CN115010489B - Mineral-based microwave dielectric ceramic material and preparation method and application thereof - Google Patents
Mineral-based microwave dielectric ceramic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a mineral-based microwave dielectric ceramic material and a preparation method and application thereof. The preparation method comprises the following steps: step 1: mixing the raw materialsCuO、MoO 3 According to CuMoO 4 Mixing the components according to the stoichiometric ratio, and performing wet ball milling to obtain slurry; step 2: drying the slurry, calcining for 6-12 hours at a certain temperature to obtain CuMoO 4 Pre-sintering the powder; and step 3: the presintering powder is dried for standby after being ball-milled by a wet method; and 4, step 4: mixing the pre-sintered powder and rectorite according to a ratio, performing wet ball milling, and drying to obtain co-fired powder; and 5: co-firing powder and a binder are mixed, granulated and pressed into green bodies; step 6: and sintering the green body for 4-8 hours at the temperature of 650-700 ℃ in the atmosphere to obtain the ceramic material. The invention prepares the mineral intrinsic crystal phase-low temperature phase co-fired medium component by low temperature co-firing, and the dielectric constant epsilon of the material r Between 11 and 13, the dielectric loss tan δ is close to 0.005.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a mineral-based microwave dielectric ceramic material and a preparation method and application thereof.
Background
With the rapid development of the next generation wireless high-frequency communication transmission technology such as 5G or even 6G, especially the communication scheme with 5G FR2 (24.25 GHz-52.6 GHz) near millimeter-level waveband proposed by the current 3GPP 38.101 protocol, higher requirements are put forward on the dielectric property of the high-frequency communication microwave dielectric material. The microwave dielectric ceramic is used as a key basic material of a resonator, a filter, a baseband antenna and a high-frequency substrate used for a microwave frequency band (300 MHz-300 GHz) military radar, satellite communication, civil mobile high-speed communication and the like, and has become one of hot spots in the research field of domestic and foreign microwave dielectric materials. The range of the dielectric constant directly determines the application aspect of the microwave dielectric ceramic. The low dielectric constant can effectively avoid signal delay, and the high dielectric constant can reduce the size of the device. The microwave dielectric ceramic material with low dielectric constant (less than or equal to 20) which meets the requirement of high-frequency and high-speed transmission is the important research and development field. The high Q multiplied by f value (wherein Q is 1/tan delta, and f is resonant frequency) of the quality factor can obviously reduce signal attenuation and ensure high-frequency insertion loss. A near-zero temperature coefficient of the resonant frequency is a guarantee of transmission temperature stability. Therefore, on the basis of ensuring relatively high quality factor and temperature reliability in the microwave frequency range, the development of a ceramic material system with a series of dielectric constants in a certain range is urgently needed.
In recent years, artificially synthesized ceramic materials having a specific natural mineral crystal structure have been extensively studied and developed for their excellent structure-activity relationship reflected in dielectric properties. Novel wolframite type microwave dielectric ceramic AZrNb 2 O 8 (A: mg, zn, co) realizes the adjustment and control of dielectric property by the replacement of A-site structure, and the performance is more outstanding 2 O 8 ) The dielectric ceramic can realize that: epsilon r =25.67, q × f =109400GHz, τ f =48.78 ppm/deg.c. Perovskite structure (ABO) 3 Type) microwave dielectric ceramic B-site ion order degree, oxygen octahedron torsion/displacement and the like can obviously influence microwave dielectric property, and Ba (Zn) is developed on the basis of the characteristic 1/3 Nb 2/3 )O 3 -Ba(Mg 1/3 Nb 2/3 )O 3 -Ba(Co 1/3 Nb 2/3 )O 3 The ternary system ultra-low loss composite perovskite microwave dielectric ceramic. By Li + And Mg 2+ Series A prepared by respectively occupying C site of tetrahedron, B site of octahedron and A site of dodecahedron in garnet structure 3 B 2 C 3 O 12 Garnet of the type, mg with a smaller ionic radius 2+ The A site entering the garnet structure can produce a hopping effect, and further has a significant influence on the dielectric property. The researches are all artificially synthesized natural mineral structure type microwave ceramics, and are all prepared by high-temperature solid-phase reaction (T is more than or equal to 1000 ℃), the lattice replacement difficulty is high, the procedures are complicated, and the power consumption is high.
Disclosure of Invention
The invention aims to provide a mineral-based microwave dielectric ceramic material which is low in raw material cost, simple in process and beneficial to industrial production, and a preparation method and application thereof, aiming at the defects in the prior art.
The invention relates to a mineral-based microwave dielectric ceramic material which comprises the following raw materials in parts by weight: 1-4 parts of rectorite, 6-9 parts of CuMoO 4 。
The preparation method of the mineral-based microwave dielectric ceramic material comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 Mixing the components according to the stoichiometric ratio, and performing wet ball milling to obtain slurry;
step 2: pre-burning: drying the slurry obtained in the step (1) to obtain dry powder, calcining the dry powder at the temperature of 550-600 ℃ for 6-12 hours to obtain CuMoO 4 Pre-sintering the powder;
and step 3: ball milling: the CuMoO obtained in the step 2 4 The presintering powder is dried for standby after being ball-milled by a wet method;
and 4, step 4: preparing materials: the CuMoO treated in the step 3 is treated 4 Mixing the pre-sintered powder and rectorite according to a ratio, performing wet ball milling, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and a binder, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4-8 hours at the temperature of 650-700 ℃ in the atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Further, in step 1, the mixed powder, alcohol and zirconia balls are placed in a zirconia pot and subjected to wet ball milling in a planetary ball mill.
Further, in step 3, the pre-sintered powder obtained in step 2 is mixed with alcohol and zirconia balls for wet ball milling.
Further, the binder in step 5 is PVA.
Further, in the step 3, the drying temperature is 80 ℃ and the drying time is 6 hours.
Further, in the step 4, the drying temperature is 80 ℃ and the drying time is 6 hours.
The application of the mineral-based microwave dielectric ceramic material in resonators, filters and dielectric antennas is described.
The method takes natural rectorite as raw material and CuMoO with low temperature phase 4 Co-firing and forming at the sintering temperature lower than 700 ℃ to prepare the low-dielectric constant range-adjustable microwave dielectric ceramic, namely the low-temperature phase CuMoO 4 Not only has the characteristic of sintering and compacting at the temperature of less than 700 ℃, but also has the property of sintering and compactingThe invention prepares the cofired medium component of mineral intrinsic crystal phase-low temperature phase on the premise of not destroying the crystalline phase of rectorite intrinsic mineral, and the dielectric constant epsilon of the material is 11-13 r The dielectric loss tan delta is close to 0.005 between 11 and 13, the raw material cost is low, the process is simple, and the method is beneficial to industrial production.
With the rise of the calcination temperature, the organic matters of impurities volatilize and the structure is modified so as to optimize the dielectric property: the method comprises the steps of removing free water and interlayer water at 100-300 ℃, shrinking a structural layer, removing aluminum hydroxyl at 300-800 ℃, keeping the structural layer stable, enabling rectorite to have a regular and stable crystal structure in silicate clay minerals, ensuring that the structure is not damaged during calcination at 800 ℃, and enabling the rectorite to have a low dielectric constant of nearly 10 and a dielectric loss value of nearly 0.001 (tested under an unsintered condition of 100 MHz) due to the uniform laminated structure (a silicon-oxygen tetrahedral layer and an aluminum-oxygen octahedral layer are stacked in 2:1).
The invention aims at the requirement of the microwave dielectric ceramic industry on the dielectric property of materials, combines the low-temperature co-firing technology, co-fires the natural minerals and the low-temperature phase components at low temperature to prepare the dielectric ceramic, utilizes the dielectric property of the natural minerals to regulate and control the dielectric property of the components of the dielectric ceramic, has the characteristics of low-temperature sintering and simple process, provides a new preparation idea, develops the dielectric property of the natural structure clay minerals, widens the application field of the clay minerals, and provides a technical scheme for the component development of the microwave dielectric ceramic.
The invention provides a mineral and low-temperature co-fired phase CuMO 4 The co-firing scheme realizes low-temperature sintering molding at 700 ℃, does not need modification doping agents and sintering aids of other components, only needs one-time pre-sintering, has simple preparation process and is beneficial to reducing the production cost.
Drawings
FIG. 1 shows rectorite and CuMoO 4 And the XRD pattern of the mineral-based microwave dielectric ceramic material prepared in example 1;
FIG. 2 is an XRD pattern of the mineral-based microwave dielectric ceramic material prepared in examples 1-5;
FIG. 3 is a thermal etched cross-sectional view of the mineral-based microwave dielectric ceramic material prepared in example 1 (the left image is a secondary electron image of the ceramic material after polishing and thermal etching, and the right image is a backscattered electron image of the ceramic material after polishing and thermal etching);
FIG. 4 is an XRD pattern of the co-fired mineral-based microwave dielectric ceramic material prepared in example 1 and Al;
FIG. 5 is a graph of the dielectric constant of the mineral-based microwave dielectric ceramic materials prepared in examples 1-5;
FIG. 6 is a graph of dielectric loss for the mineral-based microwave dielectric ceramic materials prepared in examples 1-5;
FIG. 7 is a graph of the sintering schedule of the mineral-based microwave dielectric ceramic materials prepared in examples 1-5.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
The invention provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which comprises the following specific preparation steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step (1) to obtain dry powder, and calcining the dry powder at the temperature of 550-600 ℃ for 6-12 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, carrying out wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: the CuMoO obtained in the step 3 is treated 4 Mixing the pre-sintered powder with rectorite according to a ratio, mixing with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: mixing the co-fired powder obtained in the step (4) with PVA for granulation, and pressing the granulated powder into a green blank;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4-8 hours at the temperature of 650-700 ℃ in the atmosphere to obtain the mineral-based microwave dielectric ceramic material.
The present invention is further illustrated by the following examples.
Practice of example 1
The embodiment provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step 1 to obtain dry powder, and calcining the dry powder at the temperature of 550 ℃ for 6 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, carrying out wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: the CuMoO obtained in the step 3 is treated 4 The ratio of the pre-sintered powder to rectorite is 0.9: mixing the materials according to the proportion of 0.1, mixing the mixture with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and PVA, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4 hours at the temperature of 650 ℃ in the atmospheric atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Example 2
The embodiment provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step (1) to obtain dry powder, and calcining at 550 ℃ for 6 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, performing wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: the CuMoO obtained in the step 3 is treated 4 The ratio of the pre-sintering powder to rectorite is 0.85: mixing the materials according to the proportion of 0.15, mixing the materials with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and PVA, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4-8 hours at the temperature of 650 ℃ in the atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Example 3
The embodiment provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step 1 to obtain dry powder, and calcining the dry powder at the temperature of 550 ℃ for 6 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, carrying out wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: cuMoO obtained in the step 3 4 Pre-sintering powder andrectorite according to the weight ratio of 0.8: mixing the materials according to the proportion of 0.2, mixing the materials with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and PVA, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4 hours at the temperature of 650 ℃ in the atmospheric atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Example 4
The embodiment provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which is a co-fired ceramic mainly containing 25% of rectorite, and comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step 1 to obtain dry powder, and calcining the dry powder at the temperature of 550 ℃ for 6 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, carrying out wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: the CuMoO obtained in the step 3 is treated 4 The ratio of the pre-sintering powder to rectorite is 0.75: mixing the materials according to the proportion of 0.25, mixing the materials with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and PVA, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4 hours at the temperature of 650 ℃ in the atmospheric atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Example 5
The embodiment provides a preparation method of a low-temperature co-fired low-dielectric low-loss mineral-based microwave dielectric ceramic material, which is a co-fired ceramic mainly containing 25% of rectorite, and comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 The mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill to obtain primary slurry;
step 2: pre-burning: drying the primary slurry obtained in the step 1 to obtain dry powder, and calcining the dry powder at the temperature of 550 ℃ for 6 hours to obtain pre-sintered powder;
and step 3: ball milling: mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls, carrying out wet ball milling to obtain secondary slurry, and drying to obtain CuMoO 4 Pre-burning powder;
and 4, step 4: preparing materials: cuMoO obtained in the step 3 4 The ratio of the pre-sintering powder to rectorite is 0.7: mixing the materials according to the proportion of 0.3, mixing the materials with alcohol and zirconia balls, carrying out wet ball milling to obtain third slurry, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and PVA, and pressing the granulated powder into a green body;
step 6: molding and sintering: and (4) sintering the green body obtained in the step (5) for 4 hours at the temperature of 650 ℃ in the atmospheric atmosphere to obtain the mineral-based microwave dielectric ceramic material.
Example 6
The temperature in step 2 was 600 ℃ for 12 hours, and the temperature in step 6 was 700 ℃ for 8 hours, all the same as in example 1.
Example 7
The temperature in step 2 was 580 ℃ and the time was 10 hours, and the temperature in step 6 was 680 ℃ and the time was 6 hours, and the rest was the same as in example 1.
FIG. 1 shows rectorite and CuMoO 4 And XRD patterns of the mineral-based microwave dielectric ceramic material prepared in example 1, as can be seen from FIG. 1, raw ore rectorite and CuMoO 4 And a crystal structure of a mineral-based microwave dielectric ceramic material prepared from the mineral-based microwave dielectric ceramic materialThe material XRD did not obviously find the mineral crystal phase of rectorite, thus showing that the mineral crystal phase is CuMoO after co-firing 4 Is covered.
FIG. 2 is an XRD pattern of the mineral-based microwave dielectric ceramic materials prepared in examples 1-5, from which it can be seen that the crystal structure of the co-fired ceramic is not significantly changed with the increase of the packing ratio of the rectorite.
FIG. 3 is a thermal etched cross-sectional view of the mineral-based microwave dielectric ceramic material prepared in example 1 (the left image is a secondary electron image of the ceramic material after polishing and thermal etching, and the right image is a backscattered electron image of the ceramic material after polishing and thermal etching); the left graph shows that the obvious mineral lamellar structure is uniformly distributed, compact and continuous, the energy spectrum result in the graph shows that the components of the co-fired ceramic are uniform and have no impurities, and the right graph shows that the light and shade are rectorite and CuMoO 4 Two crystal phases, which show that the two crystal phases are uniformly distributed and have the wrapping growth phenomenon.
FIG. 4 is an XRD pattern of the co-fired mineral-based microwave dielectric ceramic material prepared in example 1 and Al; the result of co-firing the co-fired ceramic and 30wt% Al powder at 650 ℃ for 2h, xrd shows that Al crystal phase still exists stably, and the metal compatibility of the co-fired ceramic and Al is good.
FIG. 5 is a graph of the dielectric constant of the mineral-based microwave dielectric ceramic material prepared in examples 1-5; as can be seen from the figure, the embodiment obtains the dielectric constant which can be adjusted arbitrarily within the range of 11-13 by introducing the rectorite with different proportions for co-firing.
FIG. 6 is a graph of dielectric loss for the mineral-based microwave dielectric ceramic materials prepared in examples 1-5; as can be seen from the figure, by introducing different proportions of rectorite for co-firing, a low loss value with dielectric loss around 0.005 is obtained.
FIG. 7 is a graph of the sintering schedule of the mineral-based microwave dielectric ceramic materials prepared in examples 1-5. The cofired ceramic with stable dielectric property is obtained by gradient heating, plastic removal and sintering, and the heating rate is controlled to be between 1 and 1.25 ℃/min.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the foregoing description is for purposes of illustration only and not by way of limitation, and that various modifications, additions and substitutions can be made to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A preparation method of a mineral-based microwave dielectric ceramic material is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparing materials: raw materials of CuO and MoO 3 According to CuMoO 4 Mixing the components according to the stoichiometric ratio, and performing wet ball milling to obtain slurry;
step 2: pre-burning: drying the slurry obtained in the step 1 to obtain dry powder, and calcining the dry powder at the temperature of 550-600 ℃ for 6-12 hours to obtain CuMoO 4 Pre-sintering the powder;
and 3, step 3: ball milling: the CuMoO obtained in the step 2 4 The presintering powder is dried for standby after being ball-milled by a wet method;
and 4, step 4: preparing materials: the CuMoO treated in the step 3 is treated 4 Mixing the pre-sintered powder and rectorite according to a ratio, performing wet ball milling, and drying to obtain co-fired powder;
and 5: granulating and pressing green bodies: blending and granulating the co-fired powder obtained in the step (4) and a binder, and pressing the granulated powder into a green body;
step 6: molding and sintering: sintering the green body obtained in the step 5 for 3~8 hours at the temperature of 650-700 ℃ in the atmospheric atmosphere to obtain a mineral-based microwave dielectric ceramic material, wherein the heating rate is 1-1.25 ℃/min;
the prepared mineral-based microwave dielectric ceramic material comprises the following raw materials in parts by weight: 1-4 parts of rectorite, 6-9 parts of CuMoO 4 。
2. The method for preparing a mineral-based microwave dielectric ceramic material as claimed in claim 1, wherein: in the step 1, the mixed powder, alcohol and zirconia balls are placed in a zirconia pot and are subjected to wet ball milling in a planetary ball mill.
3. The method for preparing a mineral-based microwave dielectric ceramic material as claimed in claim 1, wherein: and 3, mixing the pre-sintered powder obtained in the step 2 with alcohol and zirconia balls for wet ball milling.
4. The method for preparing a mineral-based microwave dielectric ceramic material as claimed in claim 1, wherein: the binder in step 5 is PVA.
5. The method for preparing a mineral-based microwave dielectric ceramic material as claimed in claim 1, wherein: in the step 3, the drying temperature is 80 ℃ and the drying time is 6h.
6. The method for preparing a mineral-based microwave dielectric ceramic material as claimed in claim 1, wherein: in step 4, the drying temperature is 80 ℃, the time is 6h.
7. A mineral-based microwave dielectric ceramic material prepared by the method of any one of claims 1 to 6.
8. Use of a mineral-based microwave dielectric ceramic material as claimed in claim 7 in resonators, filters and dielectric antennas.
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