CN101328068B

Movatterモバイル変換

Info

Publication number: CN101328068B
Application number: CN2008100631840A
Authority: CN
Inventors: 张启龙; 杨辉; 李绍纯; 史灵杭
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2008-07-28
Filing date: 2008-07-28
Publication date: 2010-12-22
Anticipated expiration: 2028-07-28
Also published as: CN101328068A

Abstract

本发明公开了一种含硼的微波介质陶瓷水基流延膜片的制备方法，包括：将分散剂、改性剂溶于去离子水中，加入Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和含硼烧结助剂球磨混合后，再加入粘结剂和消泡剂球磨混合制备水基流延浆料；将浆料流延，在30～80℃干燥得到陶瓷膜片；膜片上可印刷内电极，然后在850～950℃烧结成型。本发明中制备的浆料与硼的适应性良好，适于流延成型；陶瓷膜片表面光滑，力学性能优良，粉体颗粒分散性好，气孔分布均匀，与内电极共烧性良好。本发明制备工艺简单，无污染，成本低，适合大规模工业生产。The invention discloses a method for preparing a boron-containing microwave dielectric ceramic water-based casting film, which comprises: dissolving a dispersant and a modifier in deionized water, adding Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder After the body and boron-containing sintering aid are ball-milled and mixed, the binder and defoamer are added to ball-mill and mixed to prepare a water-based casting slurry; the slurry is cast and dried at 30-80°C to obtain a ceramic diaphragm; The internal electrodes can be printed and then sintered at 850-950°C. The slurry prepared in the invention has good adaptability to boron and is suitable for tape casting; the ceramic diaphragm has smooth surface, excellent mechanical properties, good dispersion of powder particles, uniform distribution of pores, and good co-firing with internal electrodes. The preparation process of the invention is simple, pollution-free, low in cost and suitable for large-scale industrial production.

Description

Translated fromChinese

一种含硼的微波介质陶瓷水基流延膜片的制备方法A preparation method of a boron-containing microwave dielectric ceramic water-based cast membrane

技术领域technical field

本发明涉及适用于低温共烧陶瓷(LTCC)技术的微波介质陶瓷膜片领域，特别涉及一种含硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片的制备方法。The invention relates to the field of microwave dielectric ceramic diaphragms suitable for low-temperature co-fired ceramics (LTCC) technology, in particular to a method for preparing a boron-containing Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting diaphragm.

背景技术Background technique

水基流延成型由于使用水作为溶剂，可以大幅度降低有机物的使用量，同时采用合适的添加剂(粘结剂、分散剂等)可以降低浆料粘度，提高浆料的固相体积分数，有利于提高膜片密度，而且还具有不燃、无毒、成本低等优点，应用前景十分看好，已经成为不可逆转的发展趋势。Since water-based tape casting uses water as a solvent, the amount of organic matter used can be greatly reduced. At the same time, the use of appropriate additives (binders, dispersants, etc.) can reduce the viscosity of the slurry and increase the solid phase volume fraction of the slurry. It is beneficial to increase the density of the diaphragm, and also has the advantages of non-combustibility, non-toxicity, and low cost. The application prospect is very promising, and it has become an irreversible development trend.

BORISEVICH A Y和DAVIES P K在Crystalline Structure Dielectricproperties of Li_1+x-yNb_1-x-3yTi_x+4yO₃ M-Phase Solid Solution[J][Journal of theAmerican Ceramic Society，2002，85(3)：573-578.]一文中公开了一种Li_1.075Nb_0.625Ti_0.45O₃(LNT)微波介质陶瓷，该微波介质陶瓷具有较低的烧结温度(1100℃)和良好的微波介电特性：介电常数ε_r＝55～78，品质因数Qf可达9000GHz，频率温度系数τ_f可调，如能降低烧结温度，并和LTCC技术制造工艺匹配，将是理想的LTCC介质材料。含有硼的烧结助剂可以有效地降低Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷的烧结温度，但是目前在产业化应用中存在较大的问题。含有硼的烧结助剂能与流延成型工艺中常用的粘结剂聚乙烯醇缩丁醛(PVB)或聚乙烯醇(PVA)发生胶凝反应，形成具有三维凝胶结构的PVA-B(OH)₄^-化合物，使流延浆料增稠和凝胶化，而且含有硼的陶瓷粉经流延工艺不能获得力学性能优良的膜片。有效的烧结助剂不适用于一般的流延成型工艺，极大的限制了Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷的产业应用。BORISEVICH A Y and DAVIES P K in Crystalline Structure Dielectric properties of Li_1+xy Nb_1-x-3y Ti_x+4y O₃ M-Phase Solid Solution[J][Journal of the American Ceramic Society, 2002, 85(3): 573- 578.] discloses a Li_1.075 Nb_0.625 Ti_0.45 O₃ (LNT) microwave dielectric ceramic, which has a low sintering temperature (1100°C) and good microwave dielectric properties: dielectric constant ε_r = 55-78, the quality factor Qf can reach 9000GHz, and the frequency temperature coefficient τ_f is adjustable. If the sintering temperature can be lowered and matched with the LTCC manufacturing process, it will be an ideal LTCC dielectric material. Boron-containing sintering aids can effectively reduce the sintering temperature of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramics, but there are major problems in industrial applications. The sintering aid containing boron can gel with the binder polyvinyl butyral (PVB) or polyvinyl alcohol (PVA) commonly used in the tape casting process to form PVA-B with a three-dimensional gel structure ( OH)₄^-Compounds thicken and gel the casting slurry, and ceramic powders containing boron cannot obtain membranes with excellent mechanical properties through casting process. Effective sintering aids are not suitable for general tape casting process, which greatly limits the industrial application of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramics.

目前，如何解决上述问题的相关文献报道比较少，而且效果不能满足产业要求。At present, there are relatively few relevant literature reports on how to solve the above problems, and the effect cannot meet the requirements of the industry.

发明内容Contents of the invention

本发明提供了一种含硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片的制备方法，通过添加改性剂，与硼发生配位反应，制备出性能优良、可与内电极低温共烧的水基流延膜片。本制备方法的工艺简单，无污染，成本低，适合大规模工业生产。The invention provides a method for preparing a boron-containing Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting membrane. By adding a modifier, it undergoes a coordination reaction with boron to prepare a film with excellent performance that can be used with A water-based cast membrane with low-temperature co-fired inner electrodes. The preparation method has simple process, no pollution and low cost, and is suitable for large-scale industrial production.

一种含硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片的制备方法，包括以下步骤：A preparation method of a boron-containing Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting film, comprising the following steps:

(1)将分散剂、改性剂溶于去离子水中，加入Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和含硼的烧结助剂球磨混合后，再加入粘结剂和消泡剂球磨混合制备水基流延浆料；其中浆料由下列重量百分比的原料组成：Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体40～60％，含硼的烧结助剂2～20％，分散剂1～2％，粘结剂10～20％，改性剂5～15％，消泡剂0.5～2％，余量为去离子水；(1) Dissolve the dispersant and modifier in deionized water, add Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and boron-containing sintering aids for ball milling, then add binder and defoamer Ball milling and mixing to prepare water-based casting slurry; wherein the slurry is composed of the following raw materials in weight percentage: 40-60% of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder, 2-20% of boron-containing sintering aid, 1-2% dispersant, 10-20% binder, 5-15% modifier, 0.5-2% defoamer, and the balance is deionized water;

(2)将步骤(1)制备的水基流延浆料流延，在30～80℃干燥得到陶瓷膜片，干燥时间为20～60min；(2) cast the water-based casting slurry prepared in step (1), and dry at 30-80° C. to obtain a ceramic diaphragm, and the drying time is 20-60 minutes;

(3)在步骤(2)制备的陶瓷膜片上印刷内电极，然后烧结成型。(3) Printing internal electrodes on the ceramic diaphragm prepared in step (2), and then sintering and molding.

所述含硼的烧结助剂为硼酸、氧化硼或硼硅酸盐玻璃中的一种，所述的硼硅酸盐玻璃为锌硼硅玻璃、锂硼硅玻璃等，利用其液相烧结机理，使膜片可在低温下烧结致密。The boron-containing sintering aid is one of boric acid, boron oxide or borosilicate glass, and the borosilicate glass is zinc borosilicate glass, lithium borosilicate glass, etc. , so that the diaphragm can be sintered and dense at low temperature.

所述粘结剂为聚丙烯酸乳液或聚甲基丙烯酸，用于包裹陶瓷粉体表面，并能自身固化产生相互连接的树脂架构，赋予膜片一定的强度和韧性。The binder is polyacrylic acid emulsion or polymethacrylic acid, which is used to wrap the surface of the ceramic powder, and can self-cure to form an interconnected resin structure, endowing the membrane with a certain strength and toughness.

所述分散剂为聚羧酸铵或聚丙烯酸铵，利用分散剂吸附在陶瓷粉体表面所产生的静电排斥和空间位阻作用，实现Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体在水中的良好分散。The dispersant is ammonium polycarboxylate or ammonium polyacrylate, and the electrostatic repulsion and steric hindrance produced by the adsorption of the dispersant on the surface of the ceramic powder realize Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder in water good dispersion.

所述改性剂为多羟基化合物中的一种，多羟基化合物如甘露醇、丙三醇、山梨醇等。该改性剂会和含硼的烧结助剂发生配位反应，以甘露醇、山梨醇为例，反应式如式(1)所示，从而解决硼的加入造成的浆料粘度急剧增加、膜片力学性能急剧恶化的问题。The modifying agent is one of polyhydroxy compounds, such as mannitol, glycerol, sorbitol and the like. The modifier will undergo a coordination reaction with boron-containing sintering aids. Taking mannitol and sorbitol as examples, the reaction formula is shown in formula (1), so as to solve the sharp increase in viscosity of the slurry caused by the addition of boron. The problem of sharp deterioration of the mechanical properties of the sheet.

所述消泡剂为聚硅氧烷乳液，可选用市售的W-0506型聚硅氧烷乳液。所述内电极为银内电极或银/钯内电极。可在制备的陶瓷膜片上印刷一层内电极，制备单层膜片；也可在陶瓷膜片上印刷一层内电极，然后在内电极上覆盖一层陶瓷膜片形成有效层，在有效层上再次印刷内电极，如此重复直至有效层数达到设计要求，制备出多层膜片。The defoamer is polysiloxane emulsion, and commercially available W-0506 type polysiloxane emulsion can be selected. The internal electrodes are silver internal electrodes or silver/palladium internal electrodes. A layer of internal electrodes can be printed on the prepared ceramic diaphragm to prepare a single-layer diaphragm; a layer of internal electrodes can also be printed on the ceramic diaphragm, and then a layer of ceramic diaphragm is covered on the inner electrode to form an effective layer. The internal electrodes are printed again on the first layer, and this is repeated until the number of effective layers meets the design requirements, and a multi-layer diaphragm is prepared.

所述烧结成型采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至850～950℃并保温2～4小时的方式。The sintering molding adopts the method of raising the temperature to 450° C. at a speed of 1.5° C./min and holding it for 1 hour, and then raising the temperature at a speed of 5° C./min to 850-950° C. and holding it for 2-4 hours.

本发明与现有技术相比具有以下的主要优点：Compared with the prior art, the present invention has the following main advantages:

(1)制备工艺简单，无污染，成本低，适合大规模工业生产；(1) The preparation process is simple, pollution-free, low in cost, and suitable for large-scale industrial production;

(2)添加含硼烧结助剂后，水基流延浆料的分散性好，粘度低，没有胶凝现象发生，适于流延成型；(2) After adding boron-containing sintering aids, the water-based tape casting slurry has good dispersibility, low viscosity, no gelation phenomenon, and is suitable for tape casting;

(3)制备的陶瓷膜片表面平整，气孔分布均匀，强度高，韧性好，解决了添加含硼烧结助剂后陶瓷膜片脆性过大的问题。(3) The surface of the prepared ceramic diaphragm is smooth, the distribution of pores is uniform, the strength is high, and the toughness is good, which solves the problem of excessive brittleness of the ceramic diaphragm after adding the boron-containing sintering aid.

附图说明Description of drawings

图1是实施例2中烧结后陶瓷膜片表面形貌的微观结构示意图；Fig. 1 is the microstructural schematic diagram of ceramic diaphragm surface topography after sintering in embodiment 2;

图2是实施例2中陶瓷膜片与银内电极低温共烧后其断面形貌的微观结构示意图。2 is a schematic diagram of the microstructure of the cross-sectional morphology of the ceramic diaphragm and the silver inner electrode after low-temperature co-firing in Example 2.

具体实施方式Detailed ways

结合本发明的内容提供以下实施例：Provide following embodiment in conjunction with content of the present invention:

实施例1Example 1

将2.5g聚丙烯酸铵和12.5g丙三醇溶于91.25g去离子水中，然后加入100g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和5g H₃BO₃，球磨混合12h后，加入37.5g含量为35wt％的聚丙烯酸乳液和1.25g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在60℃下干燥50min后从基带下剥离，得到厚度在100μm左右，平均孔径0.8μm，孔隙率50％的陶瓷膜片。在陶瓷膜片上印刷一层银内电极后，采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至900℃并保温2小时的方式烧结成型，制得含有硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片。Dissolve 2.5g of ammonium polyacrylate and 12.5g of glycerol in 91.25g of deionized water, then add 100g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 5g of H₃ BO₃ , and after ball milling for 12 hours, add 37.5 The polyacrylic acid emulsion with a g content of 35wt% and 1.25g W-0506 polysiloxane emulsion were ball-milled for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape-casted, and the cast membrane was dried at 60°C for 50 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.8 μm, and a porosity of 50%. After printing a layer of silver internal electrodes on the ceramic diaphragm, heat up to 450°C at a speed of 1.5°C/min and hold for 1 hour, then heat up to 900°C at a speed of 5°C/min and hold for 2 hours for sintering. , to prepare boron-containing Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting membrane.

实施例2Example 2

将2.5g聚丙烯酸铵和12.5g丙三醇溶于91.25g去离子水中，然后加入100g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和5g H₃BO₃，球磨混合12h后，加入37.5g含量为35wt％的聚丙烯酸乳液和1.25g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在60℃下干燥50min后从基带下剥离，得到厚度在100μm左右，平均孔径0.8μm，孔隙率50％的陶瓷膜片。在陶瓷膜片上印刷一层银内电极，然后在银内电极上覆盖一层陶瓷膜片形成有效层，在有效层上再次印刷银内电极，如此重复直至有效层数达到设计要求，制备出多层膜片。将多层膜片在20兆帕压力下压制成生坯，采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至900℃并保温2小时的方式烧结成型，制得含有硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片。烧结后陶瓷膜片表面的微观结构见图1，从微观结构图中可以看出，陶瓷膜片在900℃达到烧结致密，晶粒呈片状，厚度在1μm左右，陶瓷膜片烧结后微观结构均匀。陶瓷膜片与银内电极低温共烧后断面形貌的微观结构见图2，从图中可以看出，陶瓷膜片与银内电极的结合界面紧密、清晰，相互间没有分层、扩渗现象发生，表明银与陶瓷没有发生反应，二者具有良好的工艺匹配性。Dissolve 2.5g of ammonium polyacrylate and 12.5g of glycerol in 91.25g of deionized water, then add 100g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 5g of H₃ BO₃ , and after ball milling for 12 hours, add 37.5 The polyacrylic acid emulsion with a g content of 35wt% and 1.25g W-0506 polysiloxane emulsion were ball-milled for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape-casted, and the cast membrane was dried at 60°C for 50 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.8 μm, and a porosity of 50%. Print a layer of silver internal electrodes on the ceramic diaphragm, then cover the silver internal electrodes with a layer of ceramic diaphragm to form an effective layer, and print the silver internal electrodes again on the effective layer, repeating this until the number of effective layers meets the design requirements, and prepares Multilayer diaphragm. The multi-layer membrane is pressed into a green body under a pressure of 20 MPa, and the temperature is raised to 450°C at a speed of 1.5°C/min and kept for 1 hour, and then the temperature is raised to 900°C at a speed of 5°C/min and held for 2 hours. Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting film containing boron was prepared by sintering and forming. The microstructure of the surface of the ceramic diaphragm after sintering is shown in Figure 1. From the microstructure diagram, it can be seen that the ceramic diaphragm is sintered and dense at 900 °C, the grains are flake-shaped, and the thickness is about 1 μm. The microstructure of the ceramic diaphragm after sintering uniform. The microstructure of the cross-sectional morphology of the ceramic diaphragm and the silver inner electrode after low-temperature co-firing is shown in Figure 2. It can be seen from the figure that the bonding interface between the ceramic diaphragm and the silver inner electrode is tight and clear, and there is no delamination or diffusion between them. The phenomenon occurs, indicating that silver and ceramics have not reacted, and the two have good process matching.

实施例3Example 3

将3.0g聚丙烯酸铵和20g甘露醇溶于67.5g去离子水中，然后加入102.5g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和20g H₃BO₃，球磨混合12h后，加入35g含量为35wt％的聚丙烯酸乳液和2.0g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在70℃下干燥40min后从基带下剥离，得到厚度在100μm左右，平均孔径0.7μm，孔隙率46.5％的陶瓷膜片。后续印刷内电极及烧结成型的过程同实施例2。Dissolve 3.0g ammonium polyacrylate and 20g mannitol in 67.5g deionized water, then add 102.5g Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 20g H₃ BO₃ , after ball milling for 12 hours, add 35g content 35wt% polyacrylic acid emulsion and 2.0g W-0506 polysiloxane emulsion were mixed by ball milling for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape-casted, and the cast membrane was dried at 70°C for 40 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.7 μm, and a porosity of 46.5%. Subsequent processes of printing internal electrodes and sintering are the same as in Example 2.

实施例4Example 4

将5.0g聚羧酸铵和25g山梨醇溶于16.25g去离子水中，然后加入137.5g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和25g H₃BO₃，球磨混合12h后，加入37.5g聚甲基丙烯酸和3.75g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在80℃下干燥20min后从基带下剥离，得到厚度在100μm左右，平均孔径0.5μm，孔隙率40％的陶瓷膜片。后续印刷内电极及烧结成型的过程同Dissolve 5.0g of ammonium polycarboxylate and 25g of sorbitol in 16.25g of deionized water, then add 137.5g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 25g of H₃ BO₃ , after ball milling for 12 hours, add 37.5 g of polymethacrylic acid and 3.75 g of W-0506 polysiloxane emulsion were ball-milled for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape casted, and the cast membrane was dried at 80°C for 20 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.5 μm, and a porosity of 40%. The subsequent process of printing internal electrodes and sintering molding is the same as

实施例2。Example 2.

实施例5Example 5

将2.5g聚羧酸铵和30g丙三醇溶于68.75g去离子水中，然后加入102.5g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和12.5g锌硼硅玻璃，球磨混合12h后，加入30g含量为35wt％的聚丙烯酸乳液和3.75g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在60℃下干燥50min后从基带下剥离，得到厚度在100μm左右，平均孔径0.6μm，孔隙率47％的陶瓷膜片。后续印刷内电极及烧结成型的过程同实施例2。Dissolve 2.5g of ammonium polycarboxylate and 30g of glycerol in 68.75g of deionized water, then add 102.5g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 12.5g of zinc borosilicate glass, and ball mill and mix for 12 hours. 30 g of polyacrylic acid emulsion with a content of 35 wt % and 3.75 g of W-0506 polysiloxane emulsion were added, and ball milling was continued for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape casted, and the cast membrane was dried at 60°C for 50 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.6 μm, and a porosity of 47%. Subsequent processes of printing internal electrodes and sintering are the same as in Example 2.

实施例6Example 6

将2.5g聚丙烯酸铵和30g丙三醇溶于36.25g去离子水中，然后加入102.5g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和30g锂硼硅玻璃，球磨混合12h后，加入37.5g含量为35wt％的聚丙烯酸乳液和3.75g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在80℃下干燥20min后从基带下剥离，得到厚度在100μm左右，平均孔径0.5μm，孔隙率42％的陶瓷膜片。在陶瓷膜片上印刷一层银内电极，然后在银内电极上覆盖一层陶瓷膜片形成有效层，在有效层上再次印刷内电极，如此重复直至有效层数达到设计要求，制备出多层膜片。将多层膜片在20兆帕压力下压制成生坯，采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至900℃并保温4小时的方式烧结成型，制得含有硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片。Dissolve 2.5g of ammonium polyacrylate and 30g of glycerol in 36.25g of deionized water, then add 102.5g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 30g of lithium borosilicate glass, and after ball milling for 12 hours, add 37.5 The polyacrylic acid emulsion with a g content of 35wt% and 3.75g W-0506 polysiloxane emulsion were ball-milled for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape-casted, and the cast membrane was dried at 80°C for 20 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.5 μm, and a porosity of 42%. Print a layer of silver internal electrodes on the ceramic diaphragm, then cover the silver internal electrodes with a layer of ceramic diaphragm to form an effective layer, and print the internal electrodes again on the effective layer, repeating this until the number of effective layers meets the design requirements. layer membrane. The multi-layer membrane is pressed into a green body under a pressure of 20 MPa, and the temperature is raised to 450°C at a speed of 1.5°C/min and kept for 1 hour, and then heated to 900°C at a speed of 5°C/min and held for 4 hours. Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting film containing boron was prepared by sintering and forming.

实施例7Example 7

将3.0g聚丙烯酸铵和20g丙三醇溶于67.5g去离子水中，然后加入102.5g Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和20g H₃BO₃，球磨混合12h后，加入35g含量为35wt％的聚丙烯酸乳液和2.0g W-0506型聚硅氧烷乳液，继续球磨混合2h后，得到水基流延浆料。将制得的浆料进行流延成型，流延膜片在70℃下干燥40min后从基带下剥离，得到厚度在100μm左右，平均孔径0.7μm，孔隙率46.5％的陶瓷膜片。在陶瓷膜片上印刷一层银/钯内电极，然后在银/钯内电极上覆盖一层陶瓷膜片形成有效层，在有效层上再次印刷银/钯内电极，如此重复直至有效层数达到设计要求，制备出多层膜片。将多层膜片在20兆帕压力下压制成生坯，采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至900℃并保温2小时的方式烧结成型，制得含有硼的Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷水基流延膜片。Dissolve 3.0g of ammonium polyacrylate and 20g of glycerol in 67.5g of deionized water, then add 102.5g of Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and 20g of H₃ BO₃ , and after ball milling for 12 hours, add 35g The polyacrylic acid emulsion with a content of 35 wt% and 2.0 g of W-0506 type polysiloxane emulsion were ball-milled for 2 hours to obtain a water-based casting slurry. The prepared slurry was tape-casted, and the cast membrane was dried at 70°C for 40 minutes and then peeled off from the base tape to obtain a ceramic membrane with a thickness of about 100 μm, an average pore size of 0.7 μm, and a porosity of 46.5%. Print a layer of silver/palladium internal electrode on the ceramic diaphragm, then cover a layer of ceramic diaphragm on the silver/palladium internal electrode to form an effective layer, print silver/palladium internal electrode again on the effective layer, and repeat until the number of effective layers The design requirements are met, and a multi-layer diaphragm is prepared. The multi-layer membrane is pressed into a green body under a pressure of 20 MPa, and the temperature is raised to 450°C at a speed of 1.5°C/min and kept for 1 hour, and then the temperature is raised to 900°C at a speed of 5°C/min and held for 2 hours. Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic water-based casting film containing boron was prepared by sintering and forming.

以上列举的仅是本发明的若干具体实施例，显然本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。The above enumerations are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All deformations that can be directly derived or associated by those skilled in the art from the content disclosed in the present invention should be considered as the protection scope of the present invention.

Claims

Translated fromChinese

1.一种含硼的微波介质陶瓷水基流延膜片的制备方法，包括以下步骤：1. a preparation method of a boron-containing microwave dielectric ceramic water-based casting diaphragm, comprising the following steps:

(1)将分散剂、改性剂溶于去离子水中，加入Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体和含硼烧结助剂球磨混合后，再加入粘结剂和消泡剂球磨混合制备水基流延浆料；其中浆料由下列重量百分比的原料组成：Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷粉体40～60％，含硼烧结助剂2～20％，分散剂1～2％，粘结剂10～20％，改性剂5～15％，消泡剂0.5～2％，余量为去离子水；(1) Dissolve the dispersant and modifier in deionized water, add Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder and boron-containing sintering aids for ball milling, then add binder and defoamer for ball milling Mixing to prepare water-based casting slurry; wherein the slurry is composed of the following raw materials in weight percentage: Li_1.075 Nb_0.625 Ti_0.45 O₃ microwave dielectric ceramic powder 40-60%, boron-containing sintering aid 2-20%, dispersant 1-2%, binder 10-20%, modifier 5-15%, defoamer 0.5-2%, the balance is deionized water;

所述改性剂为多羟基化合物中的一种；The modifying agent is one of the polyhydroxy compounds;

(2)将步骤(1)制备的水基流延浆料流延，在30℃～80℃干燥得到陶瓷膜片，干燥时间为20～60min；(2) cast the water-based casting slurry prepared in step (1), and dry at 30°C to 80°C to obtain a ceramic diaphragm, and the drying time is 20 to 60 minutes;

2.根据权利要求1所述的制备方法，其特征在于：所述含硼烧结助剂为硼酸、氧化硼和硼硅酸盐玻璃中的一种。2. The preparation method according to claim 1, characterized in that: the boron-containing sintering aid is one of boric acid, boron oxide and borosilicate glass.

3.根据权利要求1所述的制备方法，其特征在于：所述粘结剂为聚丙烯酸乳液或聚甲基丙烯酸。3. The preparation method according to claim 1, characterized in that: the binder is polyacrylic acid emulsion or polymethacrylic acid.

4.根据权利要求1所述的制备方法，其特征在于：所述分散剂为聚羧酸铵或聚丙烯酸铵。4. The preparation method according to claim 1, characterized in that: the dispersant is ammonium polycarboxylate or ammonium polyacrylate.

5.根据权利要求1所述的制备方法，其特征在于：所述消泡剂为聚硅氧烷乳液。5. The preparation method according to claim 1, characterized in that: the defoamer is polysiloxane emulsion.

6.根据权利要求1所述的制备方法，其特征在于：所述步骤(3)中的内电极为银内电极或银/巴内电极。6. The preparation method according to claim 1, characterized in that: the internal electrode in the step (3) is a silver internal electrode or a silver/bar internal electrode.

7.根据权利要求1所述的制备方法，其特征在于：所述步骤(3)中陶瓷膜片单层印刷内电极或由若干单层印刷内电极后进行叠层。7. The preparation method according to claim 1, characterized in that: in the step (3), the internal electrodes are printed on the ceramic diaphragm in a single layer or laminated after printing internal electrodes in several single layers.

8.根据权利要求1所述的制备方法，其特征在于：所述步骤(3)中的烧结成型采用以1.5℃/min的速度升温至450℃并保温1小时，然后以5℃/min的速度升温至850～950℃并保温2～4小时的方式。8. The preparation method according to claim 1, characterized in that: the sintering molding in the step (3) is heated to 450°C at a rate of 1.5°C/min and kept at a temperature of 1 hour, and then heated at a rate of 5°C/min Speed up to 850-950°C and keep it warm for 2-4 hours.