CN114671685A - Ultralow temperature sintered microwave dielectric material Ca2V2O7-LiF and method for the production thereof - Google Patents
Ultralow temperature sintered microwave dielectric material Ca2V2O7-LiF and method for the production thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 title description 7
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000004677 Nylon Substances 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920001778 nylon Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000012776 electronic material Substances 0.000 abstract description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910014472 Ca—O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于电子材料及其制造领域，具体提供一种超低温烧结微波介质材料Ca2V2O7‑LiF及其制备方法，用以解决现有微波介质材料R2V2O7(R＝Ba,Sr,and Ca)烧结温度较高且微波介电性能平庸的问题。相比于纯相Ca2V2O7，本发明超低温微波介质材料Ca2V2O7‑LiF能够大大降低烧结温度、实现525～575℃下的超低温烧结，同时，显著提升材料的微波介电性能：Q×f值为31000～46000GHz、介电常数为11‑12、谐振频率温度系数为‑126～‑115ppm/℃，尤其Ca2V2O7‑3wt％LiF在550℃下烧结得到优异的微波介电性能：Q×f＝46476GHz、εr＝11.83、τf＝‑116.43ppm/℃，本质区别于普遍助烧剂降低烧结温度的同时牺牲材料的性能；并且，制备工艺简单、便于大规模批量化生产；在超低温共烧陶瓷领域具有广阔的应用前景。
The invention belongs to the field of electronic materials and manufacturing thereof, and specifically provides an ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF and a preparation method thereof, which are used to solve the problem of the existing microwave dielectric materials R 2 V 2 O 7 (R=Ba , Sr, and Ca) with high sintering temperature and mediocre microwave dielectric properties. Compared with pure phase Ca 2 V 2 O 7 , the ultra-low temperature microwave dielectric material Ca 2 V 2 O 7 -LiF of the present invention can greatly reduce the sintering temperature, realize ultra-low temperature sintering at 525-575 ° C, and at the same time, significantly improve the microwave dielectric of the material. Electrical properties: Q×f value is 31000～46000GHz, dielectric constant is 11‑12, resonant frequency temperature coefficient is ‑126～‑115ppm/℃, especially Ca 2 V 2 O 7 -3wt% LiF is obtained by sintering at 550℃ Excellent microwave dielectric properties: Q×f=46476GHz, ε r =11.83, τ f =‑116.43ppm/℃, which is essentially different from common sintering aids while sacrificing the performance of the material while reducing the sintering temperature; in addition, the preparation process is simple, It is convenient for large-scale batch production; it has broad application prospects in the field of ultra-low temperature co-fired ceramics.
Description
技术领域technical field
本发明属于电子材料及其制造领域，具体提供一种超低温烧结微波介质材料Ca2V2O7-LiF及其制备方法。The invention belongs to the field of electronic materials and their manufacture, and specifically provides an ultra-low temperature sintering microwave dielectric material Ca 2 V 2 O 7 -LiF and a preparation method thereof.
背景技术Background technique
超低温烧结微波介质材料是目前微波元器件的研究热点，更低的烧结温度一方面可以与更廉价的金属实现共烧，另一方面也可以大大减小能源的消耗；但是，目前多数微波介质材料的烧结温度普遍偏高，如何实现超低温烧结同时使材料具有好的微波介电性能成为研究难点。在众多微波陶瓷材料体系中，钒酸盐固有烧结温度普遍较低、微波性能优良，具有极好的应用前景，是当前超低温烧结领域的热点材料；2009年，Joung MR等人在文献“Formation Process and Microwave Dielectric Properties of the R2V2O7(R＝Ba,Sr,and Ca)Ceramics.J Am Ceram Soc 92:3092–3094.”中公开Ca2V2O7可于950℃下烧结，仅仅具有平庸的微波介电性能：εr＝12.11、Q×f＝15203GHz、τf＝-30.87ppm/℃；显然，较高的烧结温度(950℃)和平庸的微波介电性能成为了限制其应用于微波元器件的瓶颈。Ultra-low temperature sintering microwave dielectric materials is the current research hotspot of microwave components. On the one hand, lower sintering temperature can achieve co-firing with cheaper metals, and on the other hand, it can also greatly reduce energy consumption; however, most microwave dielectric materials currently The sintering temperature is generally high, and how to achieve ultra-low temperature sintering and at the same time make the material have good microwave dielectric properties has become a research difficulty. Among many microwave ceramic material systems, vanadate has generally low inherent sintering temperature and excellent microwave performance, and has excellent application prospects. It is currently a hot material in the field of ultra-low temperature sintering; in 2009, Joung MR et al. and Microwave Dielectric Properties of the R 2 V 2 O 7 (R=Ba, Sr, and Ca) Ceramics. J Am Ceram Soc 92:3092-3094.” discloses that Ca 2 V 2 O 7 can be sintered at 950°C, Only have mediocre microwave dielectric properties: ε r =12.11, Q×f=15203GHz, τ f =-30.87ppm/°C; obviously, the higher sintering temperature (950°C) and the mediocre microwave dielectric properties become limitations It is applied to the bottleneck of microwave components.
基于以上原因，本发明提供一种超低温烧结微波介质材料Ca2V2O7-LiF及其制备方法。Based on the above reasons, the present invention provides an ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF and a preparation method thereof.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于针对现有微波介质材料R2V2O7(R＝Ba,Sr,and Ca)烧结温度较高且微波介电性能平庸的问题，提供一种超低温烧结微波介质材料Ca2V2O7-LiF及其制备方法；本发明采用LiF作为助烧剂，用于实现微波介质材料于525～575℃下的超低温烧结，同时显著提升微波介质材料的微波介电性能，尤其Ca2V2O7-3wt％LiF在550℃下烧结得到优异的微波介电性能：Q×f＝46476GHz、εr＝11.83、τf＝-116.43ppm/℃。The purpose of the present invention is to provide an ultra-low temperature sintered microwave dielectric material Ca 2 for the problems of high sintering temperature and mediocre microwave dielectric properties of the existing microwave dielectric material R 2 V 2 O 7 (R=Ba, Sr, and Ca) V 2 O 7 -LiF and preparation method thereof; LiF is used as a sintering aid in the present invention to realize ultra-low temperature sintering of microwave dielectric materials at 525-575° C., and at the same time significantly improve the microwave dielectric properties of microwave dielectric materials, especially Ca 2 V 2 O 7 -3wt% LiF was sintered at 550°C to obtain excellent microwave dielectric properties: Q×f=46476GHz, ε r =11.83, τ f =-116.43ppm/°C.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical scheme adopted in the present invention is:
一种超低温烧结微波介质材料Ca2V2O7-LiF，其特征在于，所述超低温烧结微波介质材料由Ca2V2O7与LiF组成，其中，LiF相比于Ca2V2O7的质量百分比为：1～7wt％。An ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF, characterized in that the ultra-low temperature sintered microwave dielectric material is composed of Ca 2 V 2 O 7 and LiF, wherein LiF is compared with Ca 2 V 2 O 7 The mass percentage is: 1～7wt%.
进一步的，所述超低温烧结微波介质材料的主晶相为Ca2V2O7，属于三斜晶系。Further, the main crystal phase of the ultra-low temperature sintered microwave dielectric material is Ca 2 V 2 O 7 , which belongs to the triclinic system.
上述超低温烧结微波介质材料Ca2V2O7-LiF的制备方法，包括以下步骤：The preparation method of the above ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF includes the following steps:
步骤1：将V2O5、CaCO3粉体根据化学式Ca2V2O7进行配料；Step 1: prepare the V 2 O 5 and CaCO 3 powders according to the chemical formula Ca 2 V 2 O 7 ;
步骤2：将原料:去离子水:锆球按照1:2:5的质量比混合，并置于尼龙罐中球磨7～10小时，再将料浆于80～100℃烘干；Step 2: mix raw materials: deionized water: zirconium balls in a mass ratio of 1:2:5, place them in a nylon tank for ball milling for 7-10 hours, and then dry the slurry at 80-100 °C;
步骤3：将干燥粉体过筛，并于650～750℃下预烧3～5小时，得到主晶相为Ca2V2O7的预烧料；Step 3: sieve the dry powder, and pre-sinter at 650-750° C. for 3-5 hours to obtain a pre-sintered material whose main crystal phase is Ca 2 V 2 O 7 ;
步骤4：按照质量百分比1～7wt％将预烧料与LiF混合；Step 4: mix the pre-sintered material with LiF according to the mass percentage of 1-7wt%;
步骤5：按照预烧料:去离子水:锆球按照1:2:5的质量比混合，并置于尼龙罐中球磨7～10小时，再将料浆于80～100℃烘干；Step 5: Mix the pre-sintered material: deionized water: zirconium balls in a mass ratio of 1:2:5, and place them in a nylon tank for ball milling for 7-10 hours, and then dry the slurry at 80-100 °C;
步骤6：将干燥粉体用聚乙烯醇造粒，并于10～20MPa下压制成生坯；Step 6: granulate the dry powder with polyvinyl alcohol, and press it into a green body at 10-20 MPa;
步骤7：将生坯在烧结炉中于525～575℃烧结3～5小时，得到所述超低温烧结微波介质材料。Step 7: sintering the green body in a sintering furnace at 525-575° C. for 3-5 hours to obtain the ultra-low temperature sintered microwave dielectric material.
本发明的有益效果在于：The beneficial effects of the present invention are:
1.本发明提供一种超低温微波介质材料Ca2V2O7-LiF，采用LiF作为助烧剂，LiF同时具有促进烧结和提升致密度的作用；一方面LiF在烧结过程中形成液相填充于晶粒间隙，促进烧结过程中的物质运输，F-会替换钒氧多面体和钙氧多面体中的桥接氧，相比V-O和Ca-O，更弱的F-Ca和F-V键形成的晶格骨架更易断裂，从而形成了更低的玻璃化转变温度和熔点；另一方面，填充于晶粒间隙的液相有助于提升材料的致密度，进而有助于获得更高的微波介电性能；1. The present invention provides an ultra-low temperature microwave dielectric material Ca 2 V 2 O 7 -LiF, which uses LiF as a sintering aid, and LiF has the functions of promoting sintering and increasing density at the same time; on the one hand, LiF forms a liquid phase filling during the sintering process. Due to the intergranular space, which promotes material transport during sintering, F- will replace bridging oxygen in vanadium - oxygen polyhedra and calcium-oxygen polyhedra, and the lattice formed by weaker F-Ca and FV bonds than VO and Ca-O The skeleton is more easily broken, resulting in a lower glass transition temperature and melting point; on the other hand, the liquid phase filled in the grain gap helps to increase the density of the material, which in turn helps to achieve higher microwave dielectric properties ;
基于此，相比于纯相Ca2V2O7，本发明超低温微波介质材料Ca2V2O7-LiF能够大大降低烧结温度、实现525～575℃下的超低温烧结，同时，显著提升材料的微波介电性能：Q×f值为31000～46000GHz、介电常数为11-12、谐振频率温度系数为-126～-115ppm/℃，尤其Ca2V2O7-3wt％LiF在550℃下烧结得到优异的微波介电性能：Q×f＝46476GHz、εr＝11.83、τf＝-116.43ppm/℃，本质区别于普遍助烧剂降低烧结温度的同时牺牲材料的性能；Based on this, compared with pure phase Ca 2 V 2 O 7 , the ultra-low temperature microwave dielectric material Ca 2 V 2 O 7 -LiF of the present invention can greatly reduce the sintering temperature, realize ultra-low temperature sintering at 525-575 ° C, and at the same time, significantly improve the material Microwave dielectric properties: Q×f value is 31000～46000GHz, dielectric constant is 11-12, resonant frequency temperature coefficient is -126～-115ppm/℃, especially Ca 2 V 2 O 7 -3wt% LiF at 550℃ The excellent microwave dielectric properties are obtained by sintering under low temperature: Q×f=46476GHz, ε r =11.83, τ f =-116.43ppm/℃, which is essentially different from the general sintering aids that reduce the sintering temperature while sacrificing the performance of the material;
2.本发明提供上述超低温微波介质材料Ca2V2O7-LiF的制备方法，采用传统固相反应法，工艺简单、便于大规模批量化生产；2. The present invention provides a preparation method of the above-mentioned ultra-low temperature microwave dielectric material Ca 2 V 2 O 7 -LiF, which adopts a traditional solid-phase reaction method, and the process is simple and convenient for large-scale batch production;
综上所述，本发明提供的超低温烧结微波介质材料Ca2V2O7-LiF能够同时实现烧结温度的大幅度降低和微波介电性能的大幅度提升，Ca2V2O7-LiF优异的微波介电性能可满足于微波谐振器、滤波器等无源器件的要求，同时超低温烧结具有节省能源的显著优势，在超低温共烧陶瓷领域具有广阔的应用前景。To sum up, the ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF provided by the present invention can simultaneously achieve a large reduction in the sintering temperature and a large improvement in the microwave dielectric properties, and the Ca 2 V 2 O 7 -LiF is excellent in The microwave dielectric properties can meet the requirements of passive devices such as microwave resonators and filters. At the same time, ultra-low temperature sintering has the significant advantage of saving energy, and has broad application prospects in the field of ultra-low temperature co-fired ceramics.
附图说明Description of drawings
图1为实施例2中制备得超低温烧结微波介质材料的XRD图。FIG. 1 is the XRD pattern of the ultra-low temperature sintered microwave dielectric material prepared in Example 2. FIG.
图2为实施例2中制备得超低温烧结微波介质材料的SEM图。FIG. 2 is a SEM image of the ultra-low temperature sintered microwave dielectric material prepared in Example 2. FIG.
具体实施方式Detailed ways
下面结合附图和实施例对本发明做进一步详细说明。The present invention will be described in further detail below with reference to the accompanying drawings and embodiments.
本发明具体提供4个实施例，每个实施例中超低温烧结微波介质材料均由Ca2V2O7与LiF组成；实施例1～实施例4中，LiF相比于Ca2V2O7的质量百分比依次为：1wt％、3wt％、5wt％、7wt％；每个实施例中超低温烧结微波介质材料均采用以下步骤制备：The present invention specifically provides 4 examples. In each example, the ultra-low temperature sintered microwave dielectric material is composed of Ca 2 V 2 O 7 and LiF; in Examples 1 to 4, LiF is compared with Ca 2 V 2 O 7 The mass percentages are: 1wt%, 3wt%, 5wt%, 7wt%; the ultra-low temperature sintered microwave dielectric materials in each example are prepared by the following steps:
步骤1：将分析纯V2O5、CaCO3粉体根据化学式Ca2V2O7中V与Ca的摩尔比配料；Step 1: prepare the analytically pure V 2 O 5 and CaCO 3 powders according to the molar ratio of V and Ca in the chemical formula Ca 2 V 2 O 7 ;
步骤2：将原料:去离子水:锆球按照1:2:5的质量比混合，并置于尼龙罐中球磨7～10小时，球磨转速为280r/min，再将料浆于80～100℃烘干；Step 2: Mix the raw materials: deionized water: zirconium balls in a mass ratio of 1:2:5, and place them in a nylon tank for ball milling for 7 to 10 hours. ℃ drying;
步骤3：将干燥粉体通过80目的筛网，然后在650～750℃预烧3～5小时，获得主晶相为Ca2V2O7的预烧料；Step 3: passing the dry powder through an 80-mesh sieve, and then calcining at 650-750° C. for 3-5 hours to obtain a calcined material whose main crystal phase is Ca 2 V 2 O 7 ;
步骤4：根据质量百分比将预烧料与分析纯LiF混合；Step 4: Mix the pre-sintered material with analytically pure LiF according to the mass percentage;
步骤5：按照预烧料:锆球:去离子水为1:5:2的质量比混合，并置于尼龙罐中球磨7～10小时，在将料浆于80～100℃烘干；Step 5: mix according to the mass ratio of pre-sintered material: zirconium ball: deionized water is 1:5:2, and place it in a nylon tank for ball milling for 7-10 hours, and then dry the slurry at 80-100 °C;
步骤6：将干燥粉体用聚乙烯醇稀释液造粒，并于10～20MPa下压制成生坯；Step 6: granulate the dry powder with a polyvinyl alcohol diluent, and press it into a green body at 10-20 MPa;
步骤7：将生坯在烧结炉中于525～575℃烧结3～5小时，得到所述超低温微波介质材料。Step 7: sintering the green body in a sintering furnace at 525-575° C. for 3-5 hours to obtain the ultra-low temperature microwave dielectric material.
对每个实施例中制备得到的超低温烧结微波介质材料Ca2V2O7-LiF进行测试，其微波介电性能如下表所示：The ultra-low temperature sintered microwave dielectric material Ca 2 V 2 O 7 -LiF prepared in each example is tested, and its microwave dielectric properties are shown in the following table:
由上可见，上述4个实施例均实现了超低温烧结，且具有相对于纯相Ca2V2O7更优异的微波介电性能；其中，实施例2制备得超低温烧结微波介质材料Ca2V2O7-LiF的XRD图谱与SEM图像分别如图1与图2所示；由图1可见，实施例2制备得到的超低温烧结微波介质材料的晶体结构与三斜晶系的Ca2V2O7一致，LiF的加入并未导致原有晶体结构的改变；由图2可见，SEM图像中存在大量的液相(不规则相)，Ca2V2O7晶粒基本被液相包裹，同时液相也填充了晶粒的间隙，从而提升了材料的致密度，进而显著提升材料的微波介电性能。It can be seen from the above that the above-mentioned 4 examples have achieved ultra-low temperature sintering, and have better microwave dielectric properties than pure phase Ca 2 V 2 O 7 ; among them, the ultra-low temperature sintering microwave dielectric material Ca 2 V prepared in Example 2 The XRD pattern and SEM image of 2 O 7 -LiF are shown in Figure 1 and Figure 2, respectively; as can be seen from Figure 1, the crystal structure of the ultra-low temperature sintered microwave dielectric material prepared in Example 2 and the triclinic Ca 2 V 2 The addition of LiF did not change the original crystal structure; it can be seen from Figure 2 that there are a large number of liquid phases (irregular phases) in the SEM image, and the Ca 2 V 2 O 7 grains are basically wrapped by the liquid phase. At the same time, the liquid phase also fills the gaps of the crystal grains, thereby increasing the density of the material, thereby significantly improving the microwave dielectric properties of the material.
以上所述，仅为本发明的具体实施方式，本说明书中所公开的任一特征，除非特别叙述，均可被其他等效或具有类似目的的替代特征加以替换；所公开的所有特征、或所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以任何方式组合。The above descriptions are only specific embodiments of the present invention, and any feature disclosed in this specification, unless otherwise stated, can be replaced by other equivalent or alternative features with similar purposes; all the disclosed features, or All steps in a method or process, except mutually exclusive features and/or steps, may be combined in any way.
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