CN106904965B - Microwave complex phase ceramic KNaWO4-TiO2And method for preparing the same - Google Patents

Microwave complex phase ceramic KNaWO4-TiO2And method for preparing the same Download PDF

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CN106904965B
CN106904965B CN201710050202.0A CN201710050202A CN106904965B CN 106904965 B CN106904965 B CN 106904965B CN 201710050202 A CN201710050202 A CN 201710050202A CN 106904965 B CN106904965 B CN 106904965B
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石锋
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Abstract

The invention provides a microwave complex phase ceramic KNaWO4‑TiO2And a preparation method thereof, the microwave complex phase ceramic KNaWO4‑TiO2The chemical expression of (1-z) KNaWO4—zTiO2Wherein z is 0.15-0.3 molar ratio content; by K2O、Na2O、WO3And TiO2As a starting material, according to K2O：Na2O：WO3：TiO20.5 (1-z): 0.5 (1-z): (1-z): z is prepared from raw materials in a molar ratio. The ceramic has the advantages of low sintering temperature, small dielectric constant, high quality factor, small temperature coefficient of resonant frequency and continuous adjustability, and can be used for microwave substrate materials and microwave packaging ceramics.

Description

Microwave complex phase ceramic KNaWO4-TiO2And method for preparing the same
Technical Field
The invention relates to the field of electronic materials, in particular to microwave complex-phase ceramic KNaWO4-TiO2And a method for preparing the same.
Background
The microwave dielectric ceramic refers to an information functional ceramic material which is suitable for a microwave frequency band (300 MHz-3000 GHz) and has low loss and stable temperature, is widely applied to resonators, filters, capacitors, oscillators, duplexers, dielectric waveguides, substrates, antennas and the like, is a key material of modern microwave communication technologies such as mobile communication, satellite communication, Global Positioning System (GPS), military radar, Wireless Local Area Network (WLAN), internet of things (IOT) and the like, and has important significance for miniaturization of microwave components and improving selectivity of the components. With the rapid development of microwave communication technology in recent years, microwave dielectric ceramics become a hot point of domestic and foreign research, and increasingly receive high attention from various countries. The dielectric properties of the microwave dielectric ceramic mainly comprise three parameters: dielectric constant εrDielectric loss tan δ (quality factor Q1/tan δ) and resonant frequency temperature coefficient τf. The high-performance microwave dielectric ceramic is different from general functional ceramic, and it has need of meeting the requirements of large relative dielectric constant, high quality factor, resonant frequency temp. coefficient close to 0 and adjustable.
In order to reduce costs, it is necessary to prepare ceramics having a lower sintering temperature. LTCC materials are used as the basis for the whole low temperature co-fired ceramic technology, whereinThe problem of chemical compatibility between electrode materials and substrate materials is one of the main contents of research. Ag metal is selected as an electrode material mainly because of the advantages of high conductivity, relatively low cauterization point (961 ℃) and difficult oxidation in the sintering process. In order to co-sinter the LTCC material with the Ag electrode, the optimal sintering temperature of the LTCC material is not higher than 950 ℃, and the LTCC material does not have any chemical reaction with the Ag electrode. However, most ceramic dielectric materials with excellent properties have relatively high sintering temperatures, and the development of low-temperature sintered microwave ceramics is strongly required. Therefore, a novel low-temperature sintering microwave composite ceramic KNaWO is invented4-TiO2And a preparation method thereof, which solves the technical problems.
Disclosure of Invention
The invention aims to provide a microwave composite ceramic which is suitable for low-temperature sintering and has excellent dielectric property, and microwave composite ceramic KNaWO which can be used for microwave packaging and microwave substrate material in the millimeter wave field4-TiO2(ii) a The second purpose is to provide microwave complex phase ceramic KNaWO4-TiO2And a method for preparing the same.
One of the objects of the invention can be achieved by the following technical measures:
the microwave multiphase ceramic KNaWO4-TiO2The chemical expression of (1-z) KNaWO4—zTiO2Wherein z is 0.15-0.3 molar ratio content; by K2O、Na2O、 WO3And TiO2As a starting material, according to K2O：Na2O：WO3：TiO20.5 (1-z): 0.5 (1-z): (1-z): z is prepared from raw materials in a molar ratio.
One of the objects of the invention can also be achieved by the following technical measures:
further, the raw material is K2O、Na2O、WO3And TiO2According to K2O：Na2O： WO3：TiO20.5(1- (0.18-0.26)): 0.18-0.26.
Further, the raw material is K2O、Na2O、WO3And TiO2According to K2O：Na2O： WO3：TiO2The components are mixed according to a molar ratio of 0.4:0.4:0.8: 0.2.
The second purpose of the invention can be realized by the following technical measures:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The preparation method comprises the following steps:
step 1, weighing raw materials according to a raw material ratio;
step 2, putting the raw materials obtained in the step 1 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-8 hours, drying the ball-milled raw materials, and sieving to obtain powder with uniform particles;
step 3, heating the powder treated in the step 2 to 500-600 ℃, and preserving heat for 2-6 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-12 hours, and finally drying the ball-milled raw materials;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, and pressing into a green body by using a powder tablet press;
and 6, firing the blank in the air at 700-950 ℃ for 2-12 hours to obtain the product.
The second object of the present invention can also be achieved by the following technical measures:
further, the ball milling time in the step 2 is 4 hours; the temperature rise in the step 3 is 550 ℃, and the temperature is kept for 4 hours; the ball milling time in the step 4 is 6 hours; the green body described in step 6 was fired at 790 ℃ for 9 hours.
Further, the microwave complex phase ceramic KNaWO4-TiO2The method of (1) further comprises, after step 6, testing the microwave dielectric properties of the article by a network analyzer, the tested microwave dielectric properties comprising a dielectric constant εrQuality factor Qf and resonant frequency temperature coefficient tauf。
The low-temperature sintering microwave composite ceramic KNaWO of the invention4-TiO2And a preparation method thereof, which belong to the technical field of electronic materials, the ceramic uses KNaWO4Is a main crystal phase material and is made of TiO2And adjusting the temperature coefficient. With high purity NaHCO3、KHCO3、WO3And TiO2The method comprises the steps of performing ball milling, drying, sieving, polyvinyl alcohol (PVA) granulation, molding and degumming treatment on raw materials, and then sintering the raw materials in air at 700-950 ℃ for 2-12 hours. The low-temperature sintering microwave ceramic material prepared by the invention has small dielectric constant (10-15), high Q value (Qf is 30000-60000) and excellent frequency temperature coefficient (minus 30 ppm/DEG C. is less than or equal to tau)f≤+30ppm/℃)。
Drawings
FIG. 1 shows a microwave complex phase ceramic KNaWO according to the present invention4-TiO2Flow diagram of one embodiment of a method of making.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below. The formulations mentioned in the following examples are non-limiting embodiments and are only used for illustrating the present invention, and those skilled in the art can select the formulations according to the concept and material selection ratio of the present invention.
Referring to fig. 1:
in step 101, K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3：TiO20.5 (1-z): 0.5 (1-z): (1-z): and weighing the raw materials according to the molar ratio of z.
In step 102, putting the raw materials in the step 101 into a ball mill, adding deionized water and zirconia balls, and carrying out ball milling for 2-8 hours; and drying the ball-milled raw materials at 90 ℃, and sieving the dried raw materials with a 40-mesh sieve to obtain powder with uniform particles.
And 103, pre-burning the sieved powder in the step 102 at 500-600 ℃, and preserving heat for 2-6 hours at the temperature.
In step 104, putting the pre-sintered material in step 103 into a ball milling tank, adding deionized water and zirconia balls, and carrying out ball milling for 2-12 hours; and drying the ball-milled raw materials at 100 ℃.
In step 105, adding a polyvinyl alcohol PVA solution as an adhesive for granulation after drying, sieving by a 80-mesh sieve after drying to obtain powder with uniform granules, and pressing into a green body by a powder tablet press.
And 106, firing the blank in the air at 700-950 ℃ for 2-12 hours to prepare the low-temperature sintered microwave composite ceramic with the small dielectric constant.
At step 107, the article is tested for microwave dielectric properties by a network analyzer. The microwave dielectric properties tested include the dielectric constant εrDielectric loss tan δ (quality factor Q1/tan δ) and resonant frequency temperature coefficient τf。
The ceramic has the advantages of low sintering temperature, small dielectric constant, high quality factor, small temperature coefficient of resonant frequency and continuous adjustability, and can be used for microwave substrate materials and microwave packaging ceramics. The invention has simple process and no pollution in the process, and is a promising microwave dielectric material with small dielectric constant.
The following are several specific application examples of the present invention.
Example 1:
the microwave multiphase ceramic KNaWO4-TiO2Has the chemical expression of (KNaWO)4)0.7-(TiO2)0.3The preparation method comprises the following steps:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The method comprises the following steps:
step 1, high-purity K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3： TiO20.35: 0.35: 0.7: weighing raw materials according to the molar ratio of 0.3.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 8 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 90 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 600 ℃, and preserving heat for 2 hours to obtain a pre-sintering material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 12 hours, and finally drying the ball-milled raw materials at 100 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 950 ℃ for 12 hours to obtain the product. After being cooled with the furnace, the dielectric property is epsilonr＝10；Qf＝60000，τf＝-30ppm/℃。
Example 2:
the microwave multiphase ceramic KNaWO4-TiO2Has the chemical expression of (KNaWO)4)0.85-(TiO2)0.15The preparation method comprises the following steps:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The method comprises the following steps:
step 1, high-purity K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3： TiO20.425: 0.425: 0.85: the raw materials are weighed according to the molar ratio of 0.15.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 90 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 500 ℃, and preserving heat for 6 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 2 hours, and finally drying the ball-milled raw materials at 100 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 700 ℃ for 2 hours to obtain the product. After being cooled with the furnace, the dielectric property is epsilonr＝15；Qf＝30000，τf＝+30ppm/℃。
Example 3:
the microwave multiphase ceramic KNaWO4-TiO2Has the chemical expression of (KNaWO)4)0.74-(TiO2)0.26The preparation method comprises the following steps:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The method comprises the following steps:
step 1, high-purity K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3： TiO20.37: 0.37: 0.74: the raw materials are weighed according to the molar ratio of 0.26.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 6 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 90 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 680 ℃, and preserving heat for 4 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 10 hours, and finally drying the ball-milled raw materials at 100 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 860 ℃ for 6 hours to obtain the product. After being cooled with the furnace, the dielectric property is epsilonr＝12.5；Qf＝55340，τf＝-15.9ppm/℃。
Example 4:
the microwave multiphase ceramic KNaWO4-TiO2Has the chemical expression of (KNaWO)4)0.82-(TiO2)0.18The preparation method comprises the following steps:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The method comprises the following steps:
step 1, high-purity K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3： TiO20.41: 0.41: 0.82: the raw materials are weighed according to the molar ratio of 0.18.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 8 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 90 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 600 ℃, and preserving heat for 2 hours to obtain a pre-sintering material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 2 hours, and finally drying the ball-milled raw materials at 100 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 900 ℃ for 2 hours to obtain the product. After being cooled with the furnace, the dielectric property is epsilonr＝13.6；Qf＝45770，τf＝+6.2ppm/℃。
Example 5:
the microwave multiphase ceramic KNaWO4-TiO2Has the chemical expression of (KNaWO)4)0.8-(TiO2)0.2The preparation method comprises the following steps:
the microwave complex phase ceramic KNaWO is prepared by the raw materials4-TiO2The method comprises the following steps:
step 1, high-purity K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3： TiO20.4:0.4:0.8: the raw materials are weighed according to the molar ratio of 0.2.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 4 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 90 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 550 ℃, and preserving heat for 4 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 6 hours, and finally drying the ball-milled raw materials at 100 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 790 ℃ for 9 hours to obtain the product. After being cooled with the furnace, the dielectric property is epsilonr＝11.2；Qf＝59450，τf＝-28.9ppm/℃。
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed in the present invention should be covered within the protection scope of the present invention.

Claims (5)

1. Low-temperature sintered microwave complex-phase ceramic KNaWO4-TiO2Characterized in that the low-temperature sintering microwave complex-phase ceramic KNaWO4-TiO2The chemical expression of (1-z) KNaWO4—zTiO2Wherein z is 0.15-0.3 molar ratio content; by K2O、Na2O、WO3And TiO2As a starting material, according to K2O：Na2O：WO3：TiO20.5 (1-z): 0.5 (1-z): (1-z): z is prepared from raw materials in a molar ratio, and the preparation method comprises the following steps:
step 1, weighing raw materials according to a raw material ratio;
step 2, putting the raw materials obtained in the step 1 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-8 hours, drying the ball-milled raw materials, and sieving to obtain powder with uniform particles;
step 3, heating the powder treated in the step 2 to 500-600 ℃, and preserving heat for 2-6 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-12 hours, and finally drying the ball-milled raw materials;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, and pressing into a green body by using a powder tablet press;
and 6, firing the blank in the air at 700-950 ℃ for 2-12 hours to obtain the product.
2. The low-temperature sintered microwave complex-phase ceramic KNaWO according to claim 14-TiO2The preparation method of (1) is characterized in that the ball milling time in the step (2) is 4 hours; the temperature rise in the step 3 is 550 ℃, and the temperature is kept for 4 hours; the ball milling time in the step 4 is 6 hours; the green body described in step 6 was fired at 790 ℃ for 9 hours.
3. The device of claim 2, whereinWarm sintering microwave complex phase ceramic KNaWO4-TiO2Characterized in that the low-temperature sintering microwave complex-phase ceramic KNaWO4-TiO2The method of (1) further comprises, after step 6, testing the microwave dielectric properties of the article by a network analyzer, the tested microwave dielectric properties comprising a dielectric constant εrQuality factor Qf and resonant frequency temperature coefficient tauf。
4. The low-temperature sintered microwave complex-phase ceramic KNaWO according to claim 14-TiO2Characterized in that the low-temperature sintering microwave complex-phase ceramic KNaWO4-TiO2Is made of K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3：TiO20.5(1- (0.18-0.26)): 0.18-0.26.
5. The low-temperature sintered microwave complex-phase ceramic KNaWO according to claim 14-TiO2Characterized in that the low-temperature sintering microwave complex-phase ceramic KNaWO4-TiO2Is made of K2O、Na2O、WO3And TiO2According to K2O：Na2O：WO3：TiO2The components are mixed according to a molar ratio of 0.4:0.4:0.8: 0.2.
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