CN111704455A - Lithium-zinc-titanium microwave dielectric ceramic and preparation method and application thereof - Google Patents

Lithium-zinc-titanium microwave dielectric ceramic and preparation method and application thereof Download PDF

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CN111704455A
CN111704455A CN202010546345.2A CN202010546345A CN111704455A CN 111704455 A CN111704455 A CN 111704455A CN 202010546345 A CN202010546345 A CN 202010546345A CN 111704455 A CN111704455 A CN 111704455A
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dielectric ceramic
microwave dielectric
lithium
zinc
titanium
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CN111704455B (en
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刘子峰
陈晓敏
徐越
王文利
王娜娜
贺琰
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Suzhou Cheersson Precision Industry Co ltd
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Abstract

The invention discloses a lithium zinc titanium microwave dielectric ceramic and a preparation method and application thereof2O5Dispersing in absolute ethyl alcohol, mixing, ball-milling, drying to obtain premixed powder, mixing with a binder and acetic acid, pouring into a heatable mould, and carrying out temperature programming under a pressurized condition for sintering to obtain the powder; controlling the pressure under the pressurizing condition to be 300-400MPa, and carrying out temperature programming to comprise the following steps: heating from room temperature to 120-200 ℃, and preserving heat; then heating to 380 ℃ and 460 ℃, and preserving heat; and the lithium zinc titanium microwave dielectric ceramic prepared by the method and the application thereof in preparing microwave communication devices; the method can prepare the lithium-zinc-titanium microwave dielectric ceramic at extremely low sintering temperature, reduces the production cost and the production difficulty, has higher Q' f value and is properThe dielectric constant and the temperature coefficient of the resonance frequency close to zero meet the use requirement under the microwave condition.

Description

Lithium-zinc-titanium microwave dielectric ceramic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to lithium-zinc-titanium microwave dielectric ceramic, a preparation method and application thereof, which can be used for manufacturing microwave devices such as dielectric resonators, filters and the like and are applied to the field of communication.
Background
With the development of wireless communication technologies such as mobile phone communication, WIFI, satellite and radar communication, and the like gradually towards the sub-millimeter wave band direction and the beginning of popularization of 5G, microwave dielectric ceramic materials used as key components such as filters, resonators, oscillators, and the like in wireless communication systems become key materials for the development of millimeter wave communication.
With the development of microwave dielectric ceramic devices, the corresponding dielectric ceramic applied to the microwave frequency band should meet the following requirements: the dielectric constant is proper to facilitate the miniaturization of the device and the signal transmission speed, the Q multiplied by f value is ultrahigh, and the temperature coefficient of the resonant frequency is close to zero.
Li2ZnTi3O8The ceramic is a novel medium-dielectric microwave dielectric ceramic which is rapidly developed in recent years, has excellent dielectric property under a microwave frequency band, and has medium dielectric constant, lower temperature coefficient of resonant frequency and higher quality factor. The lower sintering temperature (1075 ℃) makes it a great advantage in LTCC technology applications. Furthermore, Li2ZnTi3O8The microwave dielectric ceramic has the advantages of low cost, good economy, easy realization of industrialization and the like, thereby having wide application prospect and attracting wide attention of people. But the sintering temperature is still high at present, which is not beneficial to reducing the preparation difficulty and effectively controlling the production cost.
In order to solve the above problems, the chinese invention patent CN102617127A discloses a low temperature sintered lithium-zinc-titanium series microwave dielectric ceramic made of Li2ZnTi3O8Mwt% of M, where M is an additional sintering aid and is H3BO3Or ZBS, m is more than or equal to 0 and less than or equal to 10, and m is the mass percent of the additional sintering aid; the ZBS is 60 wt% ZnO-30 wt% B2O3-10wt％SiO2Herein, thisThe patent is characterized by adding small amount of H3BO3Or a low-melting-point sintering aid such as ZBS glass and the like, so that the sintering temperature of the lithium-zinc-titanium microwave dielectric ceramic is successfully reduced to below 900 ℃, and the excellent microwave dielectric property of the lithium-zinc-titanium microwave dielectric ceramic is maintained; however, it is not negligible that the sintering temperature of this patent still requires a sintering temperature above 850 ℃.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved preparation method of lithium zinc titanium microwave dielectric ceramic, the method can prepare the lithium zinc titanium microwave dielectric ceramic at an extremely low sintering temperature, the production cost and the production difficulty are greatly reduced, and the prepared lithium zinc titanium microwave dielectric ceramic has a higher Q multiplied by f value, a proper dielectric constant and a near-zero temperature coefficient of resonance frequency, and meets the use requirements under the microwave condition.
The invention also provides the lithium-zinc-titanium microwave dielectric ceramic prepared by the method.
The invention also provides the application of the lithium-zinc-titanium microwave dielectric ceramic prepared by the method in the preparation of microwave communication devices.
In order to achieve the purpose, the invention adopts a technical scheme that: the preparation method of the lithium-zinc-titanium microwave dielectric ceramic comprises a main crystal phase material and a doping material selectively contained, wherein the main crystal phase material is Li2ZnTi3O8The doped material is Nb2O5In weight percentage, the Nb2O5In an amount of Li2ZnTi3O80 to 8wt% of;
the preparation method of the lithium-zinc-titanium microwave dielectric ceramic comprises the following steps of:
(1) mixing Li2ZnTi3O8Powder and optionally Nb2O5Dispersing in absolute ethyl alcohol, mixing, ball-milling and drying to prepare premixed powder;
(2) mixing the premixed powder, a binder for preparing the microwave dielectric ceramic and acetic acid, and pouringHeating the mold, and sintering under the condition of pressurization and temperature programming to obtain the microwave dielectric ceramic, which comprises the following chemical components: li2ZnTi3O8-Xwt％Nb2O5，0≤X≤8；
Wherein the pressure under the pressurization condition is controlled to be 300-400MPa, and the programmed temperature rise comprises the following stages: heating from room temperature to 120-200 ℃ at the speed of 1-4 ℃/min, and preserving heat; then heating from 120-200 ℃ to 380-460 ℃ at a speed of 3-8 ℃/min, and preserving the heat.
According to some preferred aspects of the invention, the Nb is present in weight percent2O5In an amount of Li2ZnTi3O80.001-4wt% of (B).
According to some preferred aspects of the present invention, in the step (1), the mass ratio of the materials, the ball milling beads and the absolute ethyl alcohol during the ball milling process is controlled to be 1: 2-4: 1.1-1.3. According to a preferred and specific aspect of the present invention, in the step (1), the mass ratio of the materials, the ball milling beads and the absolute ethyl alcohol during the ball milling process is controlled to be 1:3: 1.2.
According to some specific and preferred aspects of the present invention, in step (1), the Li2ZnTi3O8Is prepared by the following steps: weighing zinc element-containing salt or oxide thereof, titanium element-containing salt or oxide thereof and lithium element-containing salt or oxide thereof, adding absolute ethyl alcohol for ball milling, filtering and drying, and presintering at 800-1000 ℃ to prepare the material. In some embodiments of the invention, the salt of an element containing zinc or an oxide thereof includes, but is not limited to, zinc oxide, the salt of an element containing titanium or an oxide thereof includes, but is not limited to, titanium dioxide, and the salt of an element containing lithium or an oxide thereof includes, but is not limited to, lithium carbonate.
According to some preferred aspects of the present invention, in step (2), the pressure under the pressurization condition is controlled to be 300-: heating from room temperature to 120-150 ℃ at the speed of 2-4 ℃/min, and preserving heat; then raising the temperature from 150 ℃ at the speed of 4-6 ℃/min to 440 ℃ at the speed of 400 ℃ and preserving the temperature. According to a preferred and specific aspect of the present invention, in step (2), the pressure under the pressurized condition is controlled to be 300MPa, and the temperature programming includes the following stages: heating from room temperature to 150 ℃ at the speed of 3 ℃/min, and preserving heat; then the temperature is raised from 150 ℃ to 420 ℃ at the speed of 5 ℃/min, and the temperature is preserved.
According to some specific and preferred aspects of the present invention, in the step (2), the binder for preparing the microwave dielectric ceramic is polyvinyl alcohol, and the polyvinyl alcohol is added in the form of an aqueous solution of polyvinyl alcohol, and the polyvinyl alcohol is added in an amount of 6 to 10wt% based on the weight percentage of the premixed powder.
According to some preferred aspects of the invention, in step (2), the acetic acid is added as an aqueous solution of acetic acid in an amount of 10 to 20wt% based on the weight percentage of the premixed powder. In the invention, acetic acid is added into the materials before temperature rise sintering, which is beneficial to reducing the sintering temperature.
According to some preferred and specific aspects of the present invention, in the step (2), the premixed powder and the binder for preparing the microwave dielectric ceramic are mixed, sieved, and the sieved material is mixed with the acetic acid and poured into a heatable mold.
The invention provides another technical scheme that: the lithium zinc titanium microwave dielectric ceramic is prepared by the preparation method of the lithium zinc titanium microwave dielectric ceramic.
The invention provides another technical scheme that: an application of the lithium zinc titanium microwave dielectric ceramic in the preparation of microwave communication devices. The dielectric property of the lithium-zinc-titanium microwave dielectric ceramic can meet the following parameter requirements, the dielectric constant r is 26.17-27.48, the Qxf value can be higher than 65000Ghz, and tau f is approximately equal to-11 to-6 ppm/DEG C.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the method greatly reduces the production cost and the production difficulty, and the prepared microwave dielectric ceramic material obtains ideal Qxf value, nearly zero tau f value and proper dielectric constant, and can meet the use requirements under the microwave condition.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1
This example provides a lithium-zinc-titanium microwave dielectric ceramic whose chemical composition is Li2ZnTi3O8-3wt％Nb2O5The preparation method comprises the following steps:
(1) preparation of Li2ZnTi3O8Powder body
ZnO and TiO as raw materials2And Li2CO31:3:1, putting the materials obtained by proportioning, ball milling beads and absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for wet ball milling for 10 hours at a rotating speed of 180r/min to obtain slurry raw materials, putting the slurry raw materials into an oven to be dried at 60 ℃ to constant weight to obtain dry mixed materials, sieving the mixed materials by a 60-mesh sieve to disperse the mixed materials, then putting the mixed materials into a high-temperature furnace to presure for 4 hours at the presintering temperature of 900 ℃ to obtain Li2ZnTi3O8Powder;
(2) li prepared in the step (1)2ZnTi3O8Powder and Nb2O5Powder (in weight percentage, Nb)2O5Powder of Li2ZnTi3O83 wt% of the powder) and adding absolute ethyl alcohol, and placing the materials, the ball milling beads and the absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for grinding for 10 hours to form premixed slurry; mixing the obtained premixed slurryPlacing the material in a drying oven, drying at 60 deg.C to constant weight to obtain premixed powder, sieving the premixed powder with a 60 mesh standard sieve, adding polyvinyl alcohol solution (containing polyvinyl alcohol 8wt% of the premixed powder), mixing, and sieving with a 60 mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 12 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 150 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 420 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the lithium-zinc-titanium microwave dielectric ceramic, wherein the chemical composition of the lithium-zinc-titanium microwave dielectric ceramic is Li, Zn and Ti microwave dielectric ceramic2ZnTi3O8-3wt％Nb2O5。
And (3) later-stage mechanical processing: sintering the Li2ZnTi3O8-3wt％Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 2
This example provides a lithium-zinc-titanium microwave dielectric ceramic whose chemical composition is Li2ZnTi3O8-3.5wt％Nb2O5The preparation method comprises the following steps:
(1) preparation of Li2ZnTi3O8Powder body
ZnO and TiO as raw materials2And Li2CO31:3:1, putting the materials obtained by proportioning, ball milling beads and absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for wet ball milling for 10 hours at a rotating speed of 180r/min to obtain slurry raw materials, putting the slurry raw materials into an oven to be dried at 60 ℃ to constant weight to obtain dry mixed materials, sieving the mixed materials by a 60-mesh sieve to disperse the mixed materials, then putting the mixed materials into a high-temperature furnace to presure for 4 hours at the presintering temperature of 900 ℃ to obtain Li2ZnTi3O8Powder;
(2) li prepared in the step (1)2ZnTi3O8Powder and Nb2O5Powder (in weight percentage, Nb)2O5Powder of Li2ZnTi3O83.5 wt% of the powder) and adding absolute ethyl alcohol, and placing the materials, the ball milling beads and the absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for grinding for 10 hours to form premixed slurry; placing the obtained premixed slurry in a drying oven, drying at 60 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 6 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 150 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 420 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the lithium-zinc-titanium microwave dielectric ceramic, wherein the chemical composition of the lithium-zinc-titanium microwave dielectric ceramic is Li, Zn and Ti microwave dielectric ceramic2ZnTi3O8-3.5wt％Nb2O5。
And (3) later-stage mechanical processing: sintering the Li2ZnTi3O8-3.5wt％Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 3
This example provides a lithium-zinc-titanium microwave dielectric ceramic whose chemical composition is Li2ZnTi3O8-4wt％Nb2O5The preparation method comprises the following steps:
(1) preparation of Li2ZnTi3O8Powder body
ZnO and TiO as raw materials2And Li2CO31:3:1, putting the materials obtained by proportioning, ball milling beads and absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for wet ball milling for 10 hours at the rotating speed of 180r/min to obtain slurry raw materials, putting the slurry raw materials in an oven at 60 DEG CDrying to constant weight to obtain dry mixture, sieving with 60 mesh sieve, dispersing, presintering in high temperature furnace at 900 deg.C for 4 hr to obtain Li2ZnTi3O8Powder;
(2) li prepared in the step (1)2ZnTi3O8Powder and Nb2O5Powder (in weight percentage, Nb)2O5Powder of Li2ZnTi3O84wt% of the powder) and adding absolute ethyl alcohol, and placing the materials, the ball milling beads and the absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing 7 wt% of polyvinyl alcohol in the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 10wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 150 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 420 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the lithium-zinc-titanium microwave dielectric ceramic, wherein the chemical composition of the lithium-zinc-titanium microwave dielectric ceramic is Li, Zn and Ti microwave dielectric ceramic2ZnTi3O8-4wt％Nb2O5。
And (3) later-stage mechanical processing: sintering the Li2ZnTi3O8-4wt％Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 4
This example provides a lithium-zinc-titanium microwave dielectric ceramic whose chemical composition is Li2ZnTi3O8-2wt％Nb2O5The preparation method comprises the following steps:
(1) preparation of Li2ZnTi3O8Powder body
Raw material ZnO、TiO2And Li2CO31:3:1, putting the materials obtained by proportioning, ball milling beads and absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for wet ball milling for 10 hours at a rotating speed of 180r/min to obtain slurry raw materials, putting the slurry raw materials into an oven to be dried at 60 ℃ to constant weight to obtain dry mixed materials, sieving the mixed materials by a 60-mesh sieve to disperse the mixed materials, then putting the mixed materials into a high-temperature furnace to presure for 4 hours at the presintering temperature of 900 ℃ to obtain Li2ZnTi3O8Powder;
(2) li prepared in the step (1)2ZnTi3O8Powder and Nb2O5Powder (in weight percentage, Nb)2O5Powder of Li2ZnTi3O82 wt% of the powder) and adding absolute ethyl alcohol, and placing the materials, the ball milling beads and the absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 18 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 150 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 420 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the lithium-zinc-titanium microwave dielectric ceramic, wherein the chemical composition of the lithium-zinc-titanium microwave dielectric ceramic is Li, Zn and Ti microwave dielectric ceramic2ZnTi3O8-2wt％Nb2O5。
And (3) later-stage mechanical processing: sintering the Li2ZnTi3O8-2wt％Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 5
This example is aProvides a lithium-zinc-titanium microwave dielectric ceramic with the chemical composition of Li2ZnTi3O8-3wt％Nb2O5The preparation method comprises the following steps:
(1) preparation of Li2ZnTi3O8Powder body
ZnO and TiO as raw materials2And Li2CO31:3:1, putting the materials obtained by proportioning, ball milling beads and absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for wet ball milling for 10 hours at a rotating speed of 180r/min to obtain slurry raw materials, putting the slurry raw materials into an oven to be dried at 60 ℃ to constant weight to obtain dry mixed materials, sieving the mixed materials by a 60-mesh sieve to disperse the mixed materials, then putting the mixed materials into a high-temperature furnace to presure for 4 hours at the presintering temperature of 900 ℃ to obtain Li2ZnTi3O8Powder;
(2) li prepared in the step (1)2ZnTi3O8Powder and Nb2O5Powder (in weight percentage, Nb)2O5Powder of Li2ZnTi3O83 wt% of the powder) and adding absolute ethyl alcohol, and placing the materials, the ball milling beads and the absolute ethyl alcohol in a ball mill according to the mass ratio of 1:3:1.2 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 8wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 12 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 150 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the lithium-zinc-titanium microwave dielectric ceramic, wherein the chemical composition of the lithium-zinc-titanium microwave dielectric ceramic is Li, Zn and Ti microwave dielectric ceramic2ZnTi3O8-3wt％Nb2O5。
And (3) later-stage mechanical processing: sintering the Li2ZnTi3O8-3wt％Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: no acetic acid solution is added in the step (2).
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: in the step (2), the set pressurization program for pressurization to 300MPa is replaced by the set pressurization program for pressurization to 200 MPa.
Comparative example 3
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the pressure condition is replaced by 'no pressurization', namely, the temperature rise is carried out under the condition of normal pressure.
Comparative example 4
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: in the step (2), "heat preservation for 1h and then heating to 420 ℃ at a speed of 5 ℃/min and preserving heat for 2 h" is replaced by "heat preservation for 1h and then heating to 300 ℃ at a speed of 5 ℃/min and preserving heat for 2 h".
Comparative example 5
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: in the step (2), the set pressurizing program is replaced by the set pressurizing program for pressurizing to 200MPa when the pressure is increased to 300MPa, the temperature is maintained for 1h, the temperature is increased to 420 ℃ at the speed of 5 ℃/min for 2h, the temperature is maintained for 1h, and the temperature is increased to 350 ℃ at the speed of 5 ℃/min for 2 h.
Performance testing
The lithium zinc titanium microwave dielectric ceramics obtained in the above examples 1 to 5 and comparative examples 1 to 5 were ground and polished to obtain ceramic finished products with smooth surfaces, and the microwave dielectric properties at the resonant frequency of the cylindrical ceramic were measured by a Keysight E5232B vector network analyzer as shown in the following Table 1 (dielectric constant measuring System (dielectric resonator method): test jigs were connected to the vector network analyzer by cables, placed in a high and low temperature cabinet, and subjected to resonance frequency at room temperature, Q × F value, and dielectric constant measurement at room temperature, and then subjected to dielectric constant measurementHeating the sample to 125 deg.C, measuring the resonant frequency, and calculating the temperature coefficient tauf)：
TABLE 1
Figure BDA0002540295290000071
Figure BDA0002540295290000081
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Claims (10)

1. The preparation method of the lithium-zinc-titanium microwave dielectric ceramic is characterized in that the lithium-zinc-titanium microwave dielectric ceramic comprises a main crystal phase material and a selective doping material, wherein the main crystal phase material is Li2ZnTi3O8The doped material is Nb2O5In weight percentage, the Nb2O5In an amount of Li2ZnTi3O80 to 8wt% of;
the preparation method of the lithium-zinc-titanium microwave dielectric ceramic comprises the following steps of:
(1) mixing Li2ZnTi3O8Powder and optionally Nb2O5Dispersing in absolute ethyl alcohol, mixing, ball-milling and drying to prepare premixed powder;
(2) mixing the premixed powder, a binder for preparing the microwave dielectric ceramic and acetic acid, pouring the mixture into a heatable mould, and carrying out temperature programming and sintering under a pressurized condition to prepare the microwave dielectric ceramic, wherein the microwave dielectric ceramic comprises the following chemical components: li2ZnTi3O8-Xwt%Nb2O5，0≤ X ≤8；
Wherein the pressure under the pressurization condition is controlled to be 300-400MPa, and the programmed temperature rise comprises the following stages: heating from room temperature to 120-200 ℃ at the speed of 1-4 ℃/min, and preserving heat; then heating from 120-200 ℃ to 380-460 ℃ at a speed of 3-8 ℃/min, and preserving the heat.
2. The method of claim 1, wherein the Nb is calculated in weight percentage2O5In an amount of Li2ZnTi3O80.001-4wt% of (B).
3. The preparation method of the lithium zinc titanium microwave dielectric ceramic according to claim 1, wherein in the step (1), the mass ratio of the materials, the ball milling beads and the absolute ethyl alcohol is controlled to be 1: 2-4: 1.1-1.3 in the ball milling process.
4. The method for preparing Li-Zn-Ti microwave dielectric ceramic according to claim 1, wherein in step (1), the Li is2ZnTi3O8Is prepared by the following steps: weighing zinc element-containing salt or oxide thereof, titanium element-containing salt or oxide thereof and lithium element-containing salt or oxide thereof, adding absolute ethyl alcohol for ball milling, filtering and drying, and presintering at 800-1000 ℃ to prepare the material.
5. The method for preparing the lithium zinc titanium microwave dielectric ceramic as claimed in claim 1, wherein in the step (2), the pressure under the pressurization condition is controlled to be 300-350MPa, and the temperature programming comprises the following steps: heating from room temperature to 120-150 ℃ at the speed of 2-4 ℃/min, and preserving heat; then raising the temperature from 150 ℃ at the speed of 4-6 ℃/min to 440 ℃ at the speed of 400 ℃ and preserving the temperature.
6. The method for preparing lithium zinc titanium microwave dielectric ceramic according to claim 1, wherein in the step (2), the binder for preparing the microwave dielectric ceramic is polyvinyl alcohol, the polyvinyl alcohol is added in the form of an aqueous solution of polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is 6-10wt% of the premixed powder.
7. The method for preparing lithium zinc titanium microwave dielectric ceramic according to claim 1, wherein in the step (2), the acetic acid is added in the form of an aqueous solution of acetic acid, and the addition amount of the acetic acid is 10-20wt% of the premixed powder in terms of weight percentage.
8. The method according to claim 1, wherein in step (2), the premixed powder and the binder for preparing the microwave dielectric ceramic are mixed, sieved, and the sieved material is mixed with the acetic acid and poured into a heatable mold.
9. A lithium zinc titanium microwave dielectric ceramic produced by the method for producing a lithium zinc titanium microwave dielectric ceramic according to any one of claims 1 to 8.
10. Use of the lithium zinc titanium microwave dielectric ceramic of claim 9 in the preparation of microwave communication devices.
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