CN102731092B - Zr-Ti-based microwave dielectric ceramic material and preparation method thereof - Google Patents

Zr-Ti-based microwave dielectric ceramic material and preparation method thereof Download PDF

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CN102731092B
CN102731092B CN 201210227586 CN201210227586A CN102731092B CN 102731092 B CN102731092 B CN 102731092B CN 201210227586 CN201210227586 CN 201210227586 CN 201210227586 A CN201210227586 A CN 201210227586A CN 102731092 B CN102731092 B CN 102731092B
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唐斌
余盛全
钟朝位
周晓华
张树人
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a Zr-Ti-based microwave dielectric ceramic material and a preparation method of the Zr-Ti-based microwave dielectric ceramic material, and belongs to the field of information functional materials and devices. The microwave dielectric ceramic material comprises a base material and an additive; the base material is represented by (1-x)ZrTi2O6-xZnNb2O6, wherein x is more thanor equal to 0.20 and is less than or equal to 0.40; the additive comprises CuO equaling to 0.50-2.50% of the weight of the base material and MnO equaling to 0.12-0.90% of the weight of the base material; the crystalline phase of the Zr-Ti-based microwave dielectric ceramic material comprises ZrTi2O6 phase and TiO2 phase; the dielectric constant epsilon r of the microwave dielectric ceramic material is between 41 and 53; the (Q*f) value of the microwave dielectric ceramic material is between 35,000GHz and 49,000GHz; and the frequency-temperature coefficient tau f of the microwave dielectric ceramic material is adjustable on the both sides of zero. The Zr-Ti-based microwave dielectric ceramic material is prepared by a normal process, is sintering in air, and has great popularization value and practical value. The Zr-Ti-based microwave dielectric ceramic material is suitable for production of microwave communication components, such as dielectric resonators, dielectric filters, dielectric substrates, dielectric antennae and the like, in the modern communication technology.

Description

A kind of Zr-Ti base microwave medium ceramic material and preparation method thereof
Technical field
The invention belongs to electronic information function material and device technology field, relate to the Zr-Ti base microwave dielectric ceramics, especially have the novel microwave dielectric pottery of high quality factor, low frequency temperature coefficient.Can be used for making the microwave communication components and parts such as dielectric resonator, dielectric filter, medium substrate and dielectric antenna in the modern communication technology.
Background technology
Microwave-medium ceramics is that to be applied to microwave frequency band (mainly be UHF, SHF frequency range, as dielectric material and finish the pottery of one or more functions, be in recent years both at home and abroad to a focus direction of microwave dielectric material research field in the circuit of 300MHz～300GHz).Components and parts such as the resonator of making of microwave dielectric ceramic materials, filter, oscillator, attenuator, dielectric antenna, microwave integrated circuit substrate are widely used in the modern communications equipment that mobile communication, satellite communication, military radar, GPS (Global Position System) (GPS), Bluetooth technology, WLAN (wireless local area network) etc. use.Main performance requirement to microwave dielectric ceramic materials is: (1) high-k (20 ~ 100), and high dielectric constant is conducive to realize the miniaturization of components and parts, because the square root of the dielectric constant of the size of resonator and dielectric substance is inversely proportional to; (2) high quality factor (Q＞3000), the Q value of microwave dielectric ceramic materials is more big, and the insertion loss of filter is just more low; (3) low frequency temperature coefficient (0 ± 10ppm/ ℃), low frequency-temperature coefficient means that the centre frequency of device is little with variation of ambient temperature, job stability improves.In addition, the components and parts of making of microwave dielectric ceramic materials not only have advantages such as volume is little, quality light, stable performance, low price; Complicated adjustment work can also be reduced, circuit design can be simplified.
Zr-Ti base pottery is the common microwave-medium ceramics of a class.The microwave dielectric property of pure ZrTiO4 pottery is: DIELECTRIC CONSTANT r=42, Q * f=28000GHz, frequency-temperature coefficient τ f=+58ppm/ ℃.High frequency-temperature coefficient and high sintering temperature (＞1600 ℃) make pure ZrTiO 4The using value of pottery is extremely low.For (reduction) ZrTiO that is coupled 4The high-frequency temperature coefficient of pottery obtains nearly zero frequency-temperature coefficient, and in the period of 1975 ~ 1977, Japanese village field company (MurataManufacturing Company) is at ZrTiO 4The pottery the basis on by using Sn 4+Ion replaces the Zr of 20mol% 4+Ion has been developed the (Zr with low frequency temperature coefficient 0.8Sn 0.2) TiO 4Microwave-medium ceramics has welcome second breakthrough of microwave-medium ceramics research for this reason.(Zr 0.8Sn 0.2) TiO 4The typical microwave dielectric property of pottery is: DIELECTRIC CONSTANT r=38.9, Q * f=51500GHz, frequency-temperature coefficient τ f=+0.7ppm/ ℃, but sintering obtains dense micro-structure (Zr 0.8Sn 0.2) TiO 4Pottery is very difficult, reaches 1600 ℃ even work as sintering temperature.After this, for improving sintering character, with B 2O 3, ZnO, NiO, CuO, La 2O 3, Nd 2O 3Etc. oxide-doped (Zr 0.8Sn 0.2) TiO 4Microwave-medium ceramics appears in the newspapers in succession, though these ceramic sintering temperatures have dropped to 1100 ~ 1400 ℃, their microwave dielectric property all has deterioration in various degree.2003, the Korea S scholar reported another coupling (reduction) ZrTiO at " Materials Chemistry and Physics " 4The thinking of high-frequency temperature coefficient of pottery is namely used the Zn of 1/3 ratio 2+Ion and 2/3 percentage of T a 5+The compound replacement part of ion Zr 4+Ion has obtained Zr x(Zn 1/3Ta 2/3) 1-xTiO 4Microwave-medium ceramics, its sintering temperature is 1300 ℃, microwave dielectric property can be: DIELECTRIC CONSTANT r=42.5, Q * f=40200GHz, frequency-temperature coefficient τ f=+1.1ppm/ ℃.The sintering temperature of this kind Zr-Ti base microwave dielectric ceramics has had obvious reduction, and frequency-temperature coefficient also has been coupled near zero, but its major defect is exactly Ta 2O 5Expensive, increased preparation cost.By 2006, the Britain research personnel reported and have used Nb at " Journal of the American Ceramic Society " 2O 5Replace expensive Ta 2O 5, prepared by (Zn 1/3Nb 2/3) 4+The ZrTi that replaces 2O 6Pottery, they can be at 1260 ~ 1300 ℃ of densified sintering products, and its microwave dielectric property can be: DIELECTRIC CONSTANT r=47, Q * f=34000GHz, frequency-temperature coefficient τ f≈ 0ppm/ ℃, but it must be at O 2The condition that could obtain high Q * f value of middle sintering has increased the requirement to agglomerating plant, also is difficult to promote practicability.
In a word, based on Zr-Ti base pottery, study a kind of high quality factor (high Q * f value), low frequency temperature coefficient, can in air, have very big scientific research value and market value by novel microwave dielectric pottery intermediate sintering temperature, that the cost of raw material is low simultaneously.
Summary of the invention
The objective of the invention is in order to overcome the technical barrier of existing preparation Zr-Ti base microwave dielectric ceramics, provide a kind of high quality factor, low frequency temperature coefficient to the wireless communication technology that constantly develops towards high frequency, and can be in less than 1300 ℃ of air the novel Zr-Ti base microwave medium ceramic material of sintering, and the preparation technology of this microwave-medium ceramics belongs to factory's production technology commonly used, is convenient to produce in batches and application.
Technical solution of the present invention is as follows:
A kind of Zr-Ti base microwave medium ceramic material comprises base-material and additive.Described base-material is (1-x) ZrTi 2O 6-xZnNb 2O 6, 0.20≤x≤0.40 wherein; Described additive is for being equivalent to CuO and the 0.12% ~ 0.90%MnO of base-material quality 0.50% ~ 2.50%.Its crystalline phase is formed and is comprised ZrTi 2O 6Phase and TiO 2Phase, DIELECTRIC CONSTANT rBe that 41 ~ 53, Q * f value is 35000GHz ~ 49000GHz, frequency-temperature coefficient τ fAdjustable on 0 both sides.
A kind of preparation method of Zr-Ti base microwave medium ceramic material may further comprise the steps:
Step 1: batching.Select ZrO 2, ZnO, Nb 2O 5And TiO 2As raw material (purity suitable 〉=99%), according to composition formula (1-x) ZrTi 2O 6-xZnNb 2O 6The mol ratio of (0.20≤x≤0.40) is prepared burden.
Step 2 a: ball milling.The ZrO that step 1 is prepared 2, ZnO, Nb 2O 5And TiO 2Raw material carries out ball milling one time, after one time ball milling is intact 60 mesh sieves are dried and crossed to a ball milling material down in 100 ℃.A concrete ball-milling technology is: in nylon ball grinder, with the zirconium ball as abrading-ball, deionized water as ball-milling medium, ball milling 10 ~ 20 hours.
Step 3: pre-burning.With a ball milling material behind step 2 oven dry and mistake 60 mesh sieves, pre-burning is 2 ~ 5 hours under 1000 ℃ ~ 1150 ℃ temperature conditions, obtains pre-imitation frosted glass, i.e. base-material.
Step 4: doping.The MnO(purity of adding the CuO be equivalent to base-material quality 0.50% ~ 2.50% and 0.12% ~ 0.90% in the pre-imitation frosted glass of step 3 gained is suitable 〉=and 99%).
Step 5: secondary ball milling.Carry out secondary ball milling with having added the base-material behind the additive in the step 4, after secondary ball milling is intact 80 mesh sieves are dried and crossed to the secondary ball milling material down in 100 ℃.Concrete secondary ball milling technology is identical with ball-milling technology described in the step 2.
Step 6: granulation, moulding.With the secondary ball milling material behind oven dry in the step 5 and mistake 80 mesh sieves, interpolation is equivalent to polyvinyl alcohol (PVA) granulation of above-mentioned secondary ball milling material quality 7%, and is pressed into green compact under 20MPa ~ 35MPa.
Step 7: sintering.With step 6 gained green compact, be sintering 5 ~ 10 hours under 1240 ~ 1280 ℃, air conditions in temperature, obtain final Zr-Ti base microwave ceramic dielectric material.
In the Zr-Ti base microwave medium ceramic material provided by the invention, base-material partly is for synthetic Zr-Ti based ceramic powder body, ZnNb 2O 6Effect be with (Zn 1/3Nb 2/3) 4+Form replace Zr 4+Ion or Ti 4+Ion is with coupling ZrTi 2O 6The frequency-temperature coefficient that matrix is high can make the sintering temperature of whole system be reduced to about 1300 ℃ simultaneously; The main effect of adding The addition of C uO is to continue to reduce sintering temperature, and adjusts microwave dielectric property; The main effect of adding an amount of MnO improves Q * f value, and make this kind pottery can be in air sintering, and adjust other microwave dielectric properties.The sintering atmosphere of final this microwave-medium ceramics is air, and sintering temperature is at 1240 ~ 1280 ℃, DIELECTRIC CONSTANT rBe that 41 ~ 53, Q * f value is 35000GHz ~ 49000GHz, frequency-temperature coefficient τ fAdjustable on 0 both sides.
Than other many existing Zr-Ti base microwave dielectric ceramics, novel Zr-Ti base microwave dielectric ceramics provided by the invention is not only in microwave dielectric property (DIELECTRIC CONSTANT rBe that 41 ~ 53, Q * f value is 35000GHz ~ 49000GHz, frequency-temperature coefficient τ fAdjustable on 0 both sides) aspect have large improvement, and its sintering condition is simple, and (sintering atmosphere is air, sintering temperature is at 1240 ~ 1280 ℃), have very big popularization practical value, thereby be well suited for for the microwave communication components and parts such as dielectric resonator, dielectric filter, medium substrate and dielectric antenna of making modern communication technology.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the XRD collection of illustrative plates of the Zr-Ti base microwave ceramic dielectric material of 4 preparations of embodiment among the present invention.
Fig. 3 is the SEM picture of the Zr-Ti base microwave ceramic dielectric material of 4 preparations of embodiment among the present invention.
Embodiment
Novel microwave dielectric pottery provided by the invention is characterized by: be base with Zr-Ti, its one-tenth is grouped into and comprises base-material and additive two parts: base-material is (1-x) ZrTi 2O 6– xZnNb 2O 6, 0.20≤x≤0.40 wherein; Additive is CuO and the z wt%MnO that is equivalent to base-material quality y wt% after the pre-burning, wherein 0.50≤y≤2.50,0.12≤z≤0.90; Its crystalline phase is formed and is comprised ZrTi 2O 6Phase and TiO 2Phase.Base-material partly is for synthetic Zr-Ti based ceramic powder body, ZnNb 2O 6Effect be with (Zn 1/3Nb 2/3) 4+Form replace Zr 4+Ion or Ti 4+Ion is with coupling ZrTi 2O 6The frequency-temperature coefficient that matrix is high can make the sintering temperature of whole system be reduced to about 1300 ℃ simultaneously; The main effect of adding The addition of C uO is to continue to reduce sintering temperature, and adjusts microwave dielectric property; The main effect of adding an amount of MnO improves Q * f value, though this kind pottery can be in air sintering, and adjust other microwave dielectric properties.The sintering atmosphere of final this microwave-medium ceramics is air, and sintering temperature is at 1240 ~ 1280 ℃, DIELECTRIC CONSTANT rBe that 41 ~ 53, Q * f value is 35000GHz ~ 49000GHz, frequency-temperature coefficient τ fAdjustable on 0 both sides.The technology for preparing this microwave-medium ceramics simultaneously belongs to factory's production technology commonly used, is convenient to produce in batches and application.
The present invention is further elaborated below in conjunction with the drawings and specific embodiments:
Embodiment 1 ~ 9
The concrete implementation step that makes these embodiment microwave-medium ceramics is as follows:
(1) ZrO of selection purity 〉=99% 2, ZnO, Nb 2O 5And TiO 2As raw material, according to composition formula (1-x) ZrTi 2O 6-xZnNb 2O 6The mol ratio of (0.20≤x≤0.40) is prepared burden, and concrete prescription sees table 1 for details;
(2) the above-mentioned material for preparing is put into nylon ball grinder, and with the zirconium ball as abrading-ball, deionized water as ball-milling medium, carried out ball milling 10 ~ 20 hours; A ball milling material is taken out in the intact back of ball milling dries and crosses 60 mesh sieves down at 100 ℃;
(3) with a ball milling material behind above-mentioned mistake 60 mesh sieves, pre-burning is 2 ~ 5 hours under 1000 ℃ ~ 1150 ℃ temperature conditions, obtains pre-imitation frosted glass;
(4) in pre-imitation frosted glass, add additive, namely be equivalent to the CuO of base-material quality y wt% after the pre-burning and the MnO of z wt%, 0.50≤y≤2.50,0.12≤z≤0.90 wherein, concrete addition sees table 1 for details;
(5) material that has added additive is put into nylon ball grinder, and with the zirconium ball as abrading-ball, deionized water as ball-milling medium, carried out secondary ball milling 10 ~ 20 hours; The secondary ball milling material is taken out in the intact back of secondary ball milling dries and crosses 80 mesh sieves down at 100 ℃;
(6) the material of intact 80 mesh sieves of above-mentioned mistake, add the 7wt%PVA granulation, and depress to the diameter aspect ratio at 20MPa and be about 2.0 cylinder green compact;
(7) be that 1240 ~ 1280 ℃, atmosphere are sintering 5 ~ 10 hours under the conditions of air with the cylinder green compact that prepare in temperature, finally obtain novel Zr-Ti base microwave ceramic dielectric material provided by the invention.
(8) according to Hakki-Coleman dielectric resonance method, with the dielectric property under network analyzer (Agilent Technologies E5071C) the specimen high frequency.Frequency-temperature coefficient is by formula Calculate gained, wherein t 1=25 ℃, t 2=80 ℃,
Figure BDA00001847861900052
With
Figure BDA00001847861900053
It is the resonance frequency at these two temperature spots.Test result is as shown in table 1.
Table 1 embodiment 1 ~ 9 concrete one-tenth is grouped into and microwave dielectric property
Preferred plan is shown in the embodiment 4 among the present invention.The present invention also is not limited to above-mentioned 9 specific embodiments, at base-material (1-x) ZrTi 2O 6-xZnNb 2O 6The CuO of (0.20≤x≤0.40) and additive y wt%, the MnO of z wt%, wherein, 0.50≤y≤2.50,0.12 inching is carried out in liang aspect ,≤z≤0.90, and suitably adjust preparation technology and parameter, thereby the microwave-medium ceramics that obtains new excellent performance is feasible fully, but this all also belongs to the scope of the invention.

Claims (3)

1. the preparation method of a Zr-Ti base microwave medium ceramic material may further comprise the steps:
Step 1: batching; Select ZrO 2, ZnO, Nb 2O 5And TiO 2As raw material, according to composition formula (1-x) ZrTi 2O 6– xZnNb 2O 6Mol ratio prepare burden 0.20≤x≤0.40 wherein;
Step 2 a: ball milling; The ZrO that step 1 is prepared 2, ZnO, Nb 2O 5And TiO 2Raw material carries out ball milling one time, after one time ball milling is intact 60 mesh sieves are dried and crossed to a ball milling material down in 100 ℃;
Step 3: pre-burning; With a ball milling material behind step 2 oven dry and mistake 60 mesh sieves, pre-burning is 2～5 hours under 1000 ℃～1150 ℃ temperature conditions, obtains pre-imitation frosted glass, i.e. base-material;
Step 4: doping; In the pre-imitation frosted glass of step 3 gained, add and be equivalent to the CuO of base-material quality 0.50%～2.50% and 0.12%～0.90% MnO;
Step 5: secondary ball milling; Carry out secondary ball milling with having added the base-material behind the additive in the step 4, after secondary ball milling is intact 80 mesh sieves are dried and crossed to the secondary ball milling material down in 100 ℃;
Step 6: granulation, moulding; With the secondary ball milling material behind oven dry in the step 5 and mistake 80 mesh sieves, interpolation is equivalent to the polyvinyl alcohol granulation of above-mentioned secondary ball milling material quality 7%, and is pressed into green compact under 20MPa～35MPa;
Step 7: sintering; With step 6 gained green compact, be sintering 5～10 hours under 1240～1280 ℃, air conditions in temperature, obtain final Zr-Ti base microwave ceramic dielectric material;
The crystalline phase of gained Zr-Ti base microwave medium ceramic material is formed and is comprised ZrTi 2O 6Phase and TiO 2Phase, DIELECTRIC CONSTANT rBe that 41～53, Q * f value is 35000GHz～49000GHz, frequency-temperature coefficient τ fAdjustable on 0 both sides.
2. the preparation method of Zr-Ti base microwave medium ceramic material according to claim 1, it is characterized in that, a ball-milling technology is identical with secondary ball milling technology in the step 5 described in the step 2, specifically: in nylon ball grinder, with the zirconium ball as abrading-ball, deionized water as ball-milling medium, ball milling 10～20 hours.
3. the preparation method of Zr-Ti base microwave medium ceramic material according to claim 1 is characterized in that, described ZrO 2, ZnO, Nb 2O 5And TiO 2The purity of raw material and CuO and MnO additive 〉=99%.
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CN105000883A (en) * 2015-08-05 2015-10-28 天津大学 Medium temperature stabilization type microwave dielectric ceramic material used in LTCC technology
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