CN112592195A - Complex phase microwave dielectric ceramic material and preparation method thereof - Google Patents
Complex phase microwave dielectric ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN112592195A CN112592195A CN202011388776.7A CN202011388776A CN112592195A CN 112592195 A CN112592195 A CN 112592195A CN 202011388776 A CN202011388776 A CN 202011388776A CN 112592195 A CN112592195 A CN 112592195A
- Authority
- CN
- China
- Prior art keywords
- complex
- equal
- ceramic material
- main body
- microwave dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
- Control Of Motors That Do Not Use Commutators (AREA)
Abstract
The invention belongs to the technical field of materials, and particularly relates to a complex-phase microwave dielectric ceramic material and a preparation method thereof. The aluminum oxide whisker is doped in the complex phase ceramic main body, and the aluminum oxide whisker has higher mechanical strength and higher elastic modulus, so that the aluminum oxide whisker is added into the complex phase ceramic main body in a proper amount to reinforce and toughen the complex phase ceramic main body, and the bending strength and the thermal shock resistance of the complex phase ceramic main body can be greatly improved. The complex phase microwave dielectric ceramic material provided by the invention has good comprehensive performance and dielectric constant epsilonr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.CfThe dielectric resonator and the filter are +/-10 ppm/DEG C, the quality factor Qf is more than or equal to 40000, the bending strength is more than or equal to 200MPa, the thermal shock temperature is 110 ℃, the reliability is higher, the requirement of miniaturization development of microwave components such as dielectric resonators and filters can be met, the dielectric resonator and the filter can also adapt to severe working environments such as large day and night temperature difference, and the like, and the dielectric resonator and the filter have good application prospects.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a complex-phase microwave dielectric ceramic material and a preparation method thereof.
Background
In recent years, with the rapid development of mobile communication and satellite communication technologies, microwave dielectric ceramics used for dielectric resonators, filters and the like have become one of the most active research fields of functional ceramics in recent years. Wherein the magnesium titanate (MgTiO)3) The base ceramic as a traditional microwave dielectric ceramic has excellent microwave dielectric properties such as low dielectric constant, high quality factor and the like. However, because of the inherent brittleness of the ceramic, microcracks are easily generated during rapid heating or rapid cooling at high temperature, and as the microcracks rapidly increase and expand, catastrophic failures such as failure, peeling and the like of the microwave dielectric ceramic device can be caused. In addition, as the communication industry is being developed toward miniaturization, integration, and high frequency, the demand for developing high dielectric microwave dielectric materials is also increasing. Therefore, it is an important subject to develop a microwave dielectric ceramic material with high comprehensive performance.
Disclosure of Invention
The invention aims to provide a complex-phase microwave dielectric ceramic material and a preparation method thereof, and aims to solve the technical problem that the comprehensive performance of the existing complex-phase microwave dielectric ceramic material needs to be improved.
In order to achieve the above object, in one aspect of the present invention, there is provided a complex phase microwave dielectric ceramic material comprising a complex phase ceramic body and a dopant dispersed in the complex phase ceramic body, wherein the complex phase ceramic body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the dopant comprises aluminum oxide whiskers.
The aluminum oxide whisker is doped in the complex phase ceramic main body comprising calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the aluminum oxide whisker has higher mechanical strength and elastic modulus, so that the aluminum oxide whisker is properly added into the complex phase ceramic main body to reinforce and toughen the complex phase ceramic main body, thereby greatly improving the bending strength and the thermal shock resistance of the complex phase ceramic main body. The complex phase microwave dielectric ceramic material provided by the invention has good comprehensive performance and dielectric constant epsilonrIs 30-50, resonant frequency temperature coefficient tau at-40 deg.C to 85 deg.CfThe dielectric resonator and the filter are +/-10 ppm/DEG C, the quality factor Qf is more than or equal to 40000, the bending strength is more than or equal to 200MPa, the thermal shock temperature is 110 ℃, the reliability is higher, the requirement of miniaturization development of microwave components such as dielectric resonators and filters can be met, the dielectric resonator and the filter can also adapt to severe working environments such as large day and night temperature difference, and the like, and the dielectric resonator and the filter have good application prospects.
In another aspect of the present invention, a method for preparing a complex phase microwave dielectric ceramic material is provided, which comprises the following steps:
providing a complex-phase ceramic main body and a doping agent, wherein the complex-phase ceramic main body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the doping agent comprises aluminum oxide whiskers;
and mixing the complex phase ceramic main body and the dopant, and obtaining the complex phase microwave dielectric ceramic material through molding treatment and sintering treatment.
The preparation method provided by the invention has simple steps and easy implementation, and the prepared complex-phase microwave dielectric ceramic material has good comprehensive performance and dielectric constant epsilonr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.Cf+/-10 ppm/DEG C, quality factor Qf is more than or equal to 40000, bending strength is more than or equal to 200MPa, thermal shock temperature is 110 ℃, and reliability is higher.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describing an association relationship of associated objects means that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a complex phase microwave dielectric ceramic material which comprises a complex phase ceramic main body and a doping agent dispersed in the complex phase ceramic main body, wherein the complex phase ceramic main body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the doping agent comprises aluminum oxide whiskers.
In the embodiment of the invention, the aluminum oxide whisker is doped in the complex phase ceramic main body comprising calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the aluminum oxide whisker has higher mechanical strength and elastic modulus, and is added into the complex phase ceramic main body in a proper amount to have the functions of reinforcing and toughening, so that the bending strength and the thermal shock resistance of the complex phase ceramic main body can be greatly improved. The complex phase microwave dielectric ceramic material provided by the embodiment of the invention has good comprehensive performance and dielectric constant epsilonr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.CfIs +/-10 ppm/DEG C, the quality factor Qf is more than or equal to 40000, the bending strength is more than or equal to 200MPa, and the thermal shock temperatureThe temperature is 110 ℃, the reliability is stronger, the requirement of miniaturization development of microwave components such as dielectric resonators, filters and the like can be met, the device can also adapt to severe working environments such as large day and night temperature difference and the like, and the device has a good application prospect.
Alumina has a plurality of homogeneous and heterogeneous crystals, including alpha, beta, gamma, theta, rho and the like, wherein the alpha, beta and gamma are the most three; the alumina whisker has the advantages of high strength and high elastic modulus, is white, has a needle-shaped or fibrous structure, and has a hexagonal section. In some embodiments, fibrous alpha-alumina whiskers having a purity greater than 99.9% are selected and have a diameter of 0.5 μm to 1.0 μm and a length of 10 μm to 15 μm. The fibrous alpha-alumina whisker belongs to a trigonal system and has the advantages of compact structure, low activity, stability at all temperatures and best electrical property. In addition, by selecting the alumina whisker with the diameter of 0.5-1.0 μm and the length of 10-15 μm, compared with alumina whiskers with other sizes, the alumina whisker can form a synergistic system with the complex phase ceramic formed by calcium oxide, samarium oxide, titanium dioxide and alumina, thereby further improving the overall performance and the thermal shock resistance of the obtained complex phase microwave dielectric ceramic material. Specifically, typical, but not limiting, alumina whisker diameters are 0.50 μm, 0.55 μm, 0.60 μm, 0.65 μm, 0.70 μm, 0.75 μm, 0.80 μm, 0.85 μm, 0.90 μm, 0.95 μm, 1.0 μm; typical, but not limiting, alumina whiskers have a length of 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm.
In some embodiments, the composite ceramic body has a composition formula of xCaO-ySm2O3-zTiO2-mAl2O3Wherein x is more than or equal to 30% and less than or equal to 40%, y is more than or equal to 25% and less than or equal to 40%, z is more than or equal to 10% and less than or equal to 20%, m is more than or equal to 5% and less than or equal to 20%, and x + y + z + m is equal to 100%. In the complex phase ceramic main body, the molar ratio of each component greatly influences the dielectric property and the comprehensive property of the obtained complex phase microwave dielectric ceramic material. In the embodiment of the invention, the values of x, y, z and m are optimized, so that calcium oxide (CaO) and samarium oxide (Sm) can be obtained2O3) Titanium dioxide (TiO)2) And alumina (Al)2O3) The composite ceramic main body material has good comprehensive performance and can be simultaneously mixed with fibrous alpha-aluminaThe whiskers generate synergistic action to jointly form a complex phase microwave dielectric ceramic material with excellent comprehensive performance, so that the dielectric constant epsilon of the complex phase microwave dielectric ceramic materialr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.CfIs +/-10 ppm/DEG C, the quality factor Qf is more than or equal to 40000, the bending strength is more than or equal to 200MPa, and the thermal shock temperature is 110 ℃.
The complex-phase microwave dielectric ceramic material provided by the embodiment of the invention can be prepared by the following preparation method.
Correspondingly, the embodiment of the invention also provides a preparation method of the complex-phase microwave dielectric ceramic material, which comprises the following steps:
s1, providing a complex phase ceramic main body and a doping agent, wherein the complex phase ceramic main body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the doping agent comprises aluminum oxide whiskers;
and S2, mixing the complex phase ceramic main body with the dopant, and obtaining the complex phase microwave dielectric ceramic material through molding treatment and sintering treatment.
The preparation method provided by the embodiment of the invention has simple steps and is easy to implement, and the prepared complex-phase microwave dielectric ceramic material has good comprehensive performance and dielectric constant epsilonr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.Cf+/-10 ppm/DEG C, quality factor Qf is more than or equal to 40000, bending strength is more than or equal to 200MPa, thermal shock temperature is 110 ℃, and reliability is higher.
Specifically, in S1, the complex phase ceramic main body may be a complex phase ceramic including calcium oxide, samarium oxide, titanium dioxide, and aluminum oxide, which is available in the art, or a complex phase ceramic main body prepared by the preparation method provided in the embodiments of the present invention. In some embodiments, in order to achieve the synergistic effect with the alumina whisker and improve the overall performance of the obtained complex-phase microwave dielectric ceramic material, the preparation method provided by the embodiments of the present invention is preferably adopted to prepare the obtained complex-phase ceramic main body, and the steps are as follows: mixing a calcium source, a samarium source, a titanium source and an aluminum source according to a stoichiometric ratio, and sintering to obtain a complex phase ceramic main body, wherein the composition formula of the complex phase ceramic main body is xCaO-ySm2O3-zTiO2-mAl2O3Wherein x is more than or equal to 30% and less than or equal to 40%, y is more than or equal to 25% and less than or equal to 40%, z is more than or equal to 10% and less than or equal to 20%, m is more than or equal to 5% and less than or equal to 20%, and x + y + z + m is equal to 100%. Wherein, the calcium source is calcium carbonate, the samarium source is samarium oxide, the titanium source is titanium dioxide, the aluminum source is aluminum oxide, and the specific mixing method can adopt a method commonly used in the field, including but not limited to ball milling; the sintering temperature is 1000-1200 deg.C, and the sintering time is 2-5 h. Specifically, typical but non-limiting sintering process temperatures are 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃; typical but not limiting sintering treatment times are 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5 h.
The alumina whisker is used as a dopant, and the specific selection and addition amount are as described above, and are not described herein again. In some embodiments, the alumina whisker is prepared into the alumina whisker dispersion liquid in advance, so that the doping distribution effect of the alumina whisker dispersion liquid as a dopant and the multiphase ceramic main body can be further improved. Specifically, the steps for preparing the alumina whisker dispersion liquid are as follows: dispersing the alumina whisker in deionized water to obtain 10-25 wt% of alumina whisker dispersion liquid; wherein the mass ratio of the alumina whisker to the deionized water is 1 (40-60).
In S2, the method for mixing the complex phase ceramic host and the dopant may be a method commonly used in the art, including but not limited to ball milling, and the specific parameters of the ball milling may be adjusted according to the actual situation.
In some embodiments, the forming process includes the steps of granulating and processing the mixture obtained by mixing the complex phase ceramic body and the dopant into a green body. In order to facilitate granulation and subsequent processing, a proper amount of additives such as a binder, a defoaming agent, a plasticizer and the like can be added into the mixture to form powder with better fluidity; the green body can be obtained by compressing powder through a powder tablet machine.
The sintering treatment can lead the green body to generate a series of physical and chemical reactions at high temperature, and further to be converted into the complex phase microwave dielectric ceramic material. The sintering condition has obvious influence on the performance of the obtained complex phase microwave dielectric ceramic material. In some embodiments, the green body is sintered at a temperature of 1400 ℃ to 1500 ℃ for a time of 3h to 6 h. The proper sintering temperature and time are beneficial to the migration of substances and the growth of crystal grains, so that the obtained complex phase microwave dielectric ceramic material is more compact and has better performance. If the sintering temperature is too high or the sintering time is too long, the problem of overburning is easy to occur, and pores in the material cannot be removed in time, so that the dielectric loss is increased; the sintering temperature is too low or the sintering time is too short, the obtained complex phase microwave dielectric ceramic material has poor compactness and influenced dielectric property. Specifically, typical but non-limiting sintering temperatures are 1400 ℃, 1410 ℃, 1420 ℃, 1430 ℃, 1440 ℃, 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃, 1490 ℃ and 1500 ℃; typical but not limiting sintering treatment times are 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6 h.
The dielectric constant epsilon of the complex-phase microwave dielectric ceramic material prepared by the preparation method provided by the embodiment of the inventionr30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.CfThe dielectric ceramic material has the advantages of +/-10 ppm/DEG C, quality factor Qf of more than or equal to 40000, bending strength of more than or equal to 200MPa, thermal shock temperature of 110 ℃, excellent comprehensive performance, capability of meeting the requirement of miniaturization development of microwave components such as dielectric resonators, filters and the like, and stronger reliability of the obtained components.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and obviously show the advanced performance of the complex phase microwave dielectric ceramic material and the preparation method thereof according to the embodiment of the present invention, the above technical solution is exemplified by a plurality of embodiments.
Example 1
The embodiment provides a preparation method of a complex-phase microwave dielectric ceramic material, which comprises the following steps:
(11) first CaCO3、Sm2O3、TiO2And Al2O3According to the component expression xCaO-ySm2O3-zTiO2-mAl2O3The molar ratio of the ingredients is that x is more than or equal to 30% and less than or equal to 40%, y is more than or equal to 25% and less than or equal to 40%, z is more than or equal to 10% and less than or equal to 20%, m is more than or equal to 5% and less than or equal to 20%, and x + y + z + m is equal to 100%. Ball milling, drying and sievingPresintering at 1200 ℃ for 3h, and preparing a complex phase ceramic main body by adopting a solid phase reaction method;
(12) weighing fibrous alpha-alumina whisker (the diameter is 0.6 mu m, the length is 10 mu m), adding deionized water (the mass ratio of the deionized water to the alumina whisker is 1 (40-60)), and uniformly dispersing by using ultrasonic to obtain alumina whisker dispersion liquid;
(13) mixing the alumina whisker dispersion liquid prepared in the step (12) with a complex phase ceramic main body to prepare mixed slurry, ball-milling for 6 hours by a wet milling method, drying, sieving, adding a binder, a defoaming agent and a plasticizer, granulating, and pressing into a green body (the diameter is 12.9mm, and the height is 6.3mm) by a powder tablet press;
(14) and (4) sintering the green body obtained in the step (13) at 1500 ℃, and preserving heat for 5 hours to prepare the complex-phase microwave dielectric ceramic material.
Examples 2 to 12
Examples 2 to 12 are substantially the same as example 1, except that the values of x, y, z and m in the composite ceramic body and the addition amount of the alumina whiskers are as shown in table 1.
TABLE 1 composition of the complex phase microwave dielectric ceramic materials of examples 1-12
Remarking: al (Al)2O3The mass percentage of the crystal whisker is based on the mass percentage of the complex phase ceramic main body.
The dielectric properties and thermal shock resistance of the complex-phase microwave dielectric ceramic materials obtained in examples 1 to 12 are detected, granulated powder is sintered into a sample with the thickness of 3mm by 4mm by 36mm by dry pressing to test thermal shock, and a thermal shock test is tested by a single thermal shock method of a water quenching method (the thermal shock temperature delta T is the highest non-cracking temperature of the dielectric-water temperature); testing the dielectric property of the product by adopting a microwave resonant cavity method; the flexural strength of the material was measured by a three-point bending method on an Instron-1186 electronic universal tester. The test sample is in a long bar shape with a rectangular cross section, the size of the test sample is 3mm multiplied by 4mm multiplied by 36mm, four edge chamfers in the length direction are 0.1-0.3 mm multiplied by 45 degrees, and 5 test samples are tested in each group. The results are shown in Table 2.
TABLE 2 dielectric properties and thermal shock resistance of the complex phase microwave dielectric ceramic materials obtained in examples 1-12
As can be seen from tables 1 and 2, in the complex phase microwave dielectric ceramic material provided by the invention, along with the decrease of the contents of calcium oxide and titanium dioxide, the dielectric constant and the temperature coefficient of the resonant frequency of the obtained complex phase microwave dielectric ceramic material are also gradually decreased, but the quality factor is gradually increased; when x is 35%, y is 40%, z is 20%, m is 10%, Al2O3The comprehensive performance of the obtained complex phase microwave dielectric ceramic material is optimal when the mass percentage of the crystal whiskers is 15%. Meanwhile, with the increase of the content of the aluminum oxide whiskers and the samarium oxide, the thermal shock temperature of the obtained complex-phase microwave dielectric ceramic material tends to increase, but when the mass fraction of the aluminum oxide whiskers exceeds 15%, the thermal shock temperature of the obtained complex-phase microwave dielectric ceramic material does not change obviously any more, and the dielectric constant and the Qf value are reduced.
Examples 3 to 11
Examples 2-11 are essentially the same as example 1, except for the size of the alumina whiskers, as shown in Table 3.
TABLE 3 composition and whisker size of the complex phase microwave dielectric ceramic materials of examples 3-11
The dielectric properties and thermal shock resistance of the complex-phase microwave dielectric ceramic materials obtained in examples 1 to 12 are detected, granulated powder is sintered into a sample with the thickness of 3mm by 4mm by 36mm by dry pressing to test thermal shock, and a thermal shock test is tested by a single thermal shock method of a water quenching method (the thermal shock temperature delta T is the highest non-cracking temperature of the dielectric-water temperature); testing the dielectric property of the product by adopting a microwave resonant cavity method; the flexural strength of the material was measured by a three-point bending method on an Instron-1186 electronic universal tester. The test sample is in a long bar shape with a rectangular cross section, the size of the test sample is 3mm multiplied by 4mm multiplied by 36mm, four edge chamfers in the length direction are 0.1-0.3 mm multiplied by 45 degrees, and 5 test samples are tested in each group. The results are shown in Table 4.
TABLE 4 dielectric Properties and thermal shock resistances of the complex phase microwave dielectric ceramic materials obtained in examples 13 to 11
As can be seen from tables 3 and 4, the toughening effect of the invention is obvious when the alpha-alumina whisker (with the diameter of 0.6 μm, the length of 12 μm and the length-diameter ratio of 20) is added, and the toughening effect is weakened when the added alumina whisker is increased in radius and length and added in the same amount.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The complex-phase microwave dielectric ceramic material is characterized by comprising a complex-phase ceramic main body and a dopant dispersed in the complex-phase ceramic main body, wherein the complex-phase ceramic main body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the dopant comprises aluminum oxide whiskers.
2. The composite microwave dielectric ceramic material as claimed in claim 1, wherein the alumina whiskers are fibrous alpha-alumina whiskers with a diameter of 0.5 μm to 1.0 μm and a length of 10 μm to 15 μm; and/or
The weight of the alumina whisker accounts for 5-15% of the weight of the complex phase ceramic main body.
3. Root of herbaceous plantThe composite microwave dielectric ceramic material as claimed in claim 1, wherein the composite ceramic body has a composition formula of xCaO-ySm2O3-zTiO2-mAl2O3Wherein x is more than or equal to 30% and less than or equal to 40%, y is more than or equal to 25% and less than or equal to 40%, z is more than or equal to 10% and less than or equal to 20%, m is more than or equal to 5% and less than or equal to 20%, and x + y + z + m is equal to 100%.
4. The complex phase microwave dielectric ceramic material as claimed in any one of claims 1 to 3, wherein the complex phase microwave dielectric ceramic material has a dielectric constant ∈r30-50, and a temperature coefficient of resonance frequency tau at-40 deg.C to 85 deg.CfIs +/-10 ppm/DEG C, the quality factor Qf is more than or equal to 40000, the bending strength is more than or equal to 200MPa, and the thermal shock temperature is 110 ℃.
5. The preparation method of the complex-phase microwave dielectric ceramic material is characterized by comprising the following steps of:
providing a complex-phase ceramic main body and a doping agent, wherein the complex-phase ceramic main body comprises calcium oxide, samarium oxide, titanium dioxide and aluminum oxide, and the doping agent comprises aluminum oxide whiskers;
and mixing the complex phase ceramic main body and the dopant, and obtaining the complex phase microwave dielectric ceramic material through molding treatment and sintering treatment.
6. The preparation method of the complex phase microwave dielectric ceramic material as claimed in claim 5, wherein the sintering treatment temperature is 1400 ℃ to 1500 ℃, and the sintering treatment time is 3h to 6 h.
7. The preparation method of the complex phase microwave dielectric ceramic material as claimed in claim 5, wherein the preparation method of the complex phase ceramic main body comprises: mixing a calcium source, a samarium source, a titanium source and an aluminum source according to a stoichiometric ratio, and sintering to obtain the complex-phase ceramic main body.
8. The preparation method of the complex phase microwave dielectric ceramic material as claimed in claim 7, wherein the sintering treatment temperature is 1000 ℃ to 1200 ℃, and the sintering treatment time is 2h to 5 h.
9. The preparation method of the complex phase microwave dielectric ceramic material as claimed in any one of claims 5 to 8, wherein the alumina whiskers are alumina whisker dispersion liquid.
10. The preparation method of the complex phase microwave dielectric ceramic material as claimed in claim 9, wherein the preparation method of the alumina whisker dispersion liquid comprises the following steps: dispersing the alumina crystal whisker in deionized water to obtain alumina crystal whisker dispersion liquid; wherein the mass ratio of the alumina whiskers to the deionized water is 1 (40-60).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011388776.7A CN112592195A (en) | 2020-12-02 | 2020-12-02 | Complex phase microwave dielectric ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011388776.7A CN112592195A (en) | 2020-12-02 | 2020-12-02 | Complex phase microwave dielectric ceramic material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112592195A true CN112592195A (en) | 2021-04-02 |
Family
ID=75187678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011388776.7A Pending CN112592195A (en) | 2020-12-02 | 2020-12-02 | Complex phase microwave dielectric ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112592195A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321521A (en) * | 2021-05-27 | 2021-08-31 | 无锡市高宇晟新材料科技有限公司 | Alumina whisker doped low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN116969760A (en) * | 2023-08-01 | 2023-10-31 | 陕西华星电子开发有限公司 | Ca-Sm-Al-Ti-based microwave dielectric ceramic material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638317A (en) * | 2008-08-02 | 2010-02-03 | 比亚迪股份有限公司 | Fully stabilized zirconia ceramic material and preparation method thereof |
| WO2013167509A1 (en) * | 2012-05-07 | 2013-11-14 | Neoker, S.L. | Silica-surface modified alpha-alumina whiskers and uses thereof |
| CN103508744A (en) * | 2013-04-03 | 2014-01-15 | 安徽美芝精密制造有限公司 | Ceramic material, and preparation method and applications thereof |
| CN107056316A (en) * | 2017-06-20 | 2017-08-18 | 广东工业大学 | A kind of preparation method of high length-diameter ratio alumina whisker Strengthening and Toughening Ce TZP complex phase ceramics |
| CN110156465A (en) * | 2019-06-10 | 2019-08-23 | 南京信息工程大学 | A kind of preparation method of medium dielectric constant microwave medium ceramic dielectric resonator material |
| CN110563477A (en) * | 2019-09-20 | 2019-12-13 | 江苏金石研磨有限公司 | in-situ grown alumina whisker reinforced and toughened zirconium-aluminum composite ceramic material and preparation method thereof |
-
2020
- 2020-12-02 CN CN202011388776.7A patent/CN112592195A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638317A (en) * | 2008-08-02 | 2010-02-03 | 比亚迪股份有限公司 | Fully stabilized zirconia ceramic material and preparation method thereof |
| WO2013167509A1 (en) * | 2012-05-07 | 2013-11-14 | Neoker, S.L. | Silica-surface modified alpha-alumina whiskers and uses thereof |
| CN103508744A (en) * | 2013-04-03 | 2014-01-15 | 安徽美芝精密制造有限公司 | Ceramic material, and preparation method and applications thereof |
| CN107056316A (en) * | 2017-06-20 | 2017-08-18 | 广东工业大学 | A kind of preparation method of high length-diameter ratio alumina whisker Strengthening and Toughening Ce TZP complex phase ceramics |
| CN110156465A (en) * | 2019-06-10 | 2019-08-23 | 南京信息工程大学 | A kind of preparation method of medium dielectric constant microwave medium ceramic dielectric resonator material |
| CN110563477A (en) * | 2019-09-20 | 2019-12-13 | 江苏金石研磨有限公司 | in-situ grown alumina whisker reinforced and toughened zirconium-aluminum composite ceramic material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321521A (en) * | 2021-05-27 | 2021-08-31 | 无锡市高宇晟新材料科技有限公司 | Alumina whisker doped low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN113321521B (en) * | 2021-05-27 | 2023-04-07 | 无锡市高宇晟新材料科技有限公司 | Alumina whisker doped low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN116969760A (en) * | 2023-08-01 | 2023-10-31 | 陕西华星电子开发有限公司 | Ca-Sm-Al-Ti-based microwave dielectric ceramic material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112624755A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN1117708C (en) | Low temp. sinterable and low loss dielectric ceramic compositions and method thereof | |
| CN112592195A (en) | Complex phase microwave dielectric ceramic material and preparation method thereof | |
| CN112592174A (en) | Microwave dielectric ceramic material with high thermal shock resistance and preparation method thereof | |
| US4690911A (en) | Zirconia ceramics and process for producing the same | |
| CN107382313A (en) | A kind of microwave-medium ceramics of ultra high quality factor, middle low-k and nearly zero-temperature coefficient and preparation method thereof | |
| CN113321521B (en) | Alumina whisker doped low-dielectric microwave dielectric ceramic material and preparation method thereof | |
| JP5142700B2 (en) | Dielectric ceramic composition and dielectric resonator | |
| US5561090A (en) | Dielectric ceramic composition for high frequencies and method for preparation of the same | |
| EP0169077B1 (en) | Dielectric porcelain material | |
| JP2554478B2 (en) | Microwave dielectric porcelain composition | |
| JPH06333429A (en) | Dielectric porcelain composition for high frequency | |
| US5527749A (en) | Dielectric ceramic composition for high frequencies and method for preparation of the same | |
| JP2005239446A (en) | Porcelain composition and its manufacturing method | |
| JPH068209B2 (en) | High frequency dielectric ceramic composition | |
| US5182240A (en) | Dielectric ceramic composition of BaO, TiO2,Nd2 O3, Sm2 3 and Al2 O3 | |
| JPS6366795B2 (en) | ||
| US4601990A (en) | High-alumina ceramic composition | |
| JPH0742165B2 (en) | Microwave dielectric ceramics | |
| JP3699598B2 (en) | Dielectric porcelain composition | |
| JP3447971B2 (en) | Dielectric porcelain composition | |
| JPS6227373A (en) | Dielectric ceramic | |
| JP3101965B2 (en) | Dielectric porcelain composition | |
| JP3340019B2 (en) | High frequency dielectric ceramic composition | |
| JPH06293558A (en) | Alumina ceramics for dielectric material and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210402 |
|
| RJ01 | Rejection of invention patent application after publication |