CN109761601B - ZHTS microwave dielectric ceramic and preparation method thereof - Google Patents
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Abstract
The invention provides a ZHTS microwave dielectric ceramic and a preparation method thereof, wherein the ZHTS microwave dielectric ceramic has a general formula shown in a formula (I): zrxHfyTi2SnzO8+2x+2y+2z(ii) a Wherein y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1. Compared with the prior art, the ZHTS microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and the continuous adjustability of the dielectric constant of about 40 and the frequency temperature coefficient can be realized by adjusting the contents of Zr, Hf and Sn; moreover, the Hf partially replaces the Zr activated lattice structure, so that the Qf value is improved; the ZHTS microwave dielectric ceramic has stable structure, specific dielectric constant and higher Qf value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the ZHTS microwave dielectric ceramic is 38-43, the Qf is more than 51500GHz and can reach 68600GHz, and compared with other systems of microwave dielectric ceramic with the same dielectric constant, the system has large Qf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-10.9 ppm/DEG C to +23 ppm/DEG C.
Description
Technical Field
The invention relates to the technical field of microwave dielectric ceramics, in particular to a ZHTS microwave dielectric ceramic and a preparation method thereof.
Background
The mobile communication technology will step into the development stage of the fifth generation mobile communication (5G), and the 5G is to meet the requirements of people on ultra-high traffic density, ultra-high connection number density and ultra-high mobility, and can provide users with extreme business experiences such as high-definition videos, virtual reality, augmented reality, cloud desktops, online games and the like. 5G can be deeply fused with industrial facilities, medical instruments, vehicles and the like, and the 'mutual interconnection' is comprehensively realized. This will bring thousands of times of growth in data traffic, billions of device connections and diversified business requirements, and will pose a serious challenge to 5G system design, necessitating a significant increase in spectral efficiency. Various frequency selection devices made of microwave dielectric ceramics become a necessary way to improve the spectrum efficiency due to excellent performance. The microwave dielectric ceramic with the dielectric constant of about 40 is moderate in dielectric constant and low in loss, and is widely researched.
Currently, much research is being done on Ba [ (Zn, Co)1/3Nb2/3]O3High cost of raw materials and high difficulty of manufacture, and BaTi4O9–BaZn2Ti4O11Low ceramic strength of system, SrTiO3–LaAlO3High sintering temperature of the system, low ceramic strength and CaTiO3–LaAlO3The system loss is large. Therefore, the development of the microwave dielectric ceramic with the dielectric constant of about 40, low loss, continuously adjustable temperature drift, low cost and high reliability has great scientific research and market values.
Disclosure of Invention
In view of the above, the present invention aims to provide a ZHTS microwave dielectric ceramic and a preparation method thereof, wherein the dielectric constant of the ZHTS microwave dielectric ceramic provided by the present invention is about 40, the dielectric loss is low, and the temperature coefficient of the resonant frequency is continuously adjustable.
The invention provides a ZHTS microwave dielectric ceramic which has a general formula shown in a formula (I):
ZrxHfyTi2SnzO6formula (I);
in the formula (I), y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1.
Preferably, the method further comprises the following steps:
an additive;
the additive is prepared from the following components in percentage by mass (35-45): (15-25): (15-30): (5-20): (1-10) SiO2、B2O3、La2O3ZnO and MgO.
Preferably, the preparation method of the additive specifically comprises the following steps:
mixing SiO2、B2O3、La2O3And ZnO and MgO are mixed and ball-milled, then melted for 10min to 30min at 1200 ℃ to 1300 ℃, and then crushed and sieved after separation to obtain the additive.
The invention also provides a preparation method of the ZHTS microwave dielectric ceramic in the technical scheme, which comprises the following steps:
a) ZrO 2 is mixed with2、HfO2、TiO2And SnO2After mixing, carrying out primary grinding treatment, and then carrying out presintering to obtain a presintering material; then, carrying out secondary grinding treatment on the obtained pre-sintering material to obtain powder;
b) adding an adhesive into the powder obtained in the step a) for granulation forming to obtain a ceramic green body; and sintering the obtained ceramic green body to obtain the ZHTS microwave dielectric ceramic.
Preferably, the first grinding treatment in step a) specifically comprises the following steps:
mixing the mixed raw materials, zirconium balls and water in a proportion of 1: (3-4): (2-3), ball-milling for 3-5 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
Preferably, the temperature of the pre-sintering in the step a) is 950-1150 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 3-4 h.
Preferably, the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the mass ratio of the powder to the adhesive is 100: (15-25).
Preferably, the granulation molding process in the step b) specifically comprises the following steps:
adding an adhesive into the microwave dielectric ceramic powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90 mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain the ceramic green body.
Preferably, the sintering temperature in the step b) is 1200-1400 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 2-4 h.
Preferably, the step a) further comprises:
and mixing the obtained pre-sintered material with an additive, and then carrying out secondary grinding treatment to obtain powder.
The invention provides a ZHTS microwave dielectric ceramic and a preparation method thereof, wherein the ZHTS microwave dielectric ceramic has a general formula shown in a formula (I): zrxHfyTi2SnzO6(ii) a Wherein y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1. Compared with the prior art, the ZHTS microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and the continuous adjustability of the dielectric constant of about 40 and the frequency temperature coefficient can be realized by adjusting the contents of Zr, Hf and Sn; moreover, the Hf partially replaces the Zr activated lattice structure, so that the Qf value is improved; the ZHTS microwave dielectric ceramic has stable structure, specific dielectric constant and higher Qf value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the ZHTS microwave dielectric ceramic is 38-43, the Qf is more than 51500GHz and can reach 68600GHz, and compared with other systems of microwave dielectric ceramic with the same dielectric constant, the system has large Qf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-10.9 ppm/DEG C to +23 ppm/DEG C.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature, low cost, no toxicity, no environmental pollution, suitability for large-scale industrialization and wide development prospect, and meets the requirement of environmental protection.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a ZHTS microwave dielectric ceramic which has a general formula shown in a formula (I):
ZrxHfyTi2SnzO6formula (I);
in the formula (I), y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1.
In the present invention, x is 0.47. ltoreq. x.ltoreq.1, preferably 0.485. ltoreq. x.ltoreq.0.985; in the preferred embodiment of the present invention, x is 0.485, 0.575, 0.65, 0.665, 0.68, 0.755, 0.845, 0.985.
In the present invention, 0. ltoreq. y.ltoreq.0.03, preferably 0.015.
In the invention, z is more than or equal to 0 and less than or equal to 0.5; in the preferred embodiment of the present invention, z takes values of 0, 0.14, 0.23, 0.32, 0.41, 0.5, respectively.
In the present invention, the ZHTS microwave dielectric ceramic is prepared from ZrO at the above stoichiometric ratio2、HfO2、TiO2And SnO2Compounding; the ZHTS microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and can realize the continuous adjustment of the dielectric constant of about 40 and the frequency temperature coefficient by adjusting the contents of Zr, Hf and Sn; moreover, the Hf partially replaces the Zr activated lattice structure, so that the Qf value is improved; the ZHTS microwave dielectric ceramic has stable structure, specific dielectric constant and higher Qf value, and the temperature coefficient of the resonant frequency is continuously adjustable.
In the present invention, the ZHTS microwave dielectric ceramic preferably further comprises:
and (3) an additive.
In the invention, the additive is preferably prepared from the following components in a mass ratio of (35-45): (15-25): (15-30): (5-20): (1-10) SiO2、B2O3、La2O3ZnO and MgO, and more preferably a mixture of ZnO and MgO in a mass ratio of 40: 18: 25: 15: SiO of 22、B2O3、La2O3ZnO and MgO.
In the present invention, the preparation method of the additive is preferably specifically:
mixing SiO2、B2O3、La2O3Mixing ZnO and MgO, ball-milling, melting at 1200-1300 ℃ for 10-30 min, separating, crushing and sieving to obtain the additive;
more preferably:
mixing SiO2、B2O3、La2O3And ZnO and MgO are mixed and ball-milled, then melted for 20min at 1250 ℃, and then crushed and sieved after separation to obtain the additive.
The ball milling equipment is not particularly limited in the present invention, and a ball mill known to those skilled in the art may be used. In the present invention, the time for the ball milling is preferably 20 to 30 hours, and more preferably 24 hours. In the present invention, the separation is preferably performed by extraction with water, and the present invention is not particularly limited thereto. The process of the present invention is not particularly limited, and the crushing method known to those skilled in the art may be used. In the present invention, the size of the mesh of the screen is preferably 150 to 250 mesh, and more preferably 200 mesh. By adopting the preparation method, the refined additive can be obtained, and the subsequent use is convenient.
In the invention, the amount of the additive is preferably 0.1-2% of the mass of the ZHTS microwave dielectric ceramic, and more preferably 0.4-1.2% of the mass of the pre-sintering material.
In the invention, the additive can reduce the sintering temperature, inhibit the reduction of titanium and improve the Qf value.
The invention also provides a preparation method of the ZHTS microwave dielectric ceramic in the technical scheme, which comprises the following steps:
a) ZrO 2 is mixed with2、HfO2、TiO2And SnO2After mixing, carrying out primary grinding treatment, and then carrying out presintering to obtain a presintering material; then, carrying out secondary grinding treatment on the obtained pre-sintering material to obtain powder;
b) adding an adhesive into the powder obtained in the step a) for granulation forming to obtain a ceramic green body; and sintering the obtained ceramic green body to obtain the ZHTS microwave dielectric ceramic.
The invention firstly uses ZrO2、HfO2、TiO2And SnO2After mixing, carrying out primary grinding treatment, and then carrying out presintering to obtain a presintering material; and then, carrying out secondary grinding treatment on the obtained pre-sintering material to obtain powder. Invention for the ZrO2、HfO2、TiO2And SnO2The source of (A) is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the ZrO2、HfO2、TiO2And SnO2The amount of (A) is calculated according to the stoichiometric ratio in the general formula shown in formula (I).
In the present invention, the first grinding process preferably includes:
mixing the mixed raw materials, zirconium balls and water in a proportion of 1: (3-4): (2-3), ball-milling for 3-5 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after primary grinding treatment;
more preferably:
mixing the mixed raw materials, zirconium balls and water in a proportion of 1: 3: 2, ball milling for 4 hours at the rotating speed of 250r/min, and then drying at 120 ℃ to obtain a mixed material after the first grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the mixed material after the first grinding treatment is obtained, the obtained mixed material is presintered to obtain a presintering material. In the invention, the pre-sintering temperature is preferably 950-1150 ℃, and more preferably 950-1050 ℃; the temperature rise rate of the pre-sintering is preferably 3 ℃/min to 8 ℃/min, and more preferably 3 ℃/min; the heat preservation time of the pre-sintering is preferably 3 to 4 hours, and more preferably 3 hours.
After the pre-sintering material is obtained, the obtained pre-sintering material is ground for the second time to obtain powder. Before the second grinding treatment, the method preferably further comprises the steps of cooling the pre-sintered material; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
In the present invention, the second grinding process is the same as the first grinding process, and preferably specifically includes:
mixing the obtained pre-sintering material, zirconium balls and water in a proportion of 1: (3-4): (2-3), ball-milling for 3-5 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after the second grinding treatment;
more preferably:
mixing the obtained pre-sintering material, zirconium balls and water in a proportion of 1: 3: 2, ball-milling for 4 hours at the rotating speed of 250r/min, and then drying at 120 ℃ to obtain a mixed material after the second grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
In the present invention, after obtaining the pre-sintered material, the method preferably further comprises:
and mixing the obtained pre-sintered material with an additive, and then carrying out secondary grinding treatment to obtain powder. In the present invention, the additive is the same as that described in the above technical solution, and is not described herein again. In the present invention, the amount of the additive is preferably 0.1% to 2% by mass of the pre-fired material, and more preferably 0.4% to 1.2% by mass of the pre-fired material.
After the powder is obtained, adding an adhesive into the obtained powder for granulation molding to obtain a ceramic green body; and sintering the obtained ceramic green body to obtain the ZHTS microwave dielectric ceramic. In the invention, the adhesive has enough viscosity, can ensure good formability and mechanical strength of the green body, and can be completely volatilized after high-temperature calcination, so that residual impurities of the adhesive are not left in the green body. In the present invention, the binder is preferably a polyvinyl alcohol aqueous solution with a mass percentage of 6% to 8%, and more preferably a polyvinyl alcohol aqueous solution with a mass percentage of 6%. In the present invention, the polyvinyl alcohol is converted into CO after high-temperature calcination (subsequent sintering process)2And H2O, can be completely volatilized.
In the present invention, the mass ratio of the powder to the binder is preferably 100: (15-25), more preferably 100: 20.
in the present invention, the granulation molding process preferably includes:
adding an adhesive into the microwave dielectric ceramic powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90 mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain a ceramic green body;
more preferably:
and adding an adhesive into the microwave dielectric ceramic powder, granulating and grinding for 1h, sieving by using an 80-mesh sieve, and pressing and molding the obtained powder under the pressure of 100MPa to obtain a ceramic green body. In the invention, the granulating and grinding process can uniformly mix the powder and the adhesive and granulate.
In the present invention, the ceramic green body is preferably a thin cylindrical green body having a thickness of 4mm to 10mm and a diameter of 8mm to 20mm, and more preferably a thin cylindrical green body having a thickness of 6mm and a diameter of 13mm (a cylinder having a diameter to height ratio of about 2.0).
In the invention, the sintering temperature is preferably 1200-1400 ℃, and more preferably 1300-1400 ℃; the heating rate of the sintering is preferably 3-8 ℃/min, and more preferably 3 ℃/min; the heat preservation time for sintering is preferably 2h to 4h, and more preferably 3 h.
After sintering, the invention preferably also comprises cooling the sintered product to obtain the ZHTS microwave dielectric ceramic; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
The preparation method provided by the invention has the advantages of simple process, low sintering temperature, low cost, no toxicity, no pollution to the environment, suitability for large-scale industrialization and very wide development prospect, and meets the requirement of environmental protection.
The invention provides a ZHTS microwave dielectric ceramic and a preparation method thereof, wherein the ZHTS microwave dielectric ceramic has a general formula shown in a formula (I): zrxHfyTi2SnzO6(ii) a Wherein y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1. Compared with the prior art, the ZHTS microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and the continuous adjustability of the dielectric constant of about 40 and the frequency temperature coefficient can be realized by adjusting the contents of Zr, Hf and Sn; moreover, the Hf partially replaces the Zr activated lattice structure, so that the Qf value is improved; the ZHTS microwave dielectric ceramic has stable structure, specific dielectric constant and higher Qf value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the ZHTS microwave dielectric ceramic is 38-43, the Qf is more than 51500GHz and can reach 68600GHz, and compared with other systems of microwave dielectric ceramic with the same dielectric constant, the system has large Qf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-10.9 ppm/DEG C to +23 ppm/DEG C.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature, low cost, no toxicity, no environmental pollution, suitability for large-scale industrialization and wide development prospect, and meets the requirement of environmental protection.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials of the medicines used in the following examples of the present invention are all commercially available products; wherein the adhesive is a polyvinyl alcohol aqueous solution with the mass percentage of 6%; the additive is a composite oxide and is prepared from the following components in a mass ratio of 40: 18: 25: 15: SiO of 22、B2O3、La2O3ZnO and MgO, and the preparation method specifically comprises the following steps:
mixing SiO2、B2O3、La2O3And ZnO and MgO are mixed and ball-milled for 24 hours, dried and sieved, then melted for 20 minutes at 1250 ℃, then extracted and separated by deionized water, and sieved by a 200-mesh sieve after being crushed to obtain the additive.
Example 1
(1) 71.762g of ZrO were weighed out in the proportions x 0.68, y 0 and z 0.322、136.964g TiO2And 41.274gSnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3:2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material, zirconium balls and deionized water in a proportion of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (with the pressure of 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1400 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The tests on various performances of the ZHTS microwave dielectric ceramic provided in embodiment 1 of the present invention specifically include:
polishing the surface of the prepared ceramic sample by a metallographic and flannelette medium, and measuring the dielectric constant epsilon by adopting an Agilent 5061B network analyzer according to a Hakki-Coleman methodrAnd tan delta, and calculating to obtain a quality factor Qf; in addition, the measurement of the temperature coefficient of the resonant frequency is to directly connect a network analyzer with a constant temperature box, test the change value of the resonant frequency in the temperature range of 20-85 ℃, and then calculate tau according to the formula shown in formula (II)fA value;
the test results of various properties of the ZHTS microwave dielectric ceramic provided in example 1 of the present invention are shown in table 1.
Example 2
(1) 69.866g of ZrO were weighed out in the proportions 0.665 x, 0.015 y and 0.32 z2、2.692g HfO2、136.353g TiO2And 41.09g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere), and raising the temperature rateAt 3 ℃/min, and then cooling along with the furnace to obtain a pre-sintered material; mixing the pre-sintering material, zirconium balls and deionized water in a proportion of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (with the pressure of 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1400 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 2 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 1.
Example 3
(1) 67.986g of ZrO were weighed out in the proportions x 0.65, y 0.03 and z 0.322、5.36g HfO2、135.764g TiO2And 40.907g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material, zirconium balls and deionized water in a proportion of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (with the pressure of 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1400 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 3 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 1.
TABLE 1 Performance data of the ZHTS microwave dielectric ceramics provided in the embodiments 1 to 3 of the present invention
| x | y | z | εr | Qf(GHz) | τf(ppm/℃) | |
| Example 1 | 0.68 | 0 | 0.32 | 40.06 | 50780 | -0.3 |
| Example 2 | 0.665 | 0.015 | 0.32 | 40.1 | 55460 | -0.2 |
| Example 3 | 0.65 | 0.03 | 0.32 | 40.23 | 47700 | -0.1 |
Example 4
(1) 69.866g of ZrO were weighed out in the proportions 0.665 x, 0.015 y and 0.32 z2、2.692g HfO2、136.353g TiO2And 41.09g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 0.4% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (with the pressure of 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1400 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 4 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 2.
Example 5
(1) 69.866g of ZrO were weighed out in the proportions 0.665 x, 0.015 y and 0.32 z2、2.692g HfO2、136.353g TiO2And 41.09g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2 in a mass ratio of (2),ball-milling for 4h by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3h at 950 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 5 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 2.
Example 6
(1) 69.866g of ZrO were weighed out in the proportions 0.665 x, 0.015 y and 0.32 z2、2.692g HfO2、136.353g TiO2And 41.09g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 950 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with a 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1300 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 6 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 2.
Table 2 Performance data of the ZHTS microwave dielectric ceramics provided in embodiments 4 to 6 of the present invention
| x | y | z | Additive agent | εr | Qf(GHz) | τf(ppm/℃) | |
| Example 4 | 0.665 | 0.015 | 0.32 | 0.4％ | 40.11 | 57300 | -0.1 |
| Example 5 | 0.665 | 0.015 | 0.32 | 1.2％ | 40.56 | 63500 | +0.1 |
| Example 6 | 0.665 | 0.015 | 0.32 | 2％ | 39.25 | 56300 | +0.2 |
Example 7
(1) 106.673g of ZrO were weighed out in the proportions x 0.985, y 0.015 and z 02、2.775g HfO2And 140.552g TiO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 7 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 3.
Example 8
(1) 90.294g of ZrO were weighed out in the proportions x 0.845, y 0.015 and z 0.142、2.738g HfO2、138.684g TiO2And 18.284g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 8 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 3.
Example 9
(1) 79.993g of ZrO were weighed out in the proportions x 0.755, y 0.015 and z 0.232、2.715g HfO2、137.508g TiO2And 29.784g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2 in a mass ratio of (2),ball-milling for 4h by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3h at 1050 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 9 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 3.
Example 10
(1) 59.907g of ZrO were weighed out in the proportions x 0.575, y 0.015 and z 0.412、2.67g HfO2、135.216g TiO2And 52.208g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 10 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 3.
Example 11
(1) 50.112g of ZrO were weighed out in the proportions 0.485 x, 0.015 y and 0.5 z2、2.648g HfO2、134.099g TiO2And 63.142g SnO2(ii) a Mixing the raw materials, zirconium balls and deionized water in a proportion of 1: 3: 2, ball-milling for 4 hours by using a planetary mill wet method, drying at 120 ℃, pre-burning for 3 hours at 1050 ℃ (in atmospheric atmosphere) at the heating rate of 3 ℃/min, and then cooling along with a furnace to obtain a pre-burning material; mixing the pre-sintering material with an additive to obtain a mixture of the pre-sintering material and the additive, wherein the amount of the additive is 1.2% of the mass of the pre-sintering material; mixing the mixture of the pre-sintering material and the additive, zirconium balls and deionized water in a ratio of 1: 3: 2, ball milling for 4 hours by a planetary mill wet method, and drying at 120 ℃ to obtain the microwave dielectric ceramic powder.
(2) Adding an adhesive accounting for 20% of the mass of the powder into the microwave dielectric ceramic powder obtained in the step (1), granulating and grinding for 1h, sieving with an 80-mesh sieve, pressing the obtained powder (the pressure is 100MPa) into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering the obtained blank at 1350 ℃ to form ceramic, heating at the rate of 3 ℃/min, keeping the temperature for 3h, and cooling with a furnace to obtain the ZHTS microwave dielectric ceramic.
The performance of the ZHTS microwave dielectric ceramic provided in example 11 of the present invention was tested according to the test method provided in example 1, and the results are shown in table 3.
Table 3 Performance data of the ZHTS microwave dielectric ceramics provided in embodiments 7 to 11 of the present invention
| x | y | z | Additive agent | εr | Qf(GHz) | τf(ppm/℃) | |
| Example 7 | 0.985 | 0.015 | 0 | 1.2％ | 43 | 51500 | +23 |
| Example 8 | 0.845 | 0.015 | 0.14 | 1.2％ | 41.5 | 59800 | +11.8 |
| Example 9 | 0.755 | 0.015 | 0.23 | 1.2％ | 41 | 61700 | +7.9 |
| Example 10 | 0.575 | 0.015 | 0.41 | 1.2％ | 38.5 | 65300 | -6.6 |
| Example 11 | 0.485 | 0.015 | 0.5 | 1.2％ | 38 | 68600 | -10.9 |
As can be seen from tables 1 to 3, the dielectric constant of the ZHTS microwave dielectric ceramic provided by the invention is between 38 and 43, the Qf is more than 51500GHz and can reach 68600GHz, and compared with other microwave dielectric ceramics with the same dielectric constant, the system has large Qf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-10.9 ppm/DEG C to +23 ppm/DEG C.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature of only 1200-1400 ℃ and low cost; and the method meets the requirement of environmental protection, has no toxicity and no pollution to the environment, is suitable for large-scale industrialization, and has very wide development prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A ZHTS microwave dielectric ceramic having the general formula shown in formula (I):
ZrxHfyTi2SnzO6formula (I);
in the formula (I), x is more than or equal to 0.485 and less than or equal to 0.845, y is 0.015, and x + y + z is 1;
the ZHTS microwave dielectric ceramic further comprises:
an additive;
the additive is prepared from the following components in percentage by mass (35-45): (15-25): (15-30): (5-20): (1-10) SiO2、B2O3、La2O3ZnO and MgO;
the amount of the additive is 0.4-1.2% of the mass of the ZHTS microwave medium ceramic.
2. The microwave dielectric ceramic of claim 1, wherein the preparation method of the additive specifically comprises:
mixing SiO2、B2O3、La2O3And ZnO and MgO are mixed and ball-milled, then melted for 10min to 30min at 1200 ℃ to 1300 ℃, and then crushed and sieved after separation to obtain the additive.
3. A method of making a ZHTS microwave dielectric ceramic according to claim 1, comprising the steps of:
a) ZrO 2 is mixed with2、HfO2、TiO2And SnO2After mixing, carrying out primary grinding treatment, and then carrying out presintering to obtain a presintering material; then, carrying out secondary grinding treatment on the obtained pre-sintering material to obtain powder;
b) adding an adhesive into the powder obtained in the step a) for granulation forming to obtain a ceramic green body; and sintering the obtained ceramic green body to obtain the ZHTS microwave dielectric ceramic.
4. The preparation method according to claim 3, wherein the first grinding treatment in step a) is carried out by:
mixing the mixed raw materials, zirconium balls and water in a proportion of 1: (3-4): (2-3), ball-milling for 3-5 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
5. The preparation method according to claim 3, wherein the temperature of the pre-sintering in the step a) is 950 ℃ to 1150 ℃, the heating rate is 3 ℃/min to 8 ℃/min, and the holding time is 3h to 4 h.
6. The preparation method according to claim 3, wherein the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the mass ratio of the powder to the adhesive is 100: (15-25).
7. The preparation method according to claim 3, wherein the granulating and forming process in the step b) is specifically as follows:
adding an adhesive into the microwave dielectric ceramic powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90 mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain the ceramic green body.
8. The preparation method according to claim 3, wherein the sintering temperature in step b) is 1200-1400 ℃, the heating rate is 3-8 ℃/min, and the holding time is 2-4 h.
9. The method according to any one of claims 3 to 8, wherein the step a) further comprises:
and mixing the obtained pre-sintered material with an additive, and then carrying out secondary grinding treatment to obtain powder.
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