CN115504785A - Yttrium-excess rare earth-doped YAG microwave dielectric ceramic material and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明提供钇过量的掺稀土元素的YAG微波介质陶瓷材料及其制备方法，材料化学通式为Y_3.03‑xRe_xAl₅O₁₂，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1；本发明的制备方法包括步骤：配料、球磨、烘干过筛、预烧、干压、冷等静压成型、真空烧结、气氛控制退火。本发明材料为典型YAG微波介电陶瓷，所得材料在晶界处捕获刃型位错结构，实现低损耗特征，Q×f在160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在‑36ppm/℃～‑25ppm/℃之间。配方中不含Pb，Cd等挥发性有毒金属，性能稳定，能够满足现代微波器件的应用需求，原材料在国内供应充足，价格低廉，使高性能微波陶瓷的低成本化成为可能。

The invention provides a YAG microwave dielectric ceramic material doped with excessive yttrium rare earth elements and a preparation method thereof. The general chemical formula of the material is Y_3.03‑x Re_x Al₅ O₁₂ , Re is La³⁺ , Ce³⁺ , Nd³⁺ , One or more of Sm³⁺ , Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1; the preparation method of the present invention includes steps: batching, ball milling, baking Dry sieving, pre-firing, dry pressing, cold isostatic pressing, vacuum sintering, atmosphere controlled annealing. The material of the present invention is a typical YAG microwave dielectric ceramic, and the obtained material captures the edge dislocation structure at the grain boundary to realize low loss characteristics, Q×f is between 160,000 GHz and 200,000 GHz, and the relative permittivity ε_r is between 10 and 16 The frequency temperature coefficient τ_f is between -36ppm/℃～-25ppm/℃. The formula does not contain volatile toxic metals such as Pb and Cd, and has stable performance, which can meet the application requirements of modern microwave devices. The raw materials are abundantly supplied in China and the price is low, which makes it possible to reduce the cost of high-performance microwave ceramics.

Description

Translated fromChinese

钇过量的掺稀土元素YAG微波介质陶瓷材料及制备方法Excessive yttrium-doped rare earth element YAG microwave dielectric ceramic material and preparation method

技术领域technical field

本发明属于电子信息功能材料制备技术领域，涉及一种通过掺杂稀土元素的非化学计量比的钇铝石榴石诱导良性位错结构产生而获得超高Q值微波介质陶瓷材料及其制备方法。The invention belongs to the technical field of preparation of electronic information functional materials, and relates to a microwave dielectric ceramic material with ultra-high Q value obtained by inducing a benign dislocation structure by doping non-stoichiometric yttrium-aluminum garnet doped with rare earth elements and a preparation method thereof.

背景技术Background technique

微波介质陶瓷是指应用于微波(300MHz～300GHz)频段电路中作为介质材料并完成一种或多种功能的陶瓷，是现代通信技术中的关键基础材料，被广泛应用于介质谐振器、滤波器、介质基片、介质波导回路、微波电容、双工器、天线等微波元器件。在高频微波电路中，许多微波器件需要使用介质陶瓷材料作为基板，使得微波陶瓷介质基板材料愈来愈成为微波器件、部件与整机系统中使用的关键性基础材料。介电常数是介质陶瓷基板的关键性能，介电常数的范围往往决定基板材料的适用方向。例如，相对介电常数低于15的基板适用于高速数字电路的设计；相对介电常数15～80的基板可很好地完成高频线路的设计；相对介电常数高达20000的基板，则可使高容性器件集成到多层结构中。而发展低介电常数(≤20)的微波介质陶瓷材料以满足高频和高速的要求是微波介质陶瓷的重点研究发展方向。由于微波介质陶瓷材料的品质因数Q×f值越大，滤波器的插入损耗就越低，故高品质因素有利于实现微波器件良好选频性，而接近于零的频率温度系数τ_f意味着器件的中心频率随环境温度变化小，工作稳定性高。因此，研制在微波频率下同时具有一定范围内可调介电常数，超低损耗和接近于零的频率温度系数的微波介质陶瓷材料具有很大的应用价值。Microwave dielectric ceramics refer to ceramics that are used as dielectric materials in microwave (300MHz～300GHz) frequency band circuits and perform one or more functions. They are key basic materials in modern communication technology and are widely used in dielectric resonators and filters. , dielectric substrate, dielectric waveguide circuit, microwave capacitor, duplexer, antenna and other microwave components. In high-frequency microwave circuits, many microwave devices need to use dielectric ceramic materials as substrates, making microwave ceramic dielectric substrate materials increasingly become the key basic materials used in microwave devices, components and complete machine systems. The dielectric constant is the key performance of the dielectric ceramic substrate, and the range of the dielectric constant often determines the applicable direction of the substrate material. For example, a substrate with a relative permittivity lower than 15 is suitable for the design of high-speed digital circuits; a substrate with a relative permittivity of 15-80 can well complete the design of high-frequency circuits; a substrate with a relative permittivity as high as 20,000 can be used Enables the integration of highly capacitive devices into multilayer structures. The development of microwave dielectric ceramic materials with low dielectric constant (≤20) to meet the requirements of high frequency and high speed is the key research and development direction of microwave dielectric ceramics. Since the larger the quality factor Q×f value of microwave dielectric ceramic materials, the lower the insertion loss of the filter, so the high quality factor is conducive to the realization of good frequency selection of microwave devices, and the frequency temperature coefficient τ_f close to zero means The central frequency of the device changes little with the ambient temperature, and the working stability is high. Therefore, the development of microwave dielectric ceramic materials with adjustable dielectric constant within a certain range, ultra-low loss and close to zero frequency temperature coefficient at microwave frequencies has great application value.

钇铝石榴石，Y₃Al₅O₁₂(YAG)，在可见光到中红外波段都具有高的透过率，并且在光学、力学、热学等方面也具有优异性能，在民用加工、医疗和军事武器等领域有广泛的应用前景。目前，钇铝石榴石(Y₃Al₅O₁₂)陶瓷的光学性能已经被广泛报道，但对其的微波介电性能的系统研究还相对鲜见。Yttrium aluminum garnet, Y₃ Al₅ O₁₂ (YAG), has high transmittance in the visible light to mid-infrared band, and also has excellent performance in optics, mechanics, heat, etc., and is widely used in civil processing, medical and military Weapons and other fields have broad application prospects. At present, the optical properties of yttrium aluminum garnet (Y₃ Al₅ O₁₂ ) ceramics have been widely reported, but the systematic research on its microwave dielectric properties is relatively rare.

对钇铝石榴石探索始于上世纪90年代，《美国陶瓷学报》(Journal of TheAmerican Ceramic Society)1995年的文章《用于固态激光器的高性能多晶Nd：YAG陶瓷的制备和光学性能》(Fabrication and Optical Properties of High-PerformancePolycrystalline Nd:YAG Ceramics for Solid-State Lasers)报道了Ikesue等人使用亚微米氧化物的粉料作为原料合成了Y₃Al₅O₁₂(YAG)透明陶瓷。在该制备过程中，在对高纯度氧化铝和氧化钇原料进行球磨之后，加入SiO₂作为烧结助剂，并在1700℃的真空中烧制了YAG透明陶瓷。《铁电体》(Ferroelectrics)2009年的文章《YAG陶瓷的微波介电性能》(Microwave dielectric properties of YAG ceramics)报道了通过固相反应法制备的YAG陶瓷，在1650℃烧结24h获得的样品相对密度达99.6％，且具有优异的微波介电性能：ε_r＝10.5，Q×f＝440000GHz，τ_f＝-50ppm/℃。《陶瓷国际》(Ceramics International)2014的文章《Ga³⁺对RE₃Al₅O₁₂(Tb³⁺，Y³⁺，Er³⁺和Yb³⁺)石榴石陶瓷的烧结性和微波介电性能的影响》(The effect of Ga³⁺addition on the sinterability and microwave dielectricproperties of RE₃Al₅O₁₂(Tb³⁺,Y³⁺,Er³⁺and Yb³⁺)garnet ceramics)报道了在1650℃下烧结4小时的钇铝石榴石只能具有ε_r＝10.1，Q×f＝65,000GHz和τ_f＝-45ppm/℃的微波介电性能。并通过掺杂1wt％Nb₂O₅，钇铝石榴石微波的微波介电性能得到的部分改善：ε_r＝11.2、Q×f＝120000GHz、τ_f＝-48ppm/℃，其中Q×f值有了明显提高，但是Q×f值仍然较低，原因是此样品的相对密度太低只有96％，内部含有大量气孔存在，导致严重的介电损耗。再后来，《欧洲陶瓷学报》(Journal of the European Ceramic Society)2015年的文章《SPS烧结参数，LiF添加剂和Nd掺杂对透明YAG陶瓷的微波介电和光学性能的影响》(Effect of thespark plasma sintering parameters,LiF additive,and Nd dopant on the microwavedielectric and optical properties of transparent YAG ceramics)报道了通过热分解法制备得到纳米YAG粉末，然后共掺杂TEOS和TiO₂，在1520℃烧结5h获得钇铝石榴石微波介电陶瓷，相对密度为97.6％，微波介电性能为：ε_r＝9.9，Q×f＝71700GHz，τ_f＝-30ppm/℃，相对密度和性能仍未得到显著明显提升。The exploration of yttrium aluminum garnet began in the 1990s, and the 1995 article "High-performance polycrystalline Nd for solid-state lasers: preparation and optical properties of YAG ceramics" in "Journal of The American Ceramic Society" ( Fabrication and Optical Properties of High-Performance Polycrystalline Nd: YAG Ceramics for Solid-State Lasers) reported that Ikesue et al. used submicron oxide powder as a raw material to synthesize Y₃ Al₅ O₁₂ (YAG) transparent ceramics. In this preparation process, after ball milling high-purity alumina and yttrium oxide raw materials,_SiO2 was added as a sintering aid, and YAG transparent ceramics were fired in vacuum at 1700 °C. The 2009 article "Microwave dielectric properties of YAG ceramics" in "Ferroelectrics" reported that YAG ceramics prepared by solid-state reaction method were obtained by sintering at 1650°C for 24 hours. The density reaches 99.6%, and has excellent microwave dielectric properties: ε_r =10.5, Q×f=440000GHz, τ_f =-50ppm/℃. Ceramics International 2014 article "Sinterability and microwave dielectric properties of Ga³⁺ on RE₃ Al₅ O₁₂ (Tb³⁺ , Y³⁺ , Er³⁺ and Yb³⁺ ) garnet ceramics The effect of Ga³⁺ addition on the sinterability and microwave dielectric properties of RE₃ Al₅ O₁₂ (Tb³⁺ ,Y³⁺ ,Er³⁺ and Yb³⁺ )garnet ceramics) reported that at 1650℃ The yttrium aluminum garnet sintered for 4 hours can only have microwave dielectric properties of ε_r =10.1, Q×f =65,000 GHz and τ_f =-45 ppm/°C. And by doping 1wt% Nb₂ O₅ , the microwave dielectric properties of yttrium aluminum garnet microwave are partially improved: ε_r =11.2, Q×f=120000GHz, τ_f =-48ppm/℃, where Q×f value There is a significant improvement, but the Q×f value is still low, because the relative density of this sample is too low, only 96%, and there are a lot of pores inside, resulting in serious dielectric loss. Later, "Journal of the European Ceramic Society" (Journal of the European Ceramic Society) 2015 article "SPS sintering parameters, LiF additives and Nd doping on the microwave dielectric and optical properties of transparent YAG ceramics" (Effect of the spark plasma sintering parameters, LiF additive, and Nd dopant on the microwavedielectric and optical properties of transparent YAG ceramics) reported that nano-YAG powder was prepared by thermal decomposition method, then co-doped with TEOS and TiO₂ , and sintered at 1520°C for 5h to obtain yttrium aluminum pomegranate Stone microwave dielectric ceramics, the relative density is 97.6%, the microwave dielectric properties are: ε_r = 9.9, Q × f = 71700 GHz, τ_f = -30ppm/℃, the relative density and performance have not been significantly improved.

由此可以看出，在上述关于YAG微波介质陶瓷的研究中，不管是采用传统固相反应法，依靠球磨获得微米-亚微米陶瓷粉体，还是通过湿化学法制备纳米粉体，都还难以制备出相对密度高(≥99.5％)、不含气孔、杂质少的高质量YAG陶瓷，导致Q×f值都不高(≤120000GHz)。It can be seen that, in the above-mentioned research on YAG microwave dielectric ceramics, it is still difficult to obtain micron-submicron ceramic powders by ball milling, or to prepare nano-powders by wet chemical methods. High-quality YAG ceramics with high relative density (≥99.5%), no pores and few impurities are prepared, resulting in low Q×f values (≤120000GHz).

由于Y与各镧系元素物理性质相似，离子半径差异小，通过在掺杂稀土元素钇铝石榴石体系以实现性能优化是完全可行的思路，本发明旨在获得一种具有刃型位错结构特征，超高品质因数，频率温度系数可调，同时可在一定范围内调节介电性能的新型微波介质陶瓷，具有良好的应用前景，能满足微波通信行业需求。与此同时，还可提供一种诱导良性位错结构产生从而降低钇铝石榴石的本征损耗的方法，为低损耗石榴石陶瓷的可控合成和陶瓷基复合材料的微观结构控制提供参考。Since the physical properties of Y and the lanthanides are similar and the difference in ionic radius is small, it is completely feasible to achieve performance optimization by doping the rare earth element yttrium aluminum garnet system. The present invention aims to obtain a Features, ultra-high quality factor, adjustable frequency temperature coefficient, and a new type of microwave dielectric ceramic that can adjust the dielectric properties within a certain range, has a good application prospect and can meet the needs of the microwave communication industry. At the same time, it can also provide a method to induce the generation of benign dislocation structures to reduce the intrinsic loss of yttrium aluminum garnet, and provide a reference for the controllable synthesis of low-loss garnet ceramics and the microstructure control of ceramic matrix composites.

发明内容Contents of the invention

本发明的目的是提供一种钇过量的掺稀土元素YAG微波介质陶瓷材料，晶界处存在刃型位错缺陷，高品质因数、介电常数可调，谐振频率温度系数可调的微波介质陶瓷材料。本发明通过调整化学计量比的同时掺杂稀土元素的改性方式调控钇铝石榴石微波陶瓷材料(La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺)进行等电荷掺杂成功实现了一定程度的晶格演变，诱导良性位错结构发生，并有效调控Y₃Al₅O₁₂介电陶瓷的介电性能，制备出了高品质因数160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间，制备工艺简单，性能稳定，可靠性高，易于工业化生产。The purpose of the present invention is to provide a microwave dielectric ceramic material with excessive yttrium doped rare earth elements YAG microwave dielectric ceramics, edge dislocation defects exist at the grain boundaries, high quality factor, adjustable dielectric constant, and adjustable temperature coefficient of resonance frequency Material. The present invention controls the yttrium aluminum garnet microwave ceramic material (La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ ) isoelectrically doped to achieve a certain degree of lattice evolution, induce the occurrence of benign dislocation structures, and effectively regulate the dielectric properties of Y₃ Al₅ O₁₂ dielectric ceramics. High quality factor between 160000GHz and 200000GHz, relative permittivity ε_r between 10 and 16, frequency temperature coefficient τ_f between -36ppm/℃～-25ppm/℃, simple preparation process, stable performance and high reliability , easy for industrial production.

本发明的技术方案是：Technical scheme of the present invention is:

一种钇过量的掺稀土元素YAG微波介质陶瓷材料，材料化学通式为Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1。A YAG microwave dielectric ceramic material doped with excessive yttrium rare earth element, the general chemical formula of the material is Y_3.03-x Re_x Al₅ O₁₂ , wherein, Re is La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , One or more of Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1.

作为优选方式，所述微波介质陶瓷材料所用的原料包括三氧化二钇和三氧化二铝，以及La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃其中一种或多种；将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合，在1200～1400℃下预烧，再经过第二次球磨混合，经冷等静压成型后，在1700～1900℃下进行真空烧结且在氧气控制气氛下退火后制成。As a preferred mode, the raw materials used in the microwave dielectric ceramic material include diyttrium trioxide and dialuminum trioxide, and La₂ O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , One or more of Er₂ O₃ , Yb₂ O₃ and Lu₂ O₃ ; each component of the microwave ceramic material is compounded according to the chemical general formula, mixed by ball milling for the first time, and preheated at 1200-1400°C Sintered, mixed by ball milling for the second time, formed by cold isostatic pressing, vacuum sintered at 1700-1900°C and annealed in an oxygen-controlled atmosphere.

作为优选方式，材料晶界处存在刃型位错结构，材料Q×f在160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间。As a preferred mode, there is an edge dislocation structure at the grain boundary of the material, the material Q×f is between 160,000 GHz and 200,000 GHz, the relative permittivity ε_r is between 10 and 16, and the frequency temperature coefficient τ_f is between -36ppm/°C～ Between -25ppm/℃.

本发明还提供一种Y过量的掺稀土元素的YAG微波介质陶瓷材料的制备方法，包括以下步骤：The present invention also provides a preparation method of a YAG microwave dielectric ceramic material doped with an excessive amount of Y, comprising the following steps:

步骤1：配料；原料选自三氧化二钇和三氧化二铝粉末，以及一种或多种La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃，按照化学通式Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1，，配料形成混合物；Step 1: batching; raw materials are selected from diyttrium trioxide and aluminum oxide powder, and one or more of La₂ O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , Er₂ O₃ , Yb₂ O₃ and Lu₂ O₃ , according to the general chemical formula Y_3.03-x Re_x Al₅ O₁₂ , wherein, Re is La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , One or more of Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1, the ingredients form a mixture;

步骤2：一次球磨；以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(3～5)进行研磨4～8小时得到混合均匀的球磨料；Step 2: Ball milling once; use alumina balls as the ball milling medium, and grind for 4 to 8 hours according to the mass ratio of mixture: balls: alcohol: (4-8): (3-5) to obtain a uniform mixture Ball abrasive;

步骤3：烘干，过筛；将步骤2所得球磨料烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200～1400℃条件下预烧3～5小时得到预烧粉体；Step 4: Pre-burning; place the dry powder obtained inStep 3 in an alumina crucible, and pre-fire at 1200-1400°C for 3-5 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(3～5)进行研磨2～4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium, according to the mass ratio of mixture: ball: alcohol is 1: (4 ~ 8): (3～5) Grinding for 2～4 hours to obtain a uniformly mixed secondary ball abrasive;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺压制得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以1～5℃/min的升温速率升温并在1700～1900℃下烧结8～12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 1-5°C/min, and sinter at 1700-1900°C for 8-12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2～4℃/min的升温速率升温并在1000～1450℃下退火10～13小时，得到最终的微波介质陶瓷材料；Step 9: annealing; the sample obtained in step 8 is heated in an oxygen atmosphere furnace at a heating rate of 2-4°C/min and annealed at 1000-1450°C for 10-13 hours to obtain the final microwave dielectric ceramic material;

作为优选方式，所述步骤2和步骤5的球磨机为砂磨式球磨机。As a preferred manner, the ball mills in the step 2 andstep 5 are sand mills.

本发明通过冷等静压成型工艺为样品提供良好的致密度保证前提下，综合调控x的值来控制Y³⁺,Al³⁺，La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺离子的含量，以达到综合调控微波介电性能的目的，从而保证所制备微波介质陶瓷材料的微观形貌高度致密、无气孔和无微裂纹。所获钇铝石榴石结构材料在晶界处可以捕获少量的刃型位错结构，其高品质因数Q×f在160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间。Under the premise of providing a good density guarantee for the sample through the cold isostatic pressing forming process, the present invention comprehensively regulates the value of x to control Y³⁺ , Al³⁺ , La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , Gd³⁺ , Er³⁺ , Yb³⁺ , and Lu³⁺ ions, in order to achieve the purpose of comprehensively regulating the microwave dielectric properties, so as to ensure that the microscopic morphology of the prepared microwave dielectric ceramic materials is highly dense, free of pores and microcracks. The obtained yttrium aluminum garnet structure material can capture a small amount of edge dislocation structure at the grain boundary, its high quality factor Q×f is between 160000GHz and 200000GHz, the relative permittivity_εr is between 10 and 16, and the frequency The temperature coefficient τ_f is between -36ppm/℃～-25ppm/℃.

与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:

1.本发明配方中，通过综合调控x的值来控制稀土离子的掺杂量，以达到通过调节A位离子含量和优化配方的方式诱导良性位错结构发生，从而调控微波介电性能的目的，本发明采用冷等静压成型工艺以帮助样品获得高度致密的微观形貌，提供的微波介质陶瓷材料在性能上实现了较大提升，现有技术所制备的相关体系微波介质陶瓷材料，其ε_r在9～11之间，Q×f值在160000～200000GHz之间，其谐振频率温度系数在-30ppm/℃左右；相比之下，本发明提供的微波介质陶瓷材料具有典型的钇铝石榴石的相对介电常数ε_r在10～16之间可调，Q×f值在160000GHz～200000GHz之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间，并且性能稳定，能够满足现代微波器件的应用需求。1. In the formula of the present invention, the doping amount of rare earth ions is controlled by comprehensively regulating the value of x, so as to achieve the purpose of inducing benign dislocation structures by adjusting the content of A-site ions and optimizing the formula, thereby regulating the microwave dielectric properties , the present invention adopts the cold isostatic pressing forming process to help the sample obtain a highly dense microscopic appearance, and the provided microwave dielectric ceramic material has achieved a great improvement in performance. The microwave dielectric ceramic material of the related system prepared in the prior art, its ε_r is between 9 and 11, Q×f value is between 160000 and 200000 GHz, and its resonant frequency temperature coefficient is around -30ppm/°C; in contrast, the microwave dielectric ceramic material provided by the present invention has typical yttrium aluminum The relative permittivity ε_r of garnet is adjustable between 10 and 16, the Q×_f value is between 160000GHz and 200000GHz, the frequency temperature coefficient τf is between -36ppm/℃～-25ppm/℃, and the performance is stable , which can meet the application requirements of modern microwave devices.

2.本发明的微波介质陶瓷材料中不含Pb，Cd等挥发性有毒金属，可广泛应用于卫星通信中介质谐振器、滤波器、振荡器等微波器件中应用，绿色环保无污染，满足欧共体最新出台的RHOS(《电气、电子设备中限制使用某些有害物质指令》)和回收处理管理条例(WEEE)的严格标准要求。2. The microwave dielectric ceramic material of the present invention does not contain volatile toxic metals such as Pb and Cd, and can be widely used in microwave devices such as dielectric resonators, filters, and oscillators in satellite communications. The latest RHOS (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment Directive) and the strict standard requirements of the Recycling Management Regulations (WEEE) issued by the Community.

3.本发明制备微波介质陶瓷材料的原料在国内供应充足，价格相对低廉，使高性能微波陶瓷的低成本化成为可能，因此具有重要工业应用价值；而且本发明微波介质陶瓷材料的烧结温度均为1700～1900℃，烧结温度范围较宽，具有良好工艺适应性。3. the present invention prepares the raw material of microwave dielectric ceramic material in sufficient domestic supply, and price is relatively cheap, makes the low cost of high-performance microwave ceramic possible, therefore has important industrial application value; And the sintering temperature of microwave dielectric ceramic material of the present invention is uniform It is 1700～1900℃, the sintering temperature range is wide, and it has good process adaptability.

4.本发明配方所用原料均为简单的氧化物，不需要额外的工艺合成，完全优于需要另外单独合成的原料；本发明采用二次球磨工艺，实现材料的粒径控制。4. The raw materials used in the formula of the present invention are all simple oxides, which do not require additional process synthesis, and are completely superior to the raw materials that need to be separately synthesized; the present invention adopts a secondary ball milling process to achieve particle size control of the material.

具体实施方式以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.

附图说明Description of drawings

图1是本发明制备的微波陶瓷介质材料的TEM分析结果，表现为平行于钇铝石榴石的[111]晶轴和[100]相交的晶界的高分辨衍射图案，清晰而规则的晶面是陶瓷优异结晶度和均匀性的证明。如图所示，所选区域的电子衍射图像附近的原子平面在特定方向上发生畸变而发生位错，图中的虚线标记了明显的刃型位错线。位错提供了不消失的边界位置，从而促进了晶粒的生长，一定程度的晶格畸变和缺陷集中降低了钇铝石榴石陶瓷的相变温度。Fig. 1 is the TEM analysis result of the microwave ceramic dielectric material prepared by the present invention, showing the high-resolution diffraction pattern parallel to the [111] crystal axis of yttrium aluminum garnet and [100] intersecting grain boundary, clear and regular crystal plane Evidence of excellent crystallinity and homogeneity of ceramics. As shown in the figure, the atomic plane near the electron diffraction image of the selected region is distorted in a specific direction and a dislocation occurs, and the dotted line in the figure marks the obvious edge dislocation line. Dislocations provide non-disappearing boundary positions, thereby promoting the growth of grains, and a certain degree of lattice distortion and defect concentration reduce the phase transition temperature of yttrium aluminum garnet ceramics.

图2是本发明制备的微波陶瓷介质材料的SEM分析结果，从图2可以得出在本发明提供的成分配比和工艺条件能使晶粒得到良好生长，陶瓷形貌高度致密，无气孔存在。Fig. 2 is the SEM analysis result of the microwave ceramic dielectric material prepared by the present invention, from Fig. 2, it can be drawn that the composition ratio and process conditions provided by the present invention can make crystal grains grow well, the ceramic morphology is highly compact, and there is no pore. .

具体实施方式detailed description

实施例Example

本实施例提供一种钇过量的掺稀土元素YAG微波介质陶瓷材料，材料化学通式为Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1。This embodiment provides a rare_- earth_-dopedYAG^{microwavedielectric} ceramic material with excess^yttrium . One or more of Sm³⁺ , Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1.

所述微波介质陶瓷材料所用的原料包括三氧化二钇和三氧化二铝，以及La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃其中一种或多种；将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合，在1200～1400℃下预烧，再经过第二次球磨混合，经冷等静压成型后，在1700～1900℃下进行真空烧结且在氧气控制气氛下退火后制成。The raw materials used in the microwave dielectric ceramic material include yttrium trioxide and aluminum oxide, as well as La₂ O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , Er₂ O₃ , one or more of Yb₂ O₃ and Lu₂ O₃ ; each component of the microwave ceramic material is formulated according to the chemical general formula, mixed by ball milling for the first time, pre-fired at 1200-1400°C, and then After the second ball milling and mixing, cold isostatic pressing, vacuum sintering at 1700-1900°C and annealing under an oxygen-controlled atmosphere, it is made.

本实施例的一种Y过量的掺稀土元素的YAG微波介质陶瓷材料，其特征在于：微观形貌高度致密无气孔无微裂纹，材料晶界处存在刃型位错结构，实现低损耗特征，具有高品质因数，材料Q×f在160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间。A YAG microwave dielectric ceramic material doped with excessive Y and rare earth elements in this embodiment is characterized in that: the microscopic appearance is highly dense, no pores and no microcracks, and there is an edge dislocation structure at the grain boundary of the material, realizing low loss characteristics, With a high quality factor, the material Q×f is between 160000GHz and 200000GHz, the relative permittivity_εr is between 10 and 16, and the frequency temperature coefficient τf is between_-36ppm /℃～-25ppm/℃.

本实施例还提供一种钇过量的掺稀土元素YAG微波介质陶瓷材料的制备方法，包括以下步骤：This embodiment also provides a method for preparing a rare earth-doped YAG microwave dielectric ceramic material with excess yttrium, comprising the following steps:

步骤1：配料；原料选自三氧化二钇和三氧化二铝粉末，以及一种或多种La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃，按照化学通式Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1，，配料形成混合物；Step 1: batching; raw materials are selected from diyttrium trioxide and aluminum oxide powder, and one or more of La₂ O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , Er₂ O₃ , Yb₂ O₃ and Lu₂ O₃ , according to the general chemical formula Y_3.03-x Re_x Al₅ O₁₂ , wherein, Re is La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , One or more of Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1, the ingredients form a mixture;

步骤2：一次球磨；以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(2～5)进行研磨4～8小时得到混合均匀的球磨料；Step 2: Ball milling once; use alumina balls as the ball milling medium, and grind for 4 to 8 hours according to the mass ratio of mixture: balls: alcohol: (4-8): (2-5) to obtain a uniform mixture Ball abrasive;

步骤3：烘干，过筛；将步骤2所得球磨料烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200～1400℃条件下预烧3～5小时得到预烧粉体；Step 4: Pre-burning; place the dry powder obtained inStep 3 in an alumina crucible, and pre-fire at 1200-1400°C for 3-5 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(3～5)进行研磨2～4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium, according to the mass ratio of mixture: ball: alcohol is 1: (4 ~ 8): (3～5) Grinding for 2～4 hours to obtain a uniformly mixed secondary ball abrasive;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺压制得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以1～5℃/min的升温速率升温并在1700～1900℃下烧结8～12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 1-5°C/min, and sinter at 1700-1900°C for 8-12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2～4℃/min的升温速率升温并在1000～1450℃下退火10～13小时，得到最终的微波介质陶瓷材料；Step 9: annealing; the sample obtained in step 8 is heated in an oxygen atmosphere furnace at a heating rate of 2-4°C/min and annealed at 1000-1450°C for 10-13 hours to obtain the final microwave dielectric ceramic material;

优选的，所述步骤2和步骤5的球磨机为砂磨式球磨机。Preferably, the ball mills in step 2 andstep 5 are sand mills.

表1各实施例中各原材料的质量百分含量The mass percentage composition of each raw material in each embodiment of table 1

实施例1：Example 1:

步骤1：配料；将Y₂O₃、Al₂O₃和Ce₂O₃,分别按照54.9％、44.9％和0.2％的质量比进行备料；Step 1: batching; Y₂ O₃ , Al₂ O₃ and Ce₂ O₃ are prepared according to the mass ratio of 54.9%, 44.9% and 0.2% respectively;

步骤2：一次球磨：将得到的混合料以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的重量比为1:4:3进行球磨4小时，最后得到混合均匀的混合物；Step 2: Primary ball milling: the obtained mixture is milled with alumina balls as the ball milling medium, and absolute ethanol is used as the solvent, and the weight ratio of mixture: balls: ethanol is 1:4:3 for ball milling for 4 hours, and finally to obtain a homogeneous mixture;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200℃条件下预烧3小时得到预烧粉体；Step 4: Pre-calcining; the dry powder obtained inStep 3 is placed in an alumina crucible, and pre-fired at 1200°C for 3 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，以去无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:4:3进行研磨2小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium, and dehydrated ethanol as the solvent, according to the mass ratio of mixture: grinding ball: ethanol: 1:4:3 was ground for 2 hours to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺压制得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以1℃/min的升温速率升温并在1700℃下烧结8小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 1°C/min and sinter at 1700°C for 8 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2℃/min的升温速率升温并在1000℃下退火10小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 2° C./min and anneal at 1000° C. for 10 hours to obtain the final microwave dielectric ceramic material.

实施例2：Example 2:

步骤1：配料；将Y₂O₃、Al₂O₃和Gd₂O₃，分别按照54.9％、44.6％和0.5％的质量比进行备料，Step 1: batching; Y₂ O₃ , Al₂ O₃ and Gd₂ O₃ are prepared according to the mass ratio of 54.9%, 44.6% and 0.5% respectively,

步骤2：一次球磨；以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:5:4进行研磨4小时得到混合均匀的球磨料；Step 2: a ball mill; use alumina balls as the ball milling medium, use absolute ethanol as the solvent, and grind for 4 hours according to the mass ratio of mixture: balls: ethanol as 1:5:4 to obtain a uniformly mixed ball mill;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200℃条件下预烧3小时得到预烧粉体；Step 4: Pre-calcining; the dry powder obtained inStep 3 is placed in an alumina crucible, and pre-fired at 1200°C for 3 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:5:4进行研磨3小时得到混合均匀的二次球磨料；Step 5: Secondary ball milling; the calcined powder obtained in step 4 is ball milled for the second time, with alumina balls as the ball milling medium, and the mass ratio of mixture: balls: alcohol is 1:5:4 for grinding 3 hour to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺200Mpa压制得到生坯；Step 7: forming; put the dry powder obtained in step 6 into a forming mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以5℃/min的升温速率升温并在1800℃下烧结12小时得到样品；Step 8: sintering; put the green body obtained in step 7 in a sintering furnace, raise the temperature at a heating rate of 5°C/min, and sinter at 1800°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以4℃/min的升温速率升温并在1350℃下退火10小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 4° C./min and anneal at 1350° C. for 10 hours to obtain the final microwave dielectric ceramic material.

实施例3：Example 3:

步骤1：配料；将Y₂O₃、Al₂O₃、La₂O₃，分别按照54.9％、44.8％和0.3％的质量比进行备料；Step 1: batching; Y₂ O₃ , Al₂ O₃ , La₂ O₃ are prepared according to the mass ratio of 54.9%, 44.8% and 0.3% respectively;

步骤2：一次球磨；以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:6:3进行研磨8小时得到混合均匀的球磨料；Step 2: ball mill once; use alumina balls as the ball milling medium, and grind for 8 hours according to the mass ratio of mixture: ball: alcohol: 1:6:3 to obtain a uniformly mixed ball mill;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200℃条件下预烧3小时得到预烧粉体；Step 4: Pre-calcining; the dry powder obtained inStep 3 is placed in an alumina crucible, and pre-fired at 1200°C for 3 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，以去无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:5:5进行研磨4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium, and dehydrated ethanol as the solvent, according to the mass ratio of mixture: grinding ball: ethanol: 1:5:5 was ground for 4 hours to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺200Mpa压制得到生坯；Step 7: forming; put the dry powder obtained in step 6 into a forming mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以3℃/min的升温速率升温并在1850℃下烧结12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a heating rate of 3°C/min, and sinter at 1850°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以3℃/min的升温速率升温并在1350℃下退火13小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 3°C/min and anneal at 1350°C for 13 hours to obtain the final microwave dielectric ceramic material.

实施例4：Example 4:

步骤1：将Y₂O₃、Er₂O₃和Al₂O₃，分别按照53.2％、0.9％和45.9％的质量比进行备料；Step 1: Y₂ O₃ , Er₂ O₃ and Al₂ O₃ are prepared according to the mass ratio of 53.2%, 0.9% and 45.9% respectively;

步骤2：一次球磨；以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:8:5进行研磨7小时得到混合均匀的球磨料；Step 2: a ball mill; use alumina balls as the ball milling medium, use absolute ethanol as the solvent, and grind for 7 hours according to the mass ratio of mixture: balls: ethanol as 1:8:5 to obtain a uniformly mixed ball mill;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1400℃条件下预烧5小时得到预烧粉体；Step 4: Pre-calcining; the dry powder obtained inStep 3 is placed in an alumina crucible, and pre-calcined at 1400°C for 5 hours to obtain a pre-calcined powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，按照混合料：磨球：乙醇的质量比为1:8:5进行研磨3.5小时得到混合均匀的二次球磨料；Step 5: Secondary ball milling; the calcined powder obtained in step 4 is ball milled for the second time, with alumina balls as the ball milling medium, and the mass ratio of mixture: balls: ethanol is 1:8:5 for grinding 3.5 hour to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再于冷等静压机中200Mpa压制得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then press in a cold isostatic press at 200Mpa to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以4℃/min的升温速率升温并在1900℃下烧结12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 4°C/min and sinter at 1900°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以3℃/min的升温速率升温并在1350℃下退火13小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 3°C/min and anneal at 1350°C for 13 hours to obtain the final microwave dielectric ceramic material.

实施例5：Example 5:

步骤1：配料；将Y₂O₃、Al₂O₃、Ce₂O₃和Sm₂O₃分别按照50％、45.1％、0.6％和0.3％的质量比进行备料，将Y₂O₃和Ce₂O₃的混合物作为A组基料，Al₂O₃和Sm₂O₃的混合物作为B组基料。Step 1: batching; Y₂ O₃ , Al₂ O₃ , Ce₂ O₃ and Sm₂ O₃ are prepared according to the mass ratio of 50%, 45.1%, 0.6% and 0.3% respectively, Y₂ O₃ and The mixture of Ce₂ O₃ is used as group A base material, and the mixture of Al₂ O₃ and Sm₂ O₃ is used as group B base material.

步骤2：一次球磨；A组以二氧化锆球为球磨介质，以去离子水为溶剂，按照混合料：磨球：乙醇的重量比为1:7:2进行研磨8小时。B组则以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的重量比为1:7:2进行研磨8小时，分别得到AB两组基料；Step 2: Ball milling once; in group A, zirconia balls were used as the ball milling medium, deionized water was used as the solvent, and the weight ratio of mixture: balls: ethanol was 1:7:2 for grinding for 8 hours. Group B uses alumina balls as the ball milling medium and absolute ethanol as the solvent, and grinds for 8 hours according to the weight ratio of mixture: balls: ethanol as 1:7:2, and obtains two groups of base materials of A and B respectively;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛，各自得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain dry powders;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，A组基料在1250℃下预烧保温3h，B组基料在1270℃下预烧保温4h；得到预烧粉体；Step 4: Pre-burning; put the dry powder obtained instep 3 into an alumina crucible, pre-fire the base material of group A at 1250°C for 3 hours, and pre-fire the base material of group B at 1270°C for 4 hours; get calcined powder body;

步骤5：二次球磨；将步骤4所得预烧粉体全部混合，进行第二次球磨，以二氧化铝球为球磨介质，以去无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:7:4进行研磨4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; mix all the calcined powders obtained in step 4, and perform the second ball milling, with alumina balls as the ball milling medium and dehydrated ethanol as the solvent, according to the mixture: grinding balls: ethanol The mass ratio is 1:7:4 and grinds for 4 hours to obtain the secondary ball grinding material mixed uniformly;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺200Mpa压制得到生坯；Step 7: forming; put the dry powder obtained in step 6 into a forming mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以2℃/min的升温速率升温并在1810℃下烧结12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 2°C/min and sinter at 1810°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2℃/min的升温速率升温并在1300℃下退火10小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 2° C./min and anneal at 1300° C. for 10 hours to obtain the final microwave dielectric ceramic material.

实施例6：Embodiment 6:

步骤1：将Y₂O₃、Al₂O₃和Nd₂O₃，分别按照54.8％、44.6％和0.6％的质量比进行备料；Step 1: Y₂ O₃ , Al₂ O₃ and Nd₂ O₃ are prepared according to the mass ratio of 54.8%, 44.6% and 0.6% respectively;

步骤2：一次球磨；以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:5:2进行研磨8小时得到混合均匀的球磨料；Step 2: a ball mill; use alumina balls as the ball milling medium, use absolute ethanol as the solvent, and grind for 8 hours according to the mass ratio of mixture: balls: ethanol as 1:5:2 to obtain a uniformly mixed ball mill;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1250℃条件下预烧3小时得到预烧粉体；Step 4: pre-calcining; the dry powder obtained instep 3 is placed in an alumina crucible, and pre-fired at 1250°C for 3 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以去无水乙醇为溶剂，以二氧化铝球为球磨介质，按照混合料：磨球：乙醇的质量比为1:5:3进行研磨4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to a second ball milling, using dehydrated ethanol as a solvent, and alumina balls as a ball milling medium, according to the mass ratio of mixture: balls: ethanol: 1:5:3 was ground for 4 hours to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺于冷等静压机中200Mpa压制后得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa in a cold isostatic press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以4℃/min的升温速率升温并在1750℃下烧结12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 4°C/min, and sinter at 1750°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以4℃/min的升温速率升温并在1050℃下退火13小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 4° C./min and anneal at 1050° C. for 13 hours to obtain the final microwave dielectric ceramic material.

实施例7：Embodiment 7:

步骤1：配料；将Y₂O₃、Al₂O₃、Nd₂O₃和Yb₂O₃分别按照52.4％、46.3％、0.6％和0.7％的质量比进行备料，将Y₂O₃和Nd₂O₃的混合物作为A组基料，Al₂O₃和Yb₂O₃的混合物作为B组基料。Step 1: batching; Y₂ O₃ , Al₂ O₃ , Nd₂ O₃ and Yb₂ O₃ are prepared according to the mass ratio of 52.4%, 46.3%, 0.6% and 0.7% respectively, Y₂ O₃ and The mixture of Nd₂ O₃ is used as group A base material, and the mixture of Al₂ O₃ and Yb₂ O₃ is used as group B base material.

步骤2：一次球磨；其中A组以二氧化锆球为球磨介质，以去离子水为溶剂，按照混合料：磨球：乙醇的重量比为1:6:2进行研磨8小时。B组则以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的重量比为1:6:2进行研磨8小时，分别得到AB两组基料；Step 2: Ball milling once; group A uses zirconia balls as the ball milling medium, deionized water as the solvent, and grinds for 8 hours according to the weight ratio of mixture: balls: ethanol is 1:6:2. Group B uses alumina balls as the ball milling medium and absolute ethanol as the solvent, and grinds for 8 hours according to the weight ratio of mixture: balls: ethanol as 1:6:2, and obtains two groups of base materials of A and B respectively;

步骤3：烘干，过筛；球磨后的AB两组混合物分别在110℃和70℃下烘干并过200目筛，各自得到干燥粉体；Step 3: Drying and sieving; after ball milling, the two groups of mixtures A and B were dried at 110°C and 70°C respectively and passed through a 200-mesh sieve to obtain dry powders;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，A组基料在1250℃下预烧保温3h，B组基料在1350℃下预烧保温3h；Step 4: Pre-fire; put the dry powder obtained instep 3 into an alumina crucible, pre-fire the base material of group A at 1250°C for 3 hours, and pre-fire the base material of group B at 1350°C for 3 hours;

步骤5：二次球磨；将A组基料和B组基料样品烧块粉碎混合，进行第二次球磨，以二氧化铝球为球磨介质，以去无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:6:3进行研磨4小时得到混合均匀的二次球磨料；Step 5: Secondary ball milling; crush and mix the base material samples of group A and group B, and then perform the second ball milling, using alumina balls as the ball milling medium and dehydrated ethanol as the solvent, according to the mixture: Grinding balls: the mass ratio of ethanol is 1:6:3 and ground for 4 hours to obtain a uniformly mixed secondary ball grinding material;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺于冷等静压机中200Mpa压制得到生坯；Step 7: Molding; put the dry powder obtained in Step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa in a cold isostatic press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以4℃/min的升温速率升温并在1775℃下烧结8小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 4°C/min and sinter at 1775°C for 8 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以4℃/min的升温速率升温并在1775℃下退火8小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 4°C/min and anneal at 1775°C for 8 hours to obtain the final microwave dielectric ceramic material.

实施例8：Embodiment 8:

步骤1：配料；将Y₂O₃、Lu₂O₃和Al₂O₃，分别按照54.4％、0.8％和44.8％的质量比进行备料，Step 1: batching; Y₂ O₃ , Lu₂ O₃ and Al₂ O₃ are prepared according to the mass ratio of 54.4%, 0.8% and 44.8% respectively,

步骤2：一次球磨；以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:5:3进行研磨7小时得到混合均匀的球磨料；Step 2: a ball mill; use alumina balls as the ball milling medium, and grind for 7 hours according to the mass ratio of mixture: balls: alcohol of 1:5:3 to obtain a uniformly mixed ball mill;

步骤3：烘干，过筛；将步骤2所得球磨料在70℃下烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 at 70°C and passing through a 200-mesh sieve to obtain a dry powder;

步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1315℃条件下预烧4小时得到预烧粉体；Step 4: Pre-calcining; the dry powder obtained inStep 3 is placed in an alumina crucible, and pre-fired at 1315°C for 4 hours to obtain a pre-fired powder;

步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，以无水乙醇为溶剂，按照混合料：磨球：乙醇的质量比为1:5:3进行研磨3.5小时得到混合均匀的二次球磨料；Step 5: Secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium and absolute ethanol as the solvent, according to the mass ratio of mixture: balls: ethanol is 1 :5:3 was ground for 3.5 hours to obtain a uniformly mixed secondary ball mill;

步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained instep 5 and passing through a 200-mesh sieve to obtain a dry powder;

步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺于冷等静压机中200Mpa压制得到生坯；Step 7: Molding; put the dry powder obtained in Step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press at 200Mpa in a cold isostatic press to obtain a green body;

步骤8：烧结；将步骤7所得生坯放于烧结炉中，以5℃/min的升温速率升温并在1850℃下烧结12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a heating rate of 5°C/min, and sinter at 1850°C for 12 hours to obtain a sample;

步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2℃/min的升温速率升温并在1450℃下退火11小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 2° C./min and anneal at 1450° C. for 11 hours to obtain the final microwave dielectric ceramic material.

表2各实施例采用的工艺和微波介电性能Process and microwave dielectric properties adopted by each embodiment of table 2

上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.

Claims (5)

Translated fromChinese

1.一种钇过量的掺稀土元素YAG微波介质陶瓷材料，其特征在于：材料化学通式为Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1。1. A rare earth-doped YAG microwave dielectric ceramic material with excessive yttrium, characterized in that: the general chemical formula of the material is Y_3.03-x Re_x Al₅ O₁₂ , wherein Re is La³⁺ , Ce³⁺ , Nd^{3 +} , Sm³⁺ , Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ one or more of various rare earth ions; 0.03≤x≤0.1.2.根据权利要求1所述的一种钇过量的掺稀土元素YAG微波介质陶瓷材料，其特征在于：所述微波介质陶瓷材料所用的原料包括三氧化二钇和三氧化二铝，以及La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃其中一种或多种；将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合，在1200～1400℃下预烧，再经过第二次球磨混合，经冷等静压成型后，在1700～1900℃下进行真空烧结且在氧气控制气氛下退火后制成。2. the excessive rare earth element YAG microwave dielectric ceramic material of a kind of yttrium according to claim 1 is characterized in that: the used raw material of described microwave dielectric ceramic material comprises diyttrium oxide and aluminum oxide, and La₂ One or more of O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , Er₂ O₃ , Yb₂ O₃ and Lu₂ O₃ ; According to the above chemical general formula, after the first ball milling and mixing, pre-calcination at 1200-1400°C, and then after the second ball milling and mixing, after cold isostatic pressing, vacuum sintering at 1700-1900°C And it is made after annealing under oxygen controlled atmosphere.3.根据权利要求1所述的一种钇过量的掺稀土元素YAG微波介质陶瓷材料，其特征在于：材料晶界处存在刃型位错结构，材料Q×f在160000GHz～200000GHz之间，相对介电常数ε_r在10～16之间，频率温度系数τ_f在-36ppm/℃～-25ppm/℃之间。3. A kind of yttrium-excess rare-earth-doped YAG microwave dielectric ceramic material according to claim 1, characterized in that: there is an edge dislocation structure at the grain boundary of the material, and the material Q×f is between 160,000 GHz and 200,000 GHz, relatively The dielectric constant ε_r is between 10 and 16, and the frequency temperature coefficient τ_f is between -36ppm/℃～-25ppm/℃.4.权利要求1至3任意一项所述的一种钇过量的掺稀土元素YAG微波介质陶瓷材料的制备方法，包括以下步骤：4. the preparation method of a kind of yttrium excessive doping rare earth element YAG microwave dielectric ceramic material described in any one of claims 1 to 3, comprises the following steps:步骤1：配料；原料选自三氧化二钇和三氧化二铝粉末，以及一种或多种La₂O₃，Ce₂O₃，Nd₂O₃，Sm₂O₃，Gd₂O₃，Er₂O₃，Yb₂O₃和Lu₂O₃，按照化学通式Y_3.03-xRe_xAl₅O₁₂，其中，Re为La³⁺，Ce³⁺，Nd³⁺，Sm³⁺，Gd³⁺，Er³⁺，Yb³⁺，Lu³⁺多种稀土离子中的一种或多种；0.03≤x≤0.1，，配料形成混合物；Step 1: batching; raw materials are selected from diyttrium trioxide and aluminum oxide powder, and one or more of La₂ O₃ , Ce₂ O₃ , Nd₂ O₃ , Sm₂ O₃ , Gd₂ O₃ , Er₂ O₃ , Yb₂ O₃ and Lu₂ O₃ , according to the general chemical formula Y_3.03-x Re_x Al₅ O₁₂ , wherein, Re is La³⁺ , Ce³⁺ , Nd³⁺ , Sm³⁺ , One or more of Gd³⁺ , Er³⁺ , Yb³⁺ , Lu³⁺ rare earth ions; 0.03≤x≤0.1, the ingredients form a mixture;步骤2：一次球磨；以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(3～5)进行研磨4～8小时得到混合均匀的球磨料；Step 2: Ball milling once; use alumina balls as the ball milling medium, and grind for 4 to 8 hours according to the mass ratio of mixture: balls: alcohol: (4-8): (3-5) to obtain a uniform mixture Ball abrasive;步骤3：烘干，过筛；将步骤2所得球磨料烘干并过200目筛得到干燥粉体；Step 3: drying and sieving; drying the ball mill material obtained in step 2 and passing through a 200-mesh sieve to obtain a dry powder;步骤4：预烧；将步骤3所得干燥粉体置于氧化铝坩埚中，1200～1400℃条件下预烧3～5小时得到预烧粉体；Step 4: Pre-burning; place the dry powder obtained in Step 3 in an alumina crucible, and pre-fire at 1200-1400°C for 3-5 hours to obtain a pre-fired powder;步骤5：二次球磨；将步骤4所得预烧粉体进行第二次球磨，以二氧化铝球为球磨介质，按照混合料：磨球：酒精的质量比为1:(4～8):(3～5)进行研磨2～4小时得到混合均匀的二次球磨料；Step 5: secondary ball milling; the calcined powder obtained in step 4 is subjected to the second ball milling, with alumina balls as the ball milling medium, according to the mass ratio of mixture: ball: alcohol is 1: (4 ~ 8): (3～5) Grinding for 2～4 hours to obtain a uniformly mixed secondary ball abrasive;步骤6：烘干，过筛；将步骤5所得二次球磨料烘干并过200目筛得到干燥粉体；Step 6: drying and sieving; drying the secondary ball mill material obtained in step 5 and passing through a 200-mesh sieve to obtain a dry powder;步骤7：成型；将步骤6所得干燥粉体放入成型模具中干压成型，再利用冷等静压工艺压制得到生坯；Step 7: molding; put the dry powder obtained in step 6 into a molding mold for dry pressing, and then use a cold isostatic pressing process to press to obtain a green body;步骤8：烧结；将步骤7所得生坯放于烧结炉中，以1～5℃/min的升温速率升温并在1700～1900℃下烧结8～12小时得到样品；Step 8: Sintering; put the green body obtained in Step 7 in a sintering furnace, raise the temperature at a rate of 1-5°C/min, and sinter at 1700-1900°C for 8-12 hours to obtain a sample;步骤9：退火；将步骤8所得样品在氧气气氛炉中，以2～4℃/min的升温速率升温并在1000～1450℃下退火10～13小时，得到最终的微波介质陶瓷材料。Step 9: annealing; heat up the sample obtained in step 8 in an oxygen atmosphere furnace at a heating rate of 2-4°C/min and anneal at 1000-1450°C for 10-13 hours to obtain the final microwave dielectric ceramic material.5.根据权利要求4所述的一种钇过量的掺稀土元素YAG微波介质陶瓷材料的制备方法，其特征在于：所述步骤2和步骤5的球磨机为砂磨式球磨机。5 . The preparation method of a rare earth-doped YAG microwave dielectric ceramic material with excess yttrium according to claim 4 , characterized in that: the ball mill in the step 2 and step 5 is a sand mill. 6 .

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