的制备方法，其特征在于，所述步骤（1）的原料粉末分别为La2O3、ZrO2、TiO2和MoO3粉体。
5.根据权利要求2所述的一种超低温烧结微波介质陶瓷的制备方法，其特征在于，所述步骤（4）（5）（6）中圆柱形生坯的直径为10 mm，高度为6 mm。
6.根据权利要求2所述的一种超低温烧结微波介质陶瓷的制备方法，其特征在于，所述步骤（5）中设定程序为“室温—180 min—200 ℃—180 min—350 ℃—120 min—500 ℃—240 min—500 ℃—100 min—室温”。
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