CN115180941A - high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof - Google Patents
high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN115180941A CN115180941A CN202210782067.XA CN202210782067A CN115180941A CN 115180941 A CN115180941 A CN 115180941A CN 202210782067 A CN202210782067 A CN 202210782067A CN 115180941 A CN115180941 A CN 115180941A
- Authority
- CN
- China
- Prior art keywords
- tio
- source
- microwave dielectric
- dielectric ceramic
- ceramic material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention relates to a high Q value near zero Tf composite microwave dielectric ceramic material, which comprises the following raw materials of general formula 1-a (Mg) 1‑ x Co x ) 2 TiO 4 —a(Ca 1‑3/2y M y )TiO 3 The ceramic comprises a ceramic main material with the structure and an auxiliary agent accounting for 0-15wt% of the ceramic main material; ceramic major ingredient 1-a (Mg) 1‑x Co x ) 2 TiO 4 —a(Ca 1‑3y/2 M y )TiO 3 In 0 of<a≤0.2，0<x<0.1，0<y<0.1,M element is at least one element selected from among Nd element, sm element, la element, and Nb element. The ceramic material has high quality factor, a dielectric constant of 18-23 and a temperature of 25 DEG CQ f of (1)>60000, the value of the resonance frequency Tf is close to zero; the sintering temperature of the material is only 1250-1350 ℃, the low-temperature sintering performance is greatly improved, and the material can be stably produced in large batches.
Description
Technical Field
The invention relates to a ceramic material, in particular to a high-Q-value near-zero Tf composite microwave dielectric ceramic material and a preparation method thereof.
Background
The microwave dielectric ceramic is ceramic which is used as a dielectric material in a microwave frequency band (mainly UHF and SHF frequency bands, 300MHz-300 GHz) circuit and completes one or more functions, has excellent performances such as high dielectric constant, low dielectric loss, low resonant frequency temperature coefficient and the like, is an important component of devices such as a resonator, a filter, a duplexer, an antenna, a frequency stabilization oscillator, a waveguide transmission line and the like, and can be widely applied to numerous fields such as personal portable mobile phones, microwave base stations, vehicle-mounted phones, satellite communication, military radars and the like. Especially, in recent years, with the rapid development of communication technology, the demand for microwave devices is increasing, especially the demand for filters is increasing due to the increase of the number of base stations in the 5G communication era, and ceramic dielectric filters are receiving more and more attention due to the advantages of high Q value, good frequency selection characteristic, good stability of operating frequency, small insertion loss, miniaturization, integration and the like, which becomes a hot direction in the research field of microwave dielectric materials at home and abroad in recent years. Especially with the coming of the 5G era, higher requirements are put on microwave dielectric ceramics, so that the microwave dielectric ceramics have high quality factor and low loss
Microwave dielectric ceramic materials have been extensively studied. In the existing microwave dielectric ceramic system with high Q value, most of the microwave dielectric ceramic system has higher sintering temperature, such as Al2O3; or precious metal elements such as lithium-magnesium-niobium series microwave dielectric ceramics are adopted, so that the production cost is greatly increased, and the development and utilization of microwave dielectric devices in the fields of mobile communication and the like are limited. Therefore, the Q multiplied by f is improved as much as possible, and the research on novel magnesium-titanium microwave dielectric ceramics becomes more and more important.
The existing research shows that the key for realizing the performance of the microwave dielectric ceramic device is based on the performance of the microwave dielectric ceramic material. In the prior art, there are various classification methods for microwave dielectric ceramic materials, wherein, according to the size of dielectric constant, microwave dielectric ceramic materials can be classified into three categories: one is low dielectric constant microwave dielectric ceramics, which mainly comprises A12O3, mg2SiO4, zn2SiO4, mgTiO3 and the like; the other is medium dielectric constant microwave dielectric ceramics, which mainly comprises a BaO-TiO2 system, an Ln2O3-TiO2 system, calcium-based or barium-based composite perovskite and the like; and the third is high dielectric constant microwave dielectric ceramic, which mainly comprises TiO2, caTiO3, baO-Ln2O3-TiO2, lead-based composite perovskite and the like.
The existing research shows that the key for realizing the performance of the microwave dielectric ceramic device is based on the performance of the microwave dielectric ceramic material, and although different application fields require the material to have high quality factor and stability, the dielectric constant of the microwave dielectric ceramic material is required to be different due to different application directions and frequency bands. At present, mgO-TiO2 system ceramics are mainly applied to the preparation of microwave dielectric ceramics with dielectric constants of 15-25, and in the system, the research on crystal structure materials of magnesium metatitanate MgTiO3 and magnesium orthotitanate Mg2TiO4 is more, and the application field is the most extensive. However, the MgO-TiO2 material has limited application due to its high temperature coefficient of resonance frequency (-55 ppm/deg.C), easy growth of crystal grains, and high sintering temperature (1450 deg.C).
Therefore, how to effectively reduce MgO-TiO 2 The temperature coefficient of the resonant frequency and the sintering temperature of the system material further develop the MgO-TiO2 system microwave dielectric ceramic material which has the temperature coefficient of the resonant frequency close to zero, keeps high quality factor, has low sintering temperature and is convenient for realizing industrial production.
Disclosure of Invention
In order to solve the problems, the invention provides a high Q value near-zero Tf composite microwave dielectric ceramic material which has a near-zero resonance frequency Tf value, keeps a high quality factor, has a low sintering temperature and is convenient for industrial production, and the specific technical scheme is as follows:
a high Q value near zero Tf composite microwave dielectric ceramic material comprises the following raw materials of general formula 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3/2y M y )TiO 3 The ceramic comprises a ceramic main material with the structure and an auxiliary agent accounting for 0-15wt% of the ceramic main material; the ceramic main material 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 Middle 0<a≤0.2，0<x<0.1，0<y<0.1,M element is at least one element selected from among Nd element, sm element, la element, and Nb element.
Preferably, the auxiliary agent comprises a functional additive and/or a sintering aid.
Further, the auxiliary agent comprises TiO 2 、CaTiO 3 、B 2 O 3 、MnCO 3 、CeO 2 、Al 2 O 3 、Nd 2 O 3 One or more of (a).
A preparation method for preparing any one of the high-Q near-zero Tf composite microwave dielectric ceramic materials comprises the following steps:
(1) According to 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 Stoichiometric ratio of expression magnesium source, titanium source, cobalt source, calcium source, M source, 0<a≤0.2，0<x<0.1，0<y<0.1; the M element is at least one element selected from Nd element, sm element, la element and Nb element; carrying out primary ball milling on the weighed magnesium source, titanium source, cobalt source, calcium source and M source to obtain a primary ball-milled raw material;
(2) Drying and grinding the raw materials subjected to the primary ball milling to obtain powder;
(3) Calcining the powder to obtain calcined powder, wherein the calcining temperature is 1150-1200 ℃, and the calcining time is 3-5 h; and the powder is poured into the crucible and then calcined.
(4) Taking a selected amount of said 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 Mixing calcined powder and an auxiliary agent to obtain a mixture, adding water, a dispersing agent and a surfactant to perform ball milling, premixing and dispersing, and performing sanding and redispersing treatment;
(5) And adding glue into the sanded material, performing spray granulation, and sieving the granulated powder with a 120-mesh sieve to obtain the high-Q-value near-zero Tf composite microwave dielectric ceramic material.
In step (3), 1180 ℃ is preferred. If the calcining temperature is too high, the hardness of the pre-sintered material is too high, which is not beneficial to the operation of secondary ball milling; if the calcination temperature is too low, the desired material cannot be synthesized, and the properties of the final sample are adversely affected.
Preferably, in the step (1): the auxiliary agent comprises TiO 2 、CaTiO 3 、B 2 O 3 、SiO 2 、CeO 2 、MnCO 3 、Al 2 O 3 、Nd 2 O 3 One or more of; the mass ratio of the mixture to the water is 1:0.4-0.6;
the addition amount of the dispersant and the surfactant accounts for 0.2-1.0wt% of the mass of the mixture.
Preferably, in the step (2), the glue comprises polyvinyl alcohol, PEG400, a release agent and a defoaming agent, and the total glue content in the glue is 3-10wt%.
Preferably, the step (1) further comprises solid phase synthesis of 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The method specifically comprises the following steps: weighing any Mg source, co source, ti source, ca source and M source as raw materials according to the selected stoichiometric ratio, and mixing to obtain a mixture; respectively adding water, a dispersing agent and a surfactant to carry out ball milling, premixing and dispersing, and sanding and redispersing treatment; then microwave drying the dispersed material, and calcining the dried powder at 1180 +/-15 ℃ to obtain the required 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 。
Further, the Mg source is MgO and MgCO 3 Or Mg (OH) 2 Any one or a combination of at least two of; the titanium source is TiO 2 (ii) a The cobalt source is CoO; the calcium source is CaCO 3 (ii) a The purity of the magnesium source, the titanium source, the calcium source, the cobalt source and the M source is more than 99 percent; a =0.13; x =0.03, y =0.02.
Preferably, the solid phase synthesis of 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The mass ratio of the mixture to water in the step (2) is 1; the addition amount of the dispersant and the surfactant accounts for 0.4 to 1.5 weight percent of the amount of the mixture; the step of microwave drying controls the moisture content of the material<1％。
A microwave dielectric ceramic element is prepared from any one of the composite microwave dielectric ceramic materials with high Q value and approximate zero Tf.
A preparation method of a microwave dielectric ceramic element comprises the steps of carrying out compression molding on any one of the composite microwave dielectric ceramic materials with the high Q value and the approximate zero Tf to obtain a blank body, and carrying out heat preservation sintering on the blank body at 1280-1380 ℃.
The composite microwave dielectric ceramic material enables the Tf of the material to move in the positive direction by doping Ca and Co elements, adjusts the Tf value to be close to zero, keeps a high quality factor, improves the dielectric constant to a certain degree, can reduce the sintering temperature of the material, and can meet the use requirement of a filter in microwave performance.
The composite microwave dielectric ceramic material is further added with TiO 2 、CaTiO 3 The functional auxiliary agent and/or sintering auxiliary agent effectively further optimizes the microwave performance of the material, so that the Tf of the material is further reduced to be close to 0, the dielectric constant is increased to a certain degree, the sintering temperature of the material can be reduced to 1250-1350 ℃, the material performance is further optimized, and the material can be stably produced in large batches.
Compared with the prior art, the invention has the following beneficial effects:
the high Q value near zero Tf composite microwave dielectric ceramic material provided by the invention has a high quality factor, a dielectric constant of 18-23, a Q & ltf & gt 60000 at 25 ℃, and a resonance frequency Tf value near zero, and can meet the use requirement of a filter; and the sintering temperature of the material is only 1250-1350 ℃, the low-temperature sintering performance is greatly improved, and the material can be stably produced in batches.
Drawings
FIG. 1 is an SEM topography of the composite microwave dielectric ceramic powder prepared in example 8;
FIG. 2 is a SEM microstructure of a composite microwave dielectric ceramic product prepared in example 8;
FIG. 3 is a graph of the variation trend of the composite microwave dielectric ceramic product obtained in example 8 with the corresponding sintering temperature as the abscissa and the quality factor as the ordinate;
FIG. 4 is a graph of the variation trend of the composite microwave dielectric ceramic product obtained in example 8 with the corresponding sintering temperature as the abscissa and the relative dielectric constant as the ordinate;
FIG. 5 is a graph of the variation trend of the composite microwave dielectric ceramic product obtained in example 8 with the corresponding sintering temperature as the abscissa and the relative density as the ordinate;
fig. 6 is a variation trend graph obtained by using the corresponding ambient temperature as the abscissa and the resonant frequency as the ordinate of the composite microwave dielectric ceramic product prepared in example 8.
Detailed Description
The invention will now be further described with reference to the accompanying drawings.
Examples 1 to 11
1-a (Mg) shown in Table 1 below, respectively 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The structure and the stoichiometric ratio of the material are respectively Mg (OH) 2 、CaCO 3 、CoO、TiO 2 And M, mixing to obtain a mixture, and mixing according to the following steps: the mass ratio of water is 1:1.2, adding water for mixing, adding a dispersing agent accounting for 0.5wt% of the total weight of the mixture and a surfactant accounting for 0.5wt% of the total weight of the mixture, performing ball milling treatment by using agate balls, performing primary mixing and dispersion on the materials within 4-6h, placing the materials in a sand mill, further dispersing the materials by using zirconium balls with the diameter of 0.65mm as grinding media, drying the materials after grinding by using a microwave dryer until the water content is less than 1%, sieving the dried materials by using a crusher, calcining the materials by using a push plate furnace at the calcining temperature of 1180 ℃ for 3h, and placing the calcined materials for later use to obtain 1-a (Mg) with the required structure 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 And (5) preparing materials for later use.
Taking the above systemPrepared 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 100g of materials are mixed according to the components and the dosage of the auxiliary agent (additive or sintering auxiliary agent) shown in the following table 1 to obtain a mixture, and the mixture is prepared according to the following steps: mixing water according to the mass ratio of 1.
Dissolving polyvinyl alcohol in water at 90 + -5 deg.C to obtain 10wt% polyvinyl alcohol solution, wherein the PEG400 glue is directly purchased liquid glue.
Adding 3.0wt% of polyvinyl alcohol glue solution, 1.5wt% of PEG400 glue solution, 1.2% of defoaming agent and 1.5% of release agent which account for the solid mass of the raw materials into the obtained slurry after sanding in sequence and stirring uniformly; and spray-drying and granulating by a spray dryer, controlling the inlet temperature to be 220 +/-10 ℃ and the outlet temperature to be 120 +/-0 ℃, and sieving by a 60-mesh sieve to obtain the required composite microwave medium ceramic powder material.
TABLE 1 microwave dielectric ceramic material composition and dosage table
And (3) respectively molding and sintering the granulated powder material, recording the sintering temperature of each green body, keeping the temperature for 4 hours, and respectively carrying out performance test on the microwave dielectric ceramic materials prepared in the embodiments 1-11. The test performance specifically includes:
the detection method of the embodiment of the invention comprises the following steps:
1. the diameter and thickness of the sample are measured using a vernier caliper or a micrometer.
2. The dielectric constant and the f × Q value at 25 ℃ of the prepared ceramic cylinder were measured by an agilent e5071C network analyzer using a dielectric resonator complex dielectric constant measuring device, and the resonant frequency temperature coefficient Tf was measured using a high/low temperature operating box.
The frequency temperature coefficient Tf represents a good temperature characteristic, and is calculated by respectively testing the resonant frequency f at-40 ℃, 25 ℃ and 130 ℃ according to the following formula:
[(f130℃-f-40℃)/f-40℃*170]/(ppm/℃)。
the results of the measurements and calculations are shown in Table 2 below.
TABLE 2 Performance test results of microwave dielectric ceramic materials
As shown in the above table and fig. 1 to 6, the composite microwave dielectric ceramic material of the present invention has a high quality factor, a dielectric constant of 18 to 23, f × Q >60000 at 25 ℃, and a resonance frequency Tf value close to zero, and can meet the use requirements of a filter; and the sintering temperature of the material is only 1250-1350 ℃, the low-temperature sintering performance is greatly improved, and the material can be stably produced in batches.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (11)
1. A high Q value near zero Tf composite microwave dielectric ceramic material is characterized in that the raw material composition comprises the following general formula 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3/2y M y )TiO 3 The ceramic comprises a ceramic main material with the structure and an auxiliary agent accounting for 0-15wt% of the ceramic main material; the ceramic main material 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 In 0 of<a≤0.2，0<x<0.1，0<y<0.1, M element is selected from Nd element, sm element, la elementAnd at least one of Nb elements.
2. The high Q near zero Tf composite microwave dielectric ceramic material of claim 1, wherein said additives comprise functional additives and/or sintering additives.
3. The high Q near zero Tf composite microwave dielectric ceramic material of claim 2, wherein the additive comprises TiO 2 、CaTiO 3 、B 2 O 3 、MnCO 3 、CeO 2 、Al 2 O 3 、Nd 2 O 3 One or more of (a).
4. A preparation method for preparing the high Q value near zero Tf composite microwave dielectric ceramic material of any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) According to the formula 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The stoichiometric ratio of the expression is that the magnesium source, the titanium source, the cobalt source, the calcium source and the M source are weighed, 0<a≤0.2，0<x<0.1，0<y<0.1; the M element is at least one element selected from Nd element, sm element, la element and Nb element; carrying out primary ball milling on the weighed magnesium source, titanium source, cobalt source, calcium source and M source to obtain a primary ball-milled raw material;
(2) Drying and grinding the raw materials subjected to the primary ball milling to obtain powder;
(3) Calcining the powder to obtain calcined powder, wherein the calcining temperature is 1150-1200 ℃, and the calcining time is 3-5 h; and the powder is poured into the crucible and then calcined.
(4) Taking a selected amount of said 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 Mixing calcined powder and an auxiliary agent to obtain a mixture, adding water, a dispersing agent and a surfactant to perform ball milling, premixing and dispersing, and performing sanding and redispersion treatment;
(5) And adding glue into the sanded material, performing spray granulation, and sieving the granulated powder with a 120-mesh sieve to obtain the high-Q-value near-zero Tf composite microwave dielectric ceramic material.
5. The method for preparing a high Q value near zero Tf composite microwave dielectric ceramic material as claimed in claim 4, wherein in the step (1):
the auxiliary agent comprises TiO 2 、CaTiO 3 、B 2 O 3 、SiO 2 、CeO 2 、MnCO 3 、Al 2 O 3 、Nd 2 O 3 One or more of;
the mass ratio of the mixture to the water is 1:0.4-0.6;
the addition amount of the dispersant and the surfactant accounts for 0.2-1.0wt% of the mass of the mixture.
6. The method for preparing a high Q-value near-zero Tf composite microwave dielectric ceramic material as claimed in claim 4, wherein in the step (2), the glue comprises polyvinyl alcohol, PEG400, a release agent and a defoaming agent, and the total glue content in the glue is 3-10wt%.
7. The preparation method of the high Q near zero Tf composite microwave dielectric ceramic material of any one of claims 1 to 6,
the step (1) also comprises solid phase synthesis of 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The method specifically comprises the following steps: weighing any Mg source, co source, ti source, ca source and M source as raw materials according to the selected stoichiometric ratio, and mixing to obtain a mixture; respectively adding water, a dispersing agent and a surfactant to carry out ball milling, premixing and dispersing, and sanding and redispersing treatment; then microwave drying the dispersed material, and calcining the dried powder at 1180 +/-15 ℃ to obtain the required 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 。
8. The method for preparing a high Q value near zero Tf composite microwave dielectric ceramic material of claim 7,
the Mg source is MgO and MgCO 3 Or Mg (OH) 2 Any one or a combination of at least two of;
the titanium source is TiO 2 ；
The cobalt source is CoO;
the calcium source is CaCO 3 ；
The purity of the magnesium source, the titanium source, the calcium source, the cobalt source and the M source is more than 99 percent;
a＝0.13；x＝0.03，y＝0.02。
9. the method for preparing a high Q value near zero Tf composite microwave dielectric ceramic material of claim 7,
solid phase Synthesis of 1-a (Mg) 1-x Co x ) 2 TiO 4 —a(Ca 1-3y/2 M y )TiO 3 The mass ratio of the mixture to water in the step (2) is 1-1.5;
the addition amount of the dispersant and the surfactant accounts for 0.4 to 1.5 weight percent of the amount of the mixture;
the microwave drying step controls the moisture content of the material to be less than 1%.
10. A microwave dielectric ceramic component, which is prepared from the high-Q near-zero Tf composite microwave dielectric ceramic material as claimed in any one of claims 1 to 3.
11. A method for preparing a microwave dielectric ceramic element, which is characterized in that the composite microwave dielectric ceramic material with high Q value and approximate zero Tf of any one of claims 1 to 3 is pressed and molded to obtain a green body, and the green body is sintered at 1280-1380 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210782067.XA CN115180941A (en) | 2022-07-04 | 2022-07-04 | high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210782067.XA CN115180941A (en) | 2022-07-04 | 2022-07-04 | high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115180941A true CN115180941A (en) | 2022-10-14 |
Family
ID=83515189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210782067.XA Pending CN115180941A (en) | 2022-07-04 | 2022-07-04 | high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115180941A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826833A (en) * | 1994-07-19 | 1996-01-30 | Murata Mfg Co Ltd | Production of ceramic raw material |
| JPH0912359A (en) * | 1995-04-26 | 1997-01-14 | Matsushita Electric Ind Co Ltd | Dielectric porcelain composition |
| CN102503406A (en) * | 2011-11-14 | 2012-06-20 | 电子科技大学 | Microwave device ceramic substrate material and preparation method thereof |
| CN111170734A (en) * | 2020-01-07 | 2020-05-19 | 山东国瓷功能材料股份有限公司 | Two-phase composite microwave dielectric ceramic material for filter and preparation method thereof |
| CN113998990A (en) * | 2021-10-27 | 2022-02-01 | 江苏贝孚德通讯科技股份有限公司 | Microwave dielectric ceramic material, microwave dielectric ceramic device and preparation method thereof |
-
2022
- 2022-07-04 CN CN202210782067.XA patent/CN115180941A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826833A (en) * | 1994-07-19 | 1996-01-30 | Murata Mfg Co Ltd | Production of ceramic raw material |
| JPH0912359A (en) * | 1995-04-26 | 1997-01-14 | Matsushita Electric Ind Co Ltd | Dielectric porcelain composition |
| CN102503406A (en) * | 2011-11-14 | 2012-06-20 | 电子科技大学 | Microwave device ceramic substrate material and preparation method thereof |
| CN111170734A (en) * | 2020-01-07 | 2020-05-19 | 山东国瓷功能材料股份有限公司 | Two-phase composite microwave dielectric ceramic material for filter and preparation method thereof |
| CN113998990A (en) * | 2021-10-27 | 2022-02-01 | 江苏贝孚德通讯科技股份有限公司 | Microwave dielectric ceramic material, microwave dielectric ceramic device and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHENG-LIANG HUANG ET AL.: "A new dielectric material system using (1 − x)(Mg0.95Co0.05)2TiO4–xCa0.8Sm0.4/3TiO3 at microwave frequencies", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111116186B (en) | Low-dielectric-constant two-phase composite microwave dielectric ceramic material and preparation method thereof | |
| CN105669177B (en) | Magnetodielectric Y-phase strontium hexagonal ferrite material formed by sodium replacement | |
| CN111170734B (en) | Two-phase composite microwave dielectric ceramic material for filter and preparation method thereof | |
| CN111138176B (en) | Magnesium silicate based microwave dielectric ceramic material and preparation method and application thereof | |
| CN111099892A (en) | Barium titanate-based two-phase composite microwave dielectric ceramic material and preparation method thereof | |
| CN112851344B (en) | Microwave dielectric ceramic with medium dielectric constant and preparation method thereof | |
| CN111138193B (en) | Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof | |
| CN107188557B (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN108147809B (en) | Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof | |
| CN105254293A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN111170738A (en) | Two-phase composite microwave dielectric ceramic material and preparation method and application thereof | |
| CN113105231A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN111925207B (en) | Mg3B2O6-Ba3(VO4)2Composite ceramic material and preparation method thereof | |
| CN115180941A (en) | high-Q-value near-zero Tf composite microwave dielectric ceramic material and preparation method thereof | |
| JP7196345B2 (en) | Magnetoplumbite-type hexagonal ferrite magnetic powder, method for producing the same, radio wave absorber, and method for producing the same | |
| WO2010050514A1 (en) | Dielectric ceramic and resonator using the same | |
| CN105503202A (en) | Novel low-loss Li2MgZrO4 microwave dielectric ceramic material and preparing method | |
| CN111825445B (en) | High-dielectric-constant microwave dielectric ceramic material, preparation and application thereof | |
| CN113998990A (en) | Microwave dielectric ceramic material, microwave dielectric ceramic device and preparation method thereof | |
| JP2004018365A (en) | Composition for microwave dielectric ceramic and method of manufacturing the ceramic | |
| CN111018524B (en) | Low-loss trigonal tungstate-based microwave dielectric ceramic and preparation method thereof | |
| CN113387695A (en) | Low-dielectric high-quality microwave dielectric ceramic for 5G communication and preparation method thereof | |
| CN113436823A (en) | Ferrite sintered magnet | |
| KR100444178B1 (en) | Dielectric ceramic composition of MgAl2O4 system and a method for fabricating dielectric ceramic composition using the same | |
| CN112794368A (en) | Composite material with high magnetic permeability and low dielectric constant as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |