CN109534806A - A kind of Li system microwave dielectric ceramic material and its preparation method and application - Google Patents
A kind of Li system microwave dielectric ceramic material and its preparation method and application Download PDFInfo
- Publication number
- CN109534806A CN109534806A CN201910015547.1A CN201910015547A CN109534806A CN 109534806 A CN109534806 A CN 109534806A CN 201910015547 A CN201910015547 A CN 201910015547A CN 109534806 A CN109534806 A CN 109534806A
- Authority
- CN
- China
- Prior art keywords
- sintering
- temperature
- dielectric ceramic
- microwave dielectric
- ceramic material
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- 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
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
-
- 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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- 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
- C04B2235/74—Physical characteristics
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Abstract
The present invention provides a kind of Li system microwave dielectric ceramic materials and its preparation method and application.The Li system microwave dielectric ceramic material of the invention includes major ingredient Li2CO3、SiO2And MgO, also comprising replacing material NiO.Li system microwave dielectric ceramic material of the invention has the excellent characteristics of low-k, high quality factor, high relative density and low densification temperature.The preparation method of Li system microwave dielectric ceramic material of the invention improves Li under 1120~1160 DEG C of low sintering temperatures2MgSiO4Sintering characteristic, micromorphology and the electric property of microwave dielectric ceramic, in the case where adding a small amount of sintering aid, it can be achieved that being lower than 961 DEG C of sintering temperature.
Description
Technical field
The invention belongs to microwave dielectric ceramic technical fields, are related to a kind of Li system microwave dielectric ceramic material and its preparation side
Method and purposes more particularly to a kind of Li system microwave dielectric ceramic material of low-k and its preparation method and application, especially
It is related to a kind of Li system microwave dielectric ceramic material and its preparation method and application of low sintering low-k.
Background technique
The arrival in 5G epoch proposes huge challenge to the research and development of microwave dielectric ceramic material, in order to reduce signal transmission
Delay and transmission loss, these microwave dielectric ceramic materials need that there is lower dielectric constant, higher quality factor and
Close to zero temperature coefficient of resonance frequency, and these parameters are particularly important in wireless communication field.Low-temperature co-fired ceramics
(LTCC) it is a kind of encapsulation technology with high performance-price ratio, is to realize microwave device to the side such as high frequency, high speed, lightweight, slim
To the important channel of development, therefore, reduce the sintering temperature of microwave-medium ceramics, can with low cost metal (silver,
Copper) cofiring is also the Main way studied at present.
In recent years, people have done a large amount of research, such as Zn to microwave dielectric ceramic2SiO4、Ag2MoO4、LiAlSiO4Deng
Deng these materials all have huge potential using value in the field LTCC.Silicate due to lower dielectric constant, compared with
High quality factor, therefore become the active material of production microwave device.Wherein, Li2MgSiO4Ceramic material is that a kind of production is micro-
The active material of wave device, Li2MgSiO4Ceramic material is in 1250 DEG C of sintering with ultralow dielectric constant (εr=5.1), compared with
High quality factor (Q × f=15,400GHz) and lower relative density (92%).However, being produced in ceramic material sintering process
The dielectric properties of raw stomata and material itself, which have, closely to be contacted, and lower densification degree will deteriorate quality factor and Jie
Electric constant, to influence the performance of microwave device.In addition, Li2MgSiO4The sintering temperature of ceramic material is 1250 DEG C, is much higher than
Silver point cannot achieve the common encapsulation with silver.Therefore, in order to improve Li2MgSiO4Electric property and be applied to LTCC lead
Domain should start with from improving its consistency, reducing densification temperature.
CN107382299A discloses a kind of low temperature preparation method of low dielectric microwave media ceramic, comprises the following steps: step
Rapid A: ingredient；By Li2CO3、ZnO、MgO、SiO2According to chemical general formula Li2(Mg1-xZnx)SiO4It carries out ingredient and forms mixture；Step
Rapid B: ball milling；The first uniformly mixed ball milling material is obtained after mixture obtained by step A is carried out ball milling；Step C: drying, sieving；
Sieving after the drying of first ball milling material obtained by step B is obtained into the first dry powder；Step D: pre-burning；First that step C is obtained
Dry powder pre-burning under atmospheric atmosphere, obtains pre-burning powder；Step E: ball milling；By pre-burning powder obtained by step D and LiF and low
Refractory oxides carry out secondary ball milling together, obtain the second uniformly mixed ball milling material；Step F: drying；Step E is resulting
Second ball milling material dries to obtain the second dry powder；Step G: sintering；The second dry powder that step F is obtained is in atmospheric atmosphere
Under be sintered, finally be made Li2MgSiO4Base microwave medium ceramic material.The preparation method of the invention is replaced by using ion
Generation preliminary reduction sintering temperature, and make to form liquid phase when sintering using composite sintering agent, further by Li2MgSiO4Base microwave
The sintering temperature of medium ceramic material is reduced to 900 DEG C, while promoting grain growth dense uniform.But made from the invention
Li2MgSiO4The dielectric constant of base microwave medium ceramic material is higher, is 6.3~6.5, needs to be further decreased.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of Li system microwave dielectric ceramic material and its systems
Preparation Method and purposes, the Li system microwave dielectric ceramic material have low-k (εr=5.33~5.89), high quality factor
(Q × f=11757~23320GHz), high relative density (89.1~95.9%) and low resonant frequency temperature coefficient (- 10.8
~-21.3ppm/ DEG C) excellent characteristics, it is minimum densification sintering to can be realized at 900 DEG C.
One of the objects of the present invention is to provide a kind of Li system microwave dielectric ceramic materials, for this purpose, the present invention adopts
With following technical scheme:
A kind of Li system microwave dielectric ceramic material of the invention, Li system microwave dielectric ceramic material include major ingredient
Li2CO3、SiO2And MgO, also comprising replacing material NiO.
It should be noted that Li system of the present invention microwave dielectric ceramic material refers to the microwave dielectric ceramic material containing Li
Material, refers in particular to Li2MgSiO4Microwave dielectric ceramic material.
The present invention is with Li2CO3、SiO2It is major ingredient with MgO, is to replace material with NiO, with Ni2+Ionic compartmentation part Mg2+From
Son improves the dielectric constant of Li system microwave dielectric ceramic material, improves by adjusting major ingredient and replacing the consumption proportion of material
The temperature characterisitic of Li system microwave dielectric ceramic material, so that Li system microwave dielectric ceramic material has low-k, high-quality
The excellent characteristics of factor, high relative density and low densification temperature.
Firstly, Ni2+Ionic radius beMg2+Ionic radius beUse Ni2+Ionic compartmentation
Li2MgSiO4In Mg2+Distortion of lattice will occur for ion, so as to reduce densification temperature, and in lower sintering
At a temperature of reach higher densification degree；Secondly, Mg2+Ionic polarizability beAnd Ni2+Ionic polarizability beWith the increase of theoretical ionic polarizability, dielectric constant (εr) increased trend will be shown, therefore, use Ni2+From
Son replaces Li2MgSiO4In Mg2+Ion will reduce dielectric constant；Finally, biggish with the lower ionic compartmentation radius of radius
Ion, it will so that temperature coefficient of resonance frequency (τf) increased trend is shown, therefore, use Ni2+Ionic compartmentation Li2MgSiO4
In Mg2+Ion can also improve Li2MgSiO4The temperature characterisitic of ceramic material.
Wherein, a kind of Li system microwave dielectric ceramic material of the invention includes following components by mole meter:
The sum of molar percentage of said components is 100%.
In the present invention, the molar ratio of the MgO and the NiO are (1:0.01)~(0.092:0.08), wherein NiO's
Dosage is too high or too low all cannot preferably improve Li2MgSiO4The microwave property of ceramic material, dosage is too low, Li2MgSiO4Pottery
The microwave property of porcelain takes on a new look less, and dosage is too high, and the distortion of lattice caused by a large amount of ionic compartmentations will deteriorate
Li2MgSiO4The microwave property of ceramics.
In the present invention, the Li2CO3、SiO2, MgO and NiO purity be all larger than 99%.
The second object of the present invention is to provide a kind of preparation of Li system microwave dielectric ceramic material described in the first purpose
Method improves Li under low sintering temperature2MgSiO4Sintering characteristic, micromorphology and the electric property of microwave dielectric ceramic,
The step of preparation method includes ingredient, a ball milling, pre-burning, secondary ball milling, granulating and forming and low-temperature sintering.
In the present invention, a ball milling is that the powder after ingredient is mixed postposition with deionized water to enter in ball mill to carry out
's；Preferably, the time of a ball milling is 8~12h, further preferably 12h；Preferably, the ball mill is planet
Formula ball mill.
In the present invention, the pre-burning is will to carry out heating pre-burning after the powder drying obtained after a ball milling, sieving, protect
Temperature；Preferably, the temperature of the pre-burning be 800~850 DEG C, such as pre-burning temperature be 800 DEG C, 810 DEG C, 820 DEG C, 830 DEG C,
840℃,850℃；Preferably, the rate of the heating is 2~5 DEG C/min；Preferably, the temperature of the heat preservation is 820~840
DEG C, such as the temperature of heat preservation is 820 DEG C, 825 DEG C, 830 DEG C, 835 DEG C, 840 DEG C, most preferably 830 DEG C, the time of the heat preservation
Time for 3~4h, such as heat preservation is 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h.
In the present invention, the secondary ball milling is that the powder after pre-burning is mixed postposition with deionized water to enter in ball mill to carry out
's；Preferably, the time of the secondary ball milling is 8~12h；Preferably, the ball mill is planetary ball mill.
In the present invention, the granulating and forming is that organic bond is added in the powder obtained after secondary ball milling, is made after mixing
Grain, using press and mold by graininess powder pressing at blank；Preferably, the dosage of the organic bond accounts for the powder
Quality 5~10%, such as the organic bond dosage account for the powder quality 5%, 6%, 7%, 8%,
9%, 10%.Preferably, the blank is cylindric blank；Preferably, the radius of the cylindric blank is 0.5~0.7cm,
The height of the cylindric blank is 0.5~0.7cm.
In the present invention, the low-temperature sintering is that the blank after the granulating and forming is placed in progress low temperature burning in sintering furnace
Knot；Preferably, the low sintering temperature be 1120~1160 DEG C, such as the low sintering temperature be 1120 DEG C,
1130 DEG C, 1140 DEG C, 1150 DEG C, 1160 DEG C, are more selected as 1150 DEG C；The low sintering time is 3~4h, such as low temperature
Time 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h of sintering.
Preferably, the low sintering atmosphere is air；Preferably, the low sintering heating rate is 2~5
℃/min；Preferably, it joined sintering aid when the low-temperature sintering, the low sintering temperature is 961 DEG C or less；It is preferred that
Ground, the dosage of the sintering aid is 1~5wt% of powder gross mass, such as the dosage of the sintering aid is powder gross mass
1wt%, 2wt%, 3wt%, 4wt%, 5wt%；Preferably, the sintering aid is Li2O-B2O3-Bi2O3-SiO2Glass.
As the preferred embodiment in the present invention, the preparation method of Li system microwave dielectric ceramic material includes following step
It is rapid:
1) by mole meter, 33.33% Li is weighed2CO3, 33.33% SiO2, 30.6636~33.32%
The NiO of MgO and 0.01~2.6664%；
2) after mixing the weighed powder of step 1) with deionized water, a ball milling, institute are carried out in a planetary ball mill
The time for stating a ball milling is 8~12 hours；
3) by after the drying of powder that step 2) obtains, sieving 800~850 DEG C at a temperature of carry out pre-burning, heating rate
For 2~5 DEG C/min preheating, 3~4 hours are kept the temperature at a temperature of 820~840 DEG C；
4) after mixing the powder obtained after step 3) pre-burning with deionized water, secondary ball is carried out in a planetary ball mill
Mill, the time of the secondary ball milling are 8~12 hours；
5) powder that step 4) obtains is added to the organic bond for accounting for the powder quality 5~10%, is granulated after mixing,
Using press and mold by graininess powder pressing at cylindric blank, the radius of the cylindric blank is 0.5~0.7cm,
The height of the cylindric blank is 0.5~0.7cm；
6) blank for obtaining step 5) is placed in the sintering furnace that atmosphere is air and carries out low-temperature sintering, the low-temperature sintering
Temperature be 1120~1160 DEG C, the low sintering time is 3~4h, and heating rate is 2~5 DEG C/min, is obtained described
Li system microwave dielectric ceramic material.
In the present invention, distortion of lattice caused by substitution ion is different from substituted ionic radius can reduce densification temperature
Degree, ionic polarizability difference can change dielectric constant and temperature coefficient of resonance frequency.The present invention passes through preferred high-purity
Li2CO3, MgO, NiO and SiO2For raw material, the Li of especially preferred high-purity2CO3, MgO, NiO and SiO2, by adjusting each
The proportion of raw material determines the preferred embodiment for preparing Li system microwave dielectric ceramic material；Work is prepared in above-mentioned formula and powder body material
Under the premise of skill optimizes, in conjunction with the sintering curre of high density and uniform grading, realize with high quality factor, low-k
With the low-temperature sintering of the Li system microwave dielectric ceramic material of high-compactness.
The third object of the present invention is to provide a kind of purposes of Li system microwave dielectric ceramic material described in the first purpose,
Li system microwave dielectric ceramic material is applied to low-temperature co-fired ceramics field.
Li system microwave dielectric ceramic material prepared by the present invention can be the microwave device etc. based on low temperature co-firing technology
Field solves the key technical problem in terms of following three: first, when microwave device work can be effectively reduced in high quality factor
To the loss that signal generates, therefore the material has great meaning to the promotion of microwave device performance；Second, low-k can
The delay time of signal transmission is effectively reduced, to improve the real-time of signal；Third, passing through Ni2+The substitution of ion, effectively
The intrinsic densification temperature of material is reduced, therefore (in the prior art, the dosage of sintering aid is often higher than the lesser amount of sintering aid of addition
Sintered at ultra low temperature (< 961 DEG C) 20wt%) can be realized, to reduce deterioration of the use to electric property of excessive sintering aid.
Compared with prior art, the invention has the benefit that
(1) Li system microwave dielectric ceramic material of the invention, with 5.33~5.89 low-k, 11757~
The high quality factor of 23320GHz, 89.1~95.9% high relative density and -10.8~-21.3ppm/ DEG C of low resonance frequency
The excellent characteristics of rate temperature coefficient has the sintering temperature lower than 961 DEG C, densification sintering can be realized at 900 DEG C.
(2) preparation method of Li system microwave dielectric ceramic material of the invention, in 1120~1160 DEG C of low sintering temperatures
Under, improve Li2MgSiO4Sintering characteristic, micromorphology and the electric property of microwave dielectric ceramic are adding a small amount of sintering aid
In the case of, it can be sintered in 900 DEG C of realizations.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of Li system microwave dielectric ceramic material of the invention；
Fig. 2 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of comparative example 1；
Fig. 3 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 1；
Fig. 4 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 2；
Fig. 5 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 3；
Fig. 6 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 4.
Specific embodiment
1-6 with reference to the accompanying drawing, and pass through specific embodiment to further illustrate the technical scheme of the present invention.
A kind of Li system microwave dielectric ceramic material of the invention includes following components by mole meter:
The sum of molar percentage of said components is 100%.
As shown in Figure 1, Li system microwave dielectric ceramic material preparation method of the invention include ingredient, a ball milling, pre-burning,
The step of secondary ball milling, granulating and forming and low-temperature sintering.
Embodiment 1
The Li system microwave dielectric ceramic material of the present embodiment, composition are as shown in table 1.
The preparation method of the Li system microwave dielectric ceramic material of the present embodiment comprising the steps of:
1) ingredient is carried out by the material composition and ratio of table 1；
2) after mixing the weighed powder of step 1) with deionized water, a ball milling, institute are carried out in a planetary ball mill
The time for stating a ball milling is 12 hours；
3) by after the drying of powder that step 2) obtains, sieving 830 DEG C at a temperature of carry out pre-burning, heating rate is 5 DEG C/
Min preheating keeps the temperature 3.5 hours；
4) after mixing the powder obtained after step 3) pre-burning with deionized water, secondary ball is carried out in a planetary ball mill
Mill, the time of the secondary ball milling are 12 hours；
5) powder that step 4) obtains is added to the organic bond for accounting for the powder quality 8%, is granulated after mixing, is utilized
By graininess powder pressing at cylindric blank, the radius of the cylindric blank is 0.6cm, described cylindric for press and mold
The height of blank is 0.6cm；
6) blank for obtaining step 5) is placed in the sintering furnace that atmosphere is air and carries out low-temperature sintering, the low-temperature sintering
Temperature be 1150 DEG C, the low sintering time be 3.5h, heating rate be 5 DEG C/min, obtain the Li system microwave Jie
Electroceramics material.
Embodiment 2
The Li system microwave dielectric ceramic material of the present embodiment, composition are as shown in table 1.
The preparation method of the Li system microwave dielectric ceramic material of the present embodiment is same as Example 1.
Embodiment 3
The Li system microwave dielectric ceramic material of the present embodiment, composition are as shown in table 1.
The preparation method of the Li system microwave dielectric ceramic material of the present embodiment is same as Example 1.
Embodiment 4
The Li system microwave dielectric ceramic material of the present embodiment, composition are as shown in table 1.
The preparation method of the Li system microwave dielectric ceramic material of the present embodiment is same as Example 1.
Wherein, the Li system microwave dielectric ceramic material of Examples 1 to 4 and comparative example 1~2 is carried out by the component proportion of table 1
Ingredient.
Table 1
Embodiment 5
It is in place of the difference of the present embodiment and embodiment 1, in preparation method, when low-temperature sintering joined 2wt%'s
Li2O-B2O3-Bi2O3-SiO2Glass, sintering temperature is 900 DEG C at this time.
Embodiment 6
It is in place of the difference of the present embodiment and embodiment 1, in preparation method, sintering temperature is 1120 when low-temperature sintering
DEG C, other are all the same with embodiment 1.
Embodiment 7
It is in place of the difference of the present embodiment and embodiment 1, in preparation method, sintering temperature is 1160 when low-temperature sintering
DEG C, other are all the same with embodiment 1.
Embodiment 8
It is in place of the difference of the present embodiment and embodiment 1, in preparation method, the temperature of pre-burning is 800 DEG C, other and reality
It is all the same to apply example 1.
Embodiment 9
It is in place of the difference of the present embodiment and embodiment 1, in preparation method, the temperature of pre-burning is 850 DEG C, other and reality
It is all the same to apply example 1.
Comparative example 1
Ingredient is carried out by the component of the comparative example in table 1, is not including NiO in raw material with the difference place of embodiment 1,
Sintering temperature is 1250 DEG C.
Comparative example 2
It is in place of this comparative example and the difference of embodiment 1, the molar percentage of NiO is the molar percentage of 5%, MgO
It is 28.33%, other components and preparation method and embodiment 1 are all the same.
Comparative example 3
It is in place of the difference of this comparative example and embodiment 1, only with a ball milling in preparation method, other and embodiment
1 is all the same.
Comparative example 4
It is in place of the difference of this comparative example and embodiment 1, without passing through pre-burning in preparation method, other and embodiment 1
It is all the same.
Comparative example 5
It is in place of the difference of this comparative example and embodiment 1, in preparation method, the temperature of pre-burning is 500 DEG C, other and reality
It is all the same to apply example 1.
Comparative example 6
Be in place of the difference of this comparative example and embodiment 1, in preparation method, the temperature of pre-burning is 1000 DEG C, other with
Embodiment 1 is all the same.
Comparative example 7
It is in place of this comparative example and the difference of embodiment 1, in preparation method, low sintering temperature is 1000 DEG C,
He is all the same with embodiment 1.
Comparative example 8
It is in place of this comparative example and the difference of embodiment 1, in preparation method, low sintering temperature is 1300 DEG C,
He is all the same with embodiment 1.
The Li system microwave dielectric ceramic material of Examples 1 to 9 and comparative example 1~8 is tested for the property, includes electrical property
Energy test, micro-structural test etc., test result is as shown in table 2.
Wherein, permittivity εr, quality factor q × f Agilent N5230A Network Analyzer (300MHz-
20GHz) tested；Relative density is tested with Archimedes's drainage；Scanning electron microscope image (SEM) JEOL JSM-
6490LV is tested；X-ray diffraction (XRD) is tested with DX-2700 (Haoyuan Co.).
Table 2
It can be seen from Examples 1 to 4 at 1150 DEG C, with the increase of NiO amount, the Li system microwave dielectric ceramic material
Dielectric constant, relative density and the Q × f value of material show the trend for first increasing and reducing afterwards, and in example 2, the ceramics material
Material shows best attributes；It can be seen that by embodiment 6~9, calcined temperature is 830 DEG C, when double sintering temperature is 1150 DEG C, material
Expect that performance is best；It can be seen that by comparative example 1~8, the microwave dielectric ceramic material performance as produced by 1 technique of embodiment is most
It is good；Also, the sintering aid of 2wt% is added in embodiment 5, which can be realized densification at 900 DEG C
Change sintering, and microwave dielectric property gets a promotion.
Fig. 2 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of comparative example 1；As seen from Figure 2, it passes through
After 1150 DEG C of sintering, it is not added with that Li system microwave dielectric ceramic material hole made from NiO is more, and densification degree is low.
Fig. 3 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 1；Fig. 4 is the Li of embodiment 2
It is the sintered scanning electron microscope (SEM) photograph of microwave dielectric ceramic material；Fig. 5 is after the Li system microwave dielectric ceramic material of embodiment 3 is sintered
Scanning electron microscope (SEM) photograph；Fig. 6 is the sintered scanning electron microscope (SEM) photograph of Li system microwave dielectric ceramic material of embodiment 4.It can be with by Fig. 3-6
Find out, with the increase of NiO content, the densification degree of material first rises to be declined afterwards, and the hole in corresponding material is shown
Increased trend after first reducing.
Li system microwave dielectric ceramic material of the invention, with 5.33~5.89 low-k, 11757~
The high quality factor of 23320GHz, 89.1~95.9% high relative density and -10.8~-21.3ppm/ DEG C of low resonance frequency
Densification sintering can be realized at 900 DEG C in the excellent characteristics of rate temperature coefficient.Li system microwave dielectric ceramic material of the invention
Preparation method improve Li under 1120~1160 DEG C of low sintering temperatures2MgSiO4The sintering characteristic of microwave dielectric ceramic,
Micromorphology and electric property can be sintered in the case where adding a small amount of sintering aid in 900 DEG C of realizations.
Above embodiments are only used to illustrate method detailed of the invention, and the invention is not limited to above-mentioned method detaileds, i.e.,
Do not mean that the invention must rely on the above detailed methods to implement.It should be clear to those skilled in the art, right
Any improvement of the invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode
Deng all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of Li system microwave dielectric ceramic material, which is characterized in that Li system microwave dielectric ceramic material includes major ingredient
Li2CO3、SiO2And MgO, also comprising replacing material NiO.
2. Li system according to claim 1 microwave dielectric ceramic material, which is characterized in that described by mole meter
Li system microwave dielectric ceramic material includes following components:
The sum of molar percentage of said components is 100%.
3. Li system according to claim 1 microwave dielectric ceramic material, which is characterized in that the MgO rubs with the NiO's
You are than being (1:0.01)~(0.092:0.08)；
Preferably, the Li2CO3、SiO2, MgO and NiO purity be all larger than 99%.
4. the preparation method of Li system according to claim 1 microwave dielectric ceramic material, which is characterized in that the preparation side
The step of method includes ingredient, a ball milling, pre-burning, secondary ball milling, granulating and forming and low-temperature sintering.
5. the preparation method according to claim 4, which is characterized in that a ball milling be by after ingredient powder with go
Ionized water mixing postposition, which enters, to be carried out in ball mill；
Preferably, the time of a ball milling is 8~12h；
Preferably, the secondary ball milling is that the powder after pre-burning is mixed postposition with deionized water to enter in ball mill to carry out；
Preferably, the time of the secondary ball milling is 8~12h；
Preferably, the ball mill that a ball milling and the secondary ball milling use is planetary ball mill.
6. preparation method according to claim 4 or 5, which is characterized in that the pre-burning is will to obtain after a ball milling
Heating pre-burning, heat preservation are carried out after powder drying, sieving；
Preferably, the temperature of the pre-burning is 800~850 DEG C；
Preferably, the rate of the heating is 2~5 DEG C/min；
Preferably, the temperature of the heat preservation is 820~840 DEG C, and the time of the heat preservation is 3~4h.
7. the preparation method according to one of claim 4-6, which is characterized in that the granulating and forming is will be after secondary ball milling
Organic bond is added in obtained powder, is granulated after mixing, using press and mold by graininess powder pressing at blank；
Preferably, the dosage of the organic bond accounts for the 5~10% of the quality of the powder；
Preferably, the blank is cylindric blank；
Preferably, the radius of the cylindric blank is 0.5~0.7cm, and the height of the cylindric blank is 0.5~0.7cm.
8. the preparation method according to one of claim 4-7, which is characterized in that the low-temperature sintering is granulated into described
Blank after type, which is placed in sintering furnace, carries out low-temperature sintering；
Preferably, the low sintering temperature is 1120~1160 DEG C, and the low sintering time is 3~4h；
Preferably, the low sintering atmosphere is air；
Preferably, the low sintering heating rate is 2~5 DEG C/min；
Preferably, it joined sintering aid when the low-temperature sintering, the low sintering temperature is 961 DEG C or less；
Preferably, the dosage of the sintering aid is 1~5wt% of powder gross mass；
Preferably, the sintering aid is Li2O-B2O3-Bi2O3-SiO2Glass.
9. the preparation method according to one of claim 3-8, which is characterized in that the preparation method comprises the steps of:
1) by mole meter, 33.33% Li is weighed2CO3, 33.33% SiO2, 30.6636~33.32% MgO and
0.01~2.6664% NiO；
2) after the weighed powder of step 1) being mixed with deionized water, in a planetary ball mill carry out a ball milling, described one
The time of secondary ball milling is 8~12 hours；
3) by after the drying of powder that step 2) obtains, sieving 800~850 DEG C at a temperature of carry out pre-burning, heating rate is 2~
5 DEG C/min preheating keeps the temperature 3~4 hours at a temperature of 820~840 DEG C；
4) after mixing the powder obtained after step 3) pre-burning with deionized water, secondary ball milling is carried out in a planetary ball mill,
The time of the secondary ball milling is 8~12 hours；
5) powder that step 4) obtains is added to the organic bond for accounting for the powder quality 5~10%, is granulated after mixing, is utilized
By graininess powder pressing at cylindric blank, the radius of the cylindric blank is 0.5~0.7cm, described for press and mold
The height of cylindric blank is 0.5~0.7cm；
6) blank for obtaining step 5) is placed in the sintering furnace that atmosphere is air and carries out low-temperature sintering, the low sintering temperature
Degree is 1120~1160 DEG C, and the low sintering time is 3~4h, and heating rate is 2~5 DEG C/min, obtains the Li system
Microwave dielectric ceramic material.
10. a kind of purposes of the described in any item Li system microwave dielectric ceramic materials of claim 1-3, which is characterized in that by institute
Li system microwave dielectric ceramic material is stated applied to low-temperature co-fired ceramics field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910015547.1A CN109534806A (en) | 2019-01-08 | 2019-01-08 | A kind of Li system microwave dielectric ceramic material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910015547.1A CN109534806A (en) | 2019-01-08 | 2019-01-08 | A kind of Li system microwave dielectric ceramic material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109534806A true CN109534806A (en) | 2019-03-29 |
Family
ID=65834401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910015547.1A Pending CN109534806A (en) | 2019-01-08 | 2019-01-08 | A kind of Li system microwave dielectric ceramic material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109534806A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018508A (en) * | 2019-12-31 | 2020-04-17 | 唐伟桓 | Li-series microwave dielectric ceramic material and preparation method thereof |
| CN111470864A (en) * | 2020-05-01 | 2020-07-31 | 桂林理工大学 | Silicon-based temperature-stable microwave dielectric ceramic material and preparation method thereof |
| CN111925197A (en) * | 2020-07-21 | 2020-11-13 | 深圳顺络电子股份有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN111995389A (en) * | 2020-08-26 | 2020-11-27 | 工业和信息化部电子第五研究所华东分所 | Composite dielectric ceramic material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030094774A (en) * | 2002-06-07 | 2003-12-18 | 한국과학기술연구원 | Dielectric ceramic composition and method for preparing dielectric ceramic for low temperature co-fired ceramic |
| CN106747412A (en) * | 2016-12-14 | 2017-05-31 | 电子科技大学 | A kind of Ti bases LTCC microwave dielectric ceramic materials and preparation method thereof |
| CN107382299A (en) * | 2017-08-08 | 2017-11-24 | 电子科技大学 | A kind of low temperature preparation method of low dielectric microwave media ceramic |
-
2019
- 2019-01-08 CN CN201910015547.1A patent/CN109534806A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030094774A (en) * | 2002-06-07 | 2003-12-18 | 한국과학기술연구원 | Dielectric ceramic composition and method for preparing dielectric ceramic for low temperature co-fired ceramic |
| CN106747412A (en) * | 2016-12-14 | 2017-05-31 | 电子科技大学 | A kind of Ti bases LTCC microwave dielectric ceramic materials and preparation method thereof |
| CN107382299A (en) * | 2017-08-08 | 2017-11-24 | 电子科技大学 | A kind of low temperature preparation method of low dielectric microwave media ceramic |
Non-Patent Citations (3)
| Title |
|---|
| CHEN ZHANG等: "Structure-Dependent Microwave Dielectric Properties and Middle-Temperature Sintering of Forsterite (Mg1-xNix)2SiO4 Ceramics", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| Z.W DONG等: "Microwave dielectric properties of Li(Mg1-xNix)PO4 ceramics for LTCC applications", 《CERAMICS INTERNATIONAL》 * |
| 李冉: "Li2MgSiO4基微波介质陶瓷的低温烧结及微波介电性能", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018508A (en) * | 2019-12-31 | 2020-04-17 | 唐伟桓 | Li-series microwave dielectric ceramic material and preparation method thereof |
| CN111470864A (en) * | 2020-05-01 | 2020-07-31 | 桂林理工大学 | Silicon-based temperature-stable microwave dielectric ceramic material and preparation method thereof |
| CN111470864B (en) * | 2020-05-01 | 2021-11-16 | 桂林理工大学 | Silicon-based temperature-stable microwave dielectric ceramic material and preparation method thereof |
| CN111925197A (en) * | 2020-07-21 | 2020-11-13 | 深圳顺络电子股份有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN111925197B (en) * | 2020-07-21 | 2023-01-03 | 深圳顺络电子股份有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN111995389A (en) * | 2020-08-26 | 2020-11-27 | 工业和信息化部电子第五研究所华东分所 | Composite dielectric ceramic material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109534806A (en) | A kind of Li system microwave dielectric ceramic material and its preparation method and application | |
| CN103232235B (en) | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof | |
| CN107555992B (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN108358632B (en) | Ultralow-temperature sintered high-Q x f-value microwave dielectric material and preparation method thereof | |
| CN107382299A (en) | A kind of low temperature preparation method of low dielectric microwave media ceramic | |
| CN107117967B (en) | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof | |
| CN108516826B (en) | Sn-containing intermediate microwave dielectric ceramic material and preparation method thereof | |
| CN113149645B (en) | Low-temperature sintering temperature stable composite microwave dielectric ceramic and preparation method thereof | |
| CN105347781B (en) | A kind of ceramic material and preparation method thereof | |
| JP3737773B2 (en) | Dielectric ceramic composition | |
| CN109415265A (en) | A kind of medium ceramic material and preparation method thereof | |
| CN103408299B (en) | Zinc barium titanate system ceramic low temperature sintering material and preparation method thereof | |
| CN114031402A (en) | Low-temperature sintered microwave dielectric material MgZrNb2O8And method for preparing the same | |
| CN101811869A (en) | Low-temperature sintering microwave medium ceramic material and preparation method thereof | |
| CN103467084B (en) | A kind of high-k series of lithium, niobium and titanium low-temperature sintered ceramics and preparation method thereof | |
| CN107721421B (en) | Zn-Nb-Ti LTCC material and preparation method thereof | |
| CN101462872B (en) | Low frequency microstrip aerial substrate material and preparation thereof | |
| CN105130418A (en) | Li-Nb-Ti-based microwave dielectric ceramic material | |
| CN106587991B (en) | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof | |
| CN105060887A (en) | Low-temperature sintering low loss microwave dielectric ceramic material | |
| CN112608144A (en) | Lithium-based microwave dielectric ceramic material, preparation method thereof and lithium-based microwave dielectric ceramic | |
| CN113072373A (en) | Temperature-stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and preparation method thereof | |
| CN103951429B (en) | A kind of low-temperature sintering low-loss microwave dielectric ceramic materials | |
| CN107382305B (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN102838346A (en) | Antenna substrate material using spinel ferrite as matrix and preparation method 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: 20190329 |
|
| RJ01 | Rejection of invention patent application after publication |