CN116120050B - 一种超低温烧结的ltcc陶瓷材料及其制备方法 - Google Patents
一种超低温烧结的ltcc陶瓷材料及其制备方法 Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
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Abstract
一种超低温烧结的LTCC陶瓷材料及其制备方法，属于电子元器件领域。以Li2CO3、V2O5、(NH4)2HPO4和TiO2为原料，按照分子式Li3‑2x(V1‑ xTix)2(PO4)3配制称量；将配量好的原料以无水乙醇和氧化锆球为球磨介质，在高转速下球磨；将球磨混合后的浆料烘干；烘干后研磨成粉过筛网；然后加入聚乙烯醇水溶液(PVA)进行造粒；造粒粉经过筛网后压制成圆柱生坯；将圆柱生坯放入马弗炉内排胶和烧结得到所述超低温烧结LTCC陶瓷材料。解决了现有LTCC低温共烧陶瓷技术中存在材料性能差、工艺复杂、工艺质量一致性及可靠性差、不适于批量生产、生产成本高的问题。广泛应用于现代微波电子通讯领域。
Description
技术领域
本发明属于电子元器件领域，进一步来说涉及LTCC陶瓷材料领域，具体来说，涉及一种超低温烧结的LTCC陶瓷材料及其制备方法。
背景技术
近年来，随着电子信息产业的飞速发展，与之密切相关的电子元器件的高集成、高可靠性、小型化和低成本发展已成必然趋势。为满足电子元件“小、轻、快”的发展趋势，低温共烧陶瓷技术(LTCC)因其化学稳定性好、设计灵活、布线密度高、烧结温度低且可在空气中与Au、Ag等电极进行共烧等优点，在电子工业领域得到了迅猛发展。
随着移动通信技术的不断升级，以及各类移动通信设备的更新换代和普及，对陶瓷材料提出了更苛刻的要求，要求陶瓷材料不仅可以与Al(熔点660℃)电极共烧，甚至还可以与半导体或聚合物基基板等集成共烧。因此，降低陶瓷材料烧结温度成为一个急需解决的问题，目前国内外研究最多、最常用来实现低温烧结的方法是添加单一或多种复合低熔点氧化物、低熔点玻璃等烧结助剂或者是采用化学或物理方法制备粒度较细的粉体作为原始料来实现低温烧结；其中，添加单一或多种复合低熔点氧化物、低熔点玻璃等烧结助剂虽然可以明显的降低陶瓷材料的烧结温度，但是材料的性能均会被不同程度的恶化；此外，复合低熔点氧化物、低熔点玻璃等烧结助剂都需要单独制备，制备工艺不仅繁琐且易与陶瓷材料发生化学反应生成其他相，从而增加了整个陶瓷材料制备过程中的复杂性和不稳定性。采用化学合成的粉体或者采用物理方法(如：高能球磨法)制备较细的粉体或直接采用纳米级原始粉体虽然都能获得优异的性能和较低的烧结温度，但其复杂的制备工艺、较高的成本、差的重复性、差的可控性使得不宜大批量工业化生产。
对于传统的固相反应法而言，通常是将均匀混合的原料粉末进行预烧，二次球磨、压片再烧结成陶瓷材料。虽然预烧烧过程有利于晶粒生长和形成均匀稳定的主相，但工艺相对繁琐且预烧和二次球磨过程中会大大增加引入杂质的几率，从而恶化材料的性能。
因此，进一步开发具有固有烧结温度低、原料成本低且性能优异的LTCC陶瓷材料具有重要的意义和商业价值。
有鉴于此，特提出本发明。
发明内容
本发明所要解决的技术问题是：提供一种新颖具有超低温烧结、原料成本低且性能优异的LTCC陶瓷材料以及制备方法，解决现有技术存在工艺复杂、工艺质量一致性及可靠性差、不适于批量生产的问题。
本发明的发明构思是：由于反应烧结具有制备工艺简单、烧结陶瓷产品晶粒细小均匀、性能优异、工艺质量一致性好且具有大批量生产的优势。因此，本发明采用反应烧结法制备得到具有超低温烧结的Li3-2x (V1-x Ti x )2(PO4)3陶瓷材料，通过采用TiO2进行部分离子取代V2O5，来调节Li3-2x (V1-x Ti x )2(PO4)3陶瓷的介电常数以及谐振频率温度系数的范围，扩宽Li3-2x (V1-x Ti x )2(PO4)3陶瓷的使用范围。本发明首先以Li2CO3、V2O5、(NH4)2HPO4和TiO2为原料，按照Li3-2x (V1-x Ti x )2(PO4)3化学式的化学计量比（按总质量为500g计算）进行配制，将称量所需各原料进行球磨混合均匀，再经过烘干、造粒、压制成圆柱体生坯，最后经过排胶烧结过程得到所述的一种超低温烧结的LTCC陶瓷材料。
为此，本发明提供一种超低温烧结的LTCC陶瓷材料的制备方法，包括以下步骤：
（1）以Li2CO3、V2O5、(NH4)2HPO4和TiO2为原料，按照分子式Li3-2x (V1-x Ti x )2(PO4)3的化学计量比（按总质量为500g计算）配制称量，其中0.1≤x≤1；
（2）所述化学计量比按照摩尔比：m(Li2CO3)：m(V2O5)：m(TiO2)：m((NH4)2HPO4)=(3-2x)/2 mol：(1-x) mol：2xmol：3mol进行计算配置称量，总质量按总质量为500g计算，其中0.1≤x≤1；
（3）将配量好的原料以无水乙醇和氧化锆球为球磨介质，在转速为250r/min~350r/min的高转速下球磨12h~24h；
（4）将球磨混合后的浆料在80℃~120℃下烘干；
（5）烘干后研磨成粉过60目~90目筛网；
（6）然后加入聚乙烯缩丁醛水溶液(PVB)进行造粒；
（7）造粒粉经过80目~120目的筛网进行过筛在5MPa~10MPa压力下压制成圆柱生坯；
（8）将圆柱生坯放入马弗炉内，在大气气氛下以2℃/min ~8℃/min的升温速率在450℃~550℃进行保温4h~6h排胶；
（9）再以2℃/min ~8℃/min的升温速率在600℃~700℃下烧结1h~4h得到所述超低温烧结LTCC陶瓷材料。
所述Li2CO3、V2O5、(NH4)2HPO4和TiO2为纯度≥99.9％。
所述一种超低温烧结的低介低损耗LTCC陶瓷材料，具有如下特点：
1)烧结温度低，且可调。典型烧结温度范围：600℃~700℃；
2)温度稳定性高，且可调。典型谐振频率温度系数范围：-50.09 ppm/℃~+25.4ppm/℃；
3)介电常数低，且可调。典型介电常数范围：5.5~10.2；
4)品质因数高，且可调。典型品质因数范围：50730 GHz ~88501 GHz。
该陶瓷材料能适用于LTCC技术的需要。同时，其较低的烧结温度(600℃~700℃)使得在工业生产中极大的降低了能耗。
可广泛应用于移动通讯、电子对抗、卫星通讯、北斗系统(GPS)、蓝牙技术、无线局域网(MLAN)和物联网等现代微波电子通讯领域。
附图说明
图1为超低温烧结LTCC陶瓷材料制备流程示意图。
实施方式
如图1所示，以Li3-2x (V1-x Ti x )2(PO4)3（0.1≤x≤1）系超低温烧结LTCC陶瓷材料为例，所述一种超低温烧结的LTCC陶瓷材料及其制备方法的具体实施方式如下：
本发明所述的一种超低温烧结的LTCC陶瓷材料的组成表达式为Li3-2x (V1-x Ti x )2(PO4)3，其中0.1≤x≤1，具体实施例的制备方法及性能如下：
具体实施的制备方法：
1、混料：
（1）以纯度≥99.9％的Li2CO3、V2O5、(NH4)2HPO4和TiO2为原料，按照分子式Li3-2x (V1-x Ti x )2(PO4)3的化学计量比配制称量，所述化学计量比按照摩尔比：m(Li2CO3)：m(V2O5)：m(TiO2)：m((NH4)2HPO4)=(3-2x)/2 mol：(1-x) mol：2xmol：3mol进行计算配置称量，总质量按总质量为500g计算，其中0.1≤x≤1。再将称量好的原料以无水乙醇和氧化锆球为球磨介质，在转速为250r/min~350r/min的高转速下球磨12h~24h；
2、造粒、成型：
将球磨混合后的浆料在80~100℃下烘干，烘干后研磨成粉过80目筛网；然后加入聚乙烯醇水溶液(PVA)进行造粒，造粒粉经过80目的筛网进行过筛在5~10MPa压力下压制成直径为15mm，高7~8mm的圆柱生坯；
3、排胶、烧结：
将步骤2得到的圆柱生坯放入马弗炉内，在大气气氛下以3℃/min的升温速率在500℃保温4h~6h排胶，再以5℃/min的升温速率在600℃~700℃烧结2h得到所述超低温烧结LTCC陶瓷材料；
4、性能测试：
将步骤3烧结得到的圆柱体陶瓷样品两面进行抛光，通过Hakki-Coleman介质谐振器法采用矢量网络分析仪测试样品的介电常数和品质因数(其中，测试温度为室温，测试频率为1~20G)；采用高低温试验箱测试样品在25 °C～85 °C下的中心谐振频率，利用以下公式计算谐振频率温度系数：
式中：分别表示85 °C和25 °C时的谐振频率。
所述LTCC陶瓷材料的微波介电性能如下表：
| 序号 | Li3-2x (V1-x Ti x )2(PO4)3 | 烧结温度(°C) | 介电常数 | Qxf(GHz) | Τ f (ppm/°C) |
| 1 | x=0.1 | 600 | 5.5 | 66507 | -50.09 |
| 2 | x=0.1 | 650 | 6.1 | 72589 | -48.75 |
| 3 | x=0.1 | 700 | 6.5 | 78965 | -47.56 |
| 4 | x=0.2 | 600 | 6.0 | 64258 | -40.55 |
| 5 | x=0.2 | 650 | 6.5 | 78624 | -40.58 |
| 6 | x=0.2 | 700 | 6.6 | 88501 | -4186 |
| 7 | x=0.3 | 600 | 6.2 | 63258 | -32.44 |
| 8 | x=0.3 | 650 | 6.5 | 76580 | -30.55 |
| 9 | x=0.3 | 700 | 7.1 | 83251 | -31.66 |
| 10 | x=0.4 | 600 | 6.8 | 62885 | -23.44 |
| 11 | x=0.4 | 650 | 7.3 | 76552 | -22.55 |
| 12 | x=0.4 | 700 | 7.8 | 82553 | -23.55 |
| 13 | x=0.5 | 600 | 7.2 | 62552 | -16.55 |
| 14 | x=0.5 | 650 | 7.6 | 81582 | -15.22 |
| 15 | x=0.5 | 700 | 8.6 | 77595 | -14.55 |
| 16 | x=0.6 | 600 | 7.5 | 61334 | -10.58 |
| 17 | x=0.6 | 650 | 8.2 | 80991 | -10.25 |
| 18 | x=0.6 | 700 | 9.0 | 76358 | -10.22 |
| 19 | x=0.7 | 600 | 8.3 | 60332 | -2.22 |
| 20 | x=0.7 | 650 | 8.9 | 79552 | -2.28 |
| 21 | x=0.7 | 700 | 9.2 | 75223 | -2.65 |
| 22 | x=0.8 | 600 | 8.5 | 59631 | 3.23 |
| 23 | x=0.8 | 650 | 9.2 | 76548 | 3.18 |
| 24 | x=0.8 | 700 | 9.5 | 74589 | 3.19 |
| 25 | x=0.9 | 600 | 8.8 | 55962 | 10.55 |
| 26 | x=0.9 | 650 | 9.6 | 76002 | 11.25 |
| 27 | x=0.9 | 700 | 9.9 | 73255 | 13.44 |
| 28 | x=1 | 600 | 9.2 | 50730 | 25.44 |
| 29 | x=1 | 650 | 9.8 | 75325 | 23.22 |
| 30 | x=1 | 700 | 10.2 | 70325 | 24.33 |
最后应说明的是：上述实施例仅仅是为清楚地说明所作的举例，本发明包括但不限于以上实施例，这里无需也无法对所有的实施方式予以穷举。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。凡符合本发明要求的实施方案均属于本发明的保护范围。
Claims (8)
1.一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于，所述LTCC陶瓷材料的化学组成式为Li3-2x (V1-x Ti x )2(PO4)3，其中0.6≤x≤0.9，材料组分包括Li2CO3、V2O5、(NH4)2HPO4、TiO2；
所述LTCC陶瓷材料的制备方法，包括以下步骤：
（1）以Li2CO3、V2O5、(NH4)2HPO4和TiO2为原料，按照材料的化学组成式Li3-2x (V1-x Ti x )2(PO4)3的化学计量比进行配制称量；
（2）所述化学计量比按照摩尔比：m(Li2CO3)：m(V2O5)：m(TiO2)：m((NH4)2HPO4)=(3-2x)/2mol：(1-x) mol：2xmol：3mol进行计算配置称量，总质量按500g计算，所述x 为0.6≤x≤0.9；
（3）将配量好的原料以无水乙醇和氧化锆球为球磨介质，在转速为250r/min~350r/min的高转速下球磨8~24h；
（4）将球磨混合后的浆料在80℃~120℃下烘干；
（5）烘干后研磨成粉过70目~90目筛网；
（6）然后加入聚乙烯醇水溶液进行造粒；
（7）造粒粉经过80目~120目的筛网进行过筛在5MPa~10MPa压力下压制成圆柱生坯；
（8）将圆柱生坯放入马弗炉内，在大气气氛下以2℃/min ~8℃/min的升温速率在450℃~550℃进行保温4h~6h排胶；
（9）再以2℃/min ~8℃/min的升温速率在600℃~700℃下烧结1h~4h得到所述超低温烧结LTCC陶瓷材料；
所述LTCC陶瓷材料的谐振频率温度系数范围为-10.58 ppm/℃~+13.44ppm/℃，介电常数范围为5.5~10.2，品质因数范围为50730 GHz ~88501 GHz。
2.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料，其特征在于：所述Li2CO3、V2O5、(NH4)2HPO4和TiO2纯度≥99.9％。
3.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述圆柱生坯的直径为15mm，高为7~8mm。
4.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述球磨时间为12h~24h。
5.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述烘干温度为80℃~100℃。
6.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述筛网目数为80目。
7.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述排胶升温速率为3℃/min，排胶保温温度为500℃。
8.如权利要求1所述的一种超低温烧结的LTCC陶瓷材料的制备方法，其特征在于：所述烧结的升温速率为5℃/min，烧结的时间为2h。
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