CN103214235B - A kind of preparation method of microwave dielectric ceramic materials - Google Patents
A kind of preparation method of microwave dielectric ceramic materials Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of microwave dielectric ceramic materials, including：Neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution and form the first mixed solution；Strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution and form the second mixed solution；Ammonia spirit is added in into the second mixed solution until forming vitreosol；By vitreosol drying and obtain nanometer powder through calcining；Nanometer powder is scattered in absolute ethyl alcohol, obtains suspension；First mixed solution is added in suspension until forming the colloidal sol of suspended powder；The colloidal sol of suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and presoma calcined to obtain neodymium zinc titanium strontium calcium titanium-based complex media ceramic nano-powder body.By the above-mentioned means, the present invention can reduce sintering temperature during neodymium zinc titanium strontium calcium titanium-based complex media ceramic material is prepared, while the performance of the material is improved, effectively reduce the industrial energy consumption and production cost of the material system.
Description
Technical field
The present invention relates to ceramic field, more particularly to a kind of preparation method of microwave dielectric ceramic materials.
Background technology
Microwave-medium ceramics are grown up in the past 30 years applied to microwave frequency band（Mainly UHF, SHF frequency range）Circuit
It is middle as dielectric material and to complete the new function electron ceramic material of one or more functions, mobile communication, satellite communication,
Be widely used as in the modern communications such as military radar, global positioning system, Bluetooth technology, WLAN resonator, wave filter,
The components such as dielectric substrate, medium wave circuit are the key foundation materials of modern communication technology.Jie applied to microwave circuit
Matter ceramics in addition to indispensable mechanical strength, chemical stability and ageing stability, also need to meet following dielectric properties requirement：
（1）There is relatively high permittivity ε at microwave frequenciesr, generally require εr>20, in order to microwave device miniaturization, collection
Cheng Hua；（2）There is extremely low dielectric loss, i.e. very high quality factor under microwave resonance frequency（Q）, to ensure excellent choosing
The insertion loss of frequency characteristic and reduction device in high frequency, generally requires Q × f>30000；（3）Close to zero resonant frequency temperature
Coefficient（τf）, to ensure the high stability of device resonant frequency in temperature change environment.
Neodymium zinc titanium ceramics（Nd(Zn1/2Ti1/2)O3, NZT）With relatively high dielectric constant（εr=31.55）With the product of superelevation
Prime factor Q × f values are 170000（8.5GHz）.However, NZT ceramics have high negative temperature coefficient of resonance frequency τf（-42ppm/
℃）Limit its practical application.
Existing preparation τfThe NZT base composite microwave medium ceramics that value is zero, using conventional solid china-clay method in Nd (Zn1/ 2Ti1/2)O3（NZT）Middle addition SrTiO3（ST）Ceramics form xNd (Zn1/2Ti1/2)O3—(1-x)SrTiO3Binary system.When x=
When 0.48, τfValue is zero.However this method has as a drawback that：
Conventional solid china-clay method is to select high-purity oxide or carbonate, by formula rate dispensing, through ball milling, calcining,
It mills again, adds in a certain amount of binding agent, through being granulated, after compression moulding, be sintered.This method is simple for process, pair sets
It is low for requiring, it is a kind of current most important advanced ceramics raw powder's production technology.But Nd (the Zn of this method synthesis1/2Ti1/2)
O3—SrTiO3Based composite powder has the disadvantage that：It is uneven can not to eliminate raw material micro Distribution for the mixing of mechanical means first,
Diffusion process is made to be difficult to be smoothed out, thus raw material is difficult to fully reaction and obtains high-purity purpose phase；Secondly as it refined
Journey mainly using mechanical crushing means, is readily incorporated some impurity, so as to damage the dielectric properties of material；Machinery refinement simultaneously is not
The microscopic uniformity of powder component distribution is can ensure that, so as to be difficult to ensure that composite ceramic material Nd (Zn1/2Ti1/2)O3With doping phase
Between be uniformly distributed, influence dielectric material performance；In addition, machinery refinement is difficult to make the granularity of ceramic powder to reach less than 1 μm,
Powder active obtained is poor, causes ceramic sintering temperature higher.
In addition, currently used synthesis by solid state reaction can not avoid Nd (Zn under high-temperature condition1/2Ti1/2)O3In system easily
The unstable technological deficiency of performance caused by volatile element Zn causes material prescription deviation.
The content of the invention
The invention mainly solves the technical problem of providing a kind of preparation methods of microwave dielectric ceramic materials, can make
During standby neodymium zinc titanium series ceramic material, sintering temperature is reduced, while improves the performance of the material, effectively reduces the material bodies
The industrial energy consumption and production cost of system.
In order to solve the above technical problems, one aspect of the present invention is：A kind of microwave-medium ceramics material is provided
The preparation method of material, including：
Neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution and form the first mixed solution；
Strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution and form the second mixed solution；
Ammonia spirit is added in into second mixed solution until forming vitreosol；
By vitreosol drying and obtain nanometer powder through calcining；
The nanometer powder is scattered in absolute ethyl alcohol, obtains suspension；
First mixed solution is added in the suspension until forming the colloidal sol of suspended powder；
The colloidal sol of the suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and by the presoma
Calcining obtains neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.
Wherein, described the step of neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution the first mixed solution of formation, wraps
It includes：Neodymium nitrate, zinc nitrate, butyl titanate and citric acid are dissolved in deionized water and form the first mixed solution, wherein adding in
The total moles ratio of citric acid and metal ion nitrate be 1.5~2.0:1.
Wherein, described the step of strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution the second mixed solution of formation, wraps
It includes：Strontium nitrate, calcium nitrate, butyl titanate and citric acid are dissolved in deionized water and form the second mixed solution, wherein adding in
The total moles ratio of citric acid and metal ion nitrate be 1.5~2.0:1.
Wherein, after described the step of obtaining neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body, further include：
Bonding agent, plasticiser and organic molten are added in the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body
By granulation for powders powder granule is made in the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body by liquid.
Wherein, it is described that the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body is made by powder by granulation for powders
After the step of body particle, further include：The powder granule is made to the blank of required shape.
Wherein, it is described by powder granule be made needed for shape blank the step of after, further include：By the blank through burning
Knot obtains microwave-medium ceramics.
Wherein, the step of blank obtains microwave-medium ceramics through sintering includes：
The blank at 900~1200 DEG C is sintered, when sintering time is 2~4 small, obtains microwave-medium ceramics.
Wherein, the neodymium, zinc, the salt of titanium and citric acid be dissolved in aqueous solution formed the first mixed solution the step of include：
Neodymium, zinc, the salt of titanium and citric acid are dissolved in deionized water, and add in ammonia spirit until pH forms the first mixing for 5~8
Solution.
Wherein, it is described to add in ammonia spirit into the second mixed solution until the step of forming vitreosol includes：
At 60~80 DEG C, ammonium hydroxide is added in into second mixed solution and is stirred continuously, until forming vitreosol.
Wherein, it is described that vitreosol is dry and the step of obtaining nanometer powder through calcining includes：By the vitreosol
Be dried to obtain xerogel, the xerogel calcined at 600~800 DEG C 1~2 it is small when, obtain nanometer powder.
Wherein, it is described to add in the first mixed solution in the suspension until the step of forming the colloidal sol of suspended powder is wrapped
It includes：
In the case where 60~80 DEG C are stirred, first mixed solution is added dropwise in the suspension until shape
Into the colloidal sol of suspended powder.
Wherein, it is described that the colloidal sol of suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and by described in
Presoma is calcined to include the step of obtaining neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body：
The colloidal sol of suspended powder is dried to obtain to the presoma of xerogel cladding nanometer powder at 100~150 DEG C；By institute
State presoma calcined at 600~800 DEG C 1~2 it is small when obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.
Wherein, the salt of the neodymium, zinc, titanium is according to chemical formula：(1-x)Nd(Zn1/2Ti1/2)O3+aB2O3+ bCuO's mole matches somebody with somebody
Than feeding intake, and according to 0≤a≤0.5mol%, the mol ratio of 0≤b≤1.0mol% adds at least the one of boric acid and copper oxide
Kind is into first mixed solution；The strontium, calcium, the salt of titanium are according to chemical formula：x(Sr1-yCay)TiO3Mol ratio throw
Material, wherein 0.45≤x≤0.55,0≤y≤1.0.
The beneficial effects of the invention are as follows：At present, common synthesis by solid state reaction can not avoid Nd (Zn under high-temperature condition1/ 2Ti1/2)O3The unstable technological deficiency of performance caused by Volatile Elements Zn causes material prescription deviation in system.The present invention with
Nitrate, alkoxide and the citrate of Nd, Zn, Sr, Ca, Ti element are raw material, and Nd is prepared respectively using sol-gel technology
(Zn1/2Ti1/2)O3Clear gel and (Sr, Ca) TiO3Nanometer powder, the approach that nanometer powder is coated by clear gel obtain two
Nd (the Zn of distributed mutually uniformly, with " core-shell structure copolymer " structure1/2Ti1/2)O3—(Sr,Ca)TiO3Neodymium zinc titanium-strontium calcium titanium-based complex media
Ceramic nano-powder body, while micro sintering aid B is added in a manner of solution2O3And CuO, it is uniformly distributed so as to fulfill two-phase, it can be
Under different sintering temperatures（900~1200 DEG C）Sintering has high dielectric constant（εrIt is worth for 42~58）, ultra high quality factor（Q
× f values are 60000~100000GHz）Neodymium zinc titanium-strontium calcium titanium-based composite microwave medium ceramic.So as to which the present invention can make
During standby neodymium zinc titanium-strontium calcium titanium-based complex media ceramic material, sintering temperature is reduced, while improves the performance of the material,
Effectively reduce the industrial energy consumption and production cost of the material system.
Description of the drawings
Fig. 1 is the flow chart of one embodiment of preparation method of microwave dielectric ceramic materials of the present invention；
Fig. 2 is the flow chart of another embodiment of preparation method of microwave dielectric ceramic materials of the present invention；
Fig. 3 is neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body that embodiment of the present invention four is prepared
SEM diagrams are intended to；
Fig. 4 is that the SEM diagrams for the microwave-medium ceramics that embodiment of the present invention four is prepared are intended to.
Specific embodiment
Embodiment one
In embodiment of the present invention, neodymium, zinc, titanium, strontium, the salt of calcium are respectively with neodymium nitrate, zinc nitrate, butyl titanate, nitric acid
It is illustrated exemplified by strontium and calcium nitrate, but is not limited to the scope for the metal salt that the present invention uses.That is the same terms
Under, by embodiment of the present invention neodymium, zinc, titanium, strontium, calcium salt can also be sulfate, carbonate etc., the present invention does not lift
Example is repeated one by one.Those skilled in the art are in the case where that need not make the creative labor, using its of these metals
His salt realizes the present invention, falls within the scope of protection of the invention.
Referring to Fig. 1, one embodiment of the preparation method of microwave dielectric ceramic materials of the present invention includes：
Step S101：Neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution and form the first mixed solution.Specifically, with
Neodymium nitrate, zinc nitrate, butyl titanate, boric acid, copper nitrate and the citric acid of purity more than 99% are starting material.It is expressed by chemistry
Formula Nd (Zn1/2Ti1/2)O3+aB2O3A certain proportion of neodymium nitrate, zinc nitrate, butyl titanate and citric acid are dissolved in one by+bCuO
In quantitative deionized water, the first mixed solution is formed, wherein the total moles ratio of the citric acid added in and metal ion nitrate
For 1.5~2.0:1.Then at least one of boric acid and copper nitrate is added in by a certain percentage, dissolved.Ammonium hydroxide is slowly added to institute
In the mixed solution of preparation, the pH value of mixed solution is controlled between 5~8, that is, stops adding in ammonium hydroxide, wherein 0≤a≤
0.5mol%, 0≤b≤1.0mol%.
Step S102：Strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution and form the second mixed solution.Specifically, with
Strontium nitrate, calcium nitrate, butyl titanate and the citric acid of purity more than 99% are starting material.By chemical expression (Sr1-yCay)
TiO3A certain proportion of strontium nitrate, calcium nitrate, butyl titanate and citric acid are dissolved in a certain amount of deionized water, form the
Two mixed solutions, wherein the total moles ratio of the citric acid added in and metal ion nitrate is 1.5~2.0:1, wherein 0≤y≤
1.0。
Step S103：Ammonia spirit is added in into the second mixed solution until forming vitreosol.Specifically, ammonium hydroxide is delayed
Slowly add in prepared solution, between pH value reaches 5~8, added at 60~80 DEG C and continue to stir, formed transparent molten
Glue.Since original raw material mixes in the form of a solution, atom level can be obtained or had at least more than molecular level high microcosmic uniform
The vitreosol of property.
Step S104：By vitreosol drying and obtain nanometer powder through calcining.Specifically, step S103 is formed saturating
Bright colloidal sol is placed in 100~150 DEG C of baking oven and dries, until forming xerogel；Again by the xerogel of acquisition at 600~800 DEG C
Lower calcining, when calcination time 1~2 is small, obtains (Sr1-yCay)TiO3Nanometer powder（d50=50~100nm）, Muffle furnace can be used
Carry out high-temperature calcination.
Step S105：Nanometer powder is scattered in absolute ethyl alcohol, obtains suspension.It specifically will be made from step S104
(Sr1-yCay)TiO3Nanometer powder is dispersed in absolute ethyl alcohol, is stirred and is ultrasonically treated, obtains suspension.
Step S106：First mixed solution is added in suspension until forming the colloidal sol of suspended powder.It specifically, will step
Nd (the Zn that rapid S101 is prepared1/2Ti1/2)O3Citric acid solution is added dropwise to (Sr, Ca) TiO at 60~80 DEG C3Suspension in,
And continue to stir, until forming the colloidal sol of even suspension nanometer powder.
Step S107：The colloidal sol of suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and by forerunner
Body is calcined to obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.Specifically, by colloidal sol made from step S106 in
100~150 DEG C of drying form the presoma of xerogel cladding nanometer powder.The presoma of acquisition is forged at 600~800 DEG C
It burns, when calcination time 1~2 is small, obtains neodymium zinc titanium-strontium calcium titanium (1-x) Nd (Zn1/2Ti1/2)O3—x(Sr,Ca)TiO3Compound Jie of base
Matter ceramic nano-powder body（d50=50~200nm）.
In the present embodiment, the salt of the neodymium, zinc, titanium is according to chemical formula：(1-x)Nd(Zn1/2Ti1/2)O3+aB2O3+bCuO
Mol ratio feed intake, and according to 0≤a≤0.5mol%, the mol ratio of 0≤b≤1.0mol% adds boric acid and copper oxide
At least one into first mixed solution；The strontium, calcium, the salt of titanium are according to chemical formula：x(Sr1-yCay)TiO3Mole
Proportioning feeds intake, wherein 0.45≤x≤0.55,0≤y≤1.0.
In addition, above-mentioned the step of the first mixed solution and nanometer powder is prepared, does not distinguish sequencing strictly, also
It is to say, can first prepares nanometer powder and prepare the first mixed solution again, can also first prepares the second mixed solution and prepare nanometer again
Powder.That is above-mentioned steps S101 can after step S102~step S105, can also step S102~step S105 it
Before.
The present embodiment is using the nitrate, alkoxide and citrate of Nd, Zn, Sr, Ca, Ti element as raw material, using colloidal sol-solidifying
Adhesive process prepares Nd (Zn respectively1/2Ti1/2)O3Clear gel and (Sr, Ca) TiO3Nanometer powder is received by clear gel cladding
The approach at rice flour end obtains the Nd (Zn that two-phase is evenly distributed, has " core-shell structure copolymer " structure1/2Ti1/2)O3—(Sr,Ca)TiO3Neodymium zinc
Titanium-strontium calcium titanium-based complex media ceramic nano-powder body, while micro sintering aid B is added in a manner of solution2O3And CuO, so as to real
Existing two-phase is uniformly distributed, can be under different sintering temperatures（900~1200 DEG C）Sintering has high dielectric constant（εrIt is worth for 42
~58）, ultra high quality factor（Q × f values are 60000~100000GHz）Neodymium zinc titanium-strontium calcium titanium-based composite microwave medium pottery
Porcelain.So as to, the present invention can reduce sintering temperature during neodymium zinc titanium-strontium calcium titanium-based complex media ceramic material is prepared,
The performance of the material is improved simultaneously, effectively reduces the industrial energy consumption and production cost of the material system.
Embodiment two
Referring to Fig. 2, the preparation method another embodiment of microwave dielectric ceramic materials of the present invention includes：
Step S201：Neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution and form the first mixed solution.Specifically, with
Neodymium nitrate, zinc nitrate, butyl titanate, boric acid, copper nitrate and the citric acid of purity more than 99% are starting material.It is expressed by chemistry
Formula Nd (Zn1/2Ti1/2)O3+aB2O3A certain proportion of neodymium nitrate, zinc nitrate, butyl titanate and citric acid are dissolved in one by+bCuO
In quantitative deionized water, the first mixed solution is formed, wherein the total moles ratio of the citric acid added in and metal ion nitrate
For 1.5~2.0:1.Then at least one of boric acid and copper nitrate is added in by a certain percentage, dissolved.Ammonium hydroxide is slowly added to institute
In the mixed solution of preparation, the pH value of mixed solution is controlled between 5~8, that is, stops adding in ammonium hydroxide, wherein 0≤a≤
0.5mol%, 0≤b≤1.0mol%.
Step S202：Strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution and form the second mixed solution.Specifically, with
Strontium nitrate, calcium nitrate, butyl titanate and the citric acid of purity more than 99% are starting material.By chemical expression (Sr1-yCay)
TiO3A certain proportion of strontium nitrate, calcium nitrate, butyl titanate and citric acid are dissolved in a certain amount of deionized water, form the
Two mixed solutions, wherein the total moles ratio of the citric acid added in and metal ion nitrate is 1.5~2.0:1, wherein 0≤y≤
1.0。
Step S203：Ammonia spirit is added in into the second mixed solution until forming vitreosol.Specifically, ammonium hydroxide is delayed
Slowly add in prepared solution, between pH value reaches 5~8, added at 60~80 DEG C and continue to stir, formed transparent molten
Glue.Since original raw material mixes in the form of a solution, atom level can be obtained or had at least more than molecular level high microcosmic uniform
The vitreosol of property.
Step S204：By vitreosol drying and obtain nanometer powder through calcining.Specifically, step S203 is formed saturating
Bright colloidal sol is placed in 100~150 DEG C of baking oven and dries, until forming xerogel；Again by the xerogel of acquisition at 600~800 DEG C
Lower calcining, when calcination time 1~2 is small, obtains (Sr1-yCay)TiO3Nanometer powder（d50=50~100nm）, Muffle furnace can be used
Carry out high-temperature calcination.
Step S205：Nanometer powder is scattered in absolute ethyl alcohol, obtains suspension.It specifically will be made from step S204
(Sr1-yCay)TiO3Nanometer powder is dispersed in absolute ethyl alcohol, is stirred and is ultrasonically treated, obtains suspension.
Step S206：First mixed solution is added in suspension until forming the colloidal sol of suspended powder.It specifically, will step
Nd (the Zn that rapid S201 is prepared1/2Ti1/2)O3Citric acid solution is added dropwise to (Sr, Ca) TiO at 60~80 DEG C3Suspension in,
And continue to stir, until forming the colloidal sol of even suspension nanometer powder.
Step S207：The colloidal sol of suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and by forerunner
Body is calcined to obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.Specifically, by colloidal sol made from step S206 in
100~150 DEG C of drying form the presoma of xerogel cladding nanometer powder.The presoma of acquisition is forged at 600~800 DEG C
It burns, when calcination time 1~2 is small, obtains neodymium zinc titanium-strontium calcium titanium (1-x) Nd (Zn1/2Ti1/2)O3—x(Sr,Ca)TiO3Compound Jie of base
Matter ceramic nano-powder body（d50=50~200nm）.
Step S208：Bonding agent, plasticiser are added in neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body and is had
Powder granule is made in neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body by machine solution；
It, can be into one on the basis of the above-mentioned neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body being prepared
Step carries out granulation for powders technique, i.e., bonding agent, plasticiser are added in neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body
And organic solvent, it uniformly mixes, by neodymium zinc titanium-strontium calcium titanium-based by the way of conventional granulation for powders such as mist projection granulating
Powder granule is made in complex media ceramic nano-powder body.
Step S209：Powder granule is made to the blank of required shape.
By being to obtain the green compact of required shape by powder granule compression moulding.Green compact is with manually or certainly by forcing press
Dynamic filler mode carries out two-sided compression moulding or carries out shot shaping by shot forming technique.
Step S210：Blank is obtained into microwave-medium ceramics through calcining.Specifically, blank is burnt at 900~1200 DEG C
Knot when sintering time is 2~4 small, obtains microwave-medium ceramics.
In the present embodiment, the component formula of the neodymium zinc titanium-strontium calcium titanium-based composite microwave medium ceramic is according to following chemistry
Expression formula：[(1-x)Nd(Zn1/2Ti1/2)O3+x(Sr1-yCay)TiO3]+aB2O3+ bCuO, wherein 0.45≤x≤0.55,0≤y≤
1.0,0≤a≤0.5mol%, 0≤b≤1.0mol%.
In addition, above-mentioned be prepared first mixed solution and nanometer powder the step of not stringent area identical with embodiment one
Successively order, that is to say, that can first prepare nanometer powder and prepare the first mixed solution again, can also first prepare the second mixing
Solution prepares nanometer powder again.That is above-mentioned steps S201 can be after step S202~step S205, can also be in step
Before S202~step S205.
The present embodiment is using the nitrate, alkoxide and citrate of Nd, Zn, Sr, Ca, Ti element as raw material, using colloidal sol-solidifying
Adhesive process prepares Nd (Zn respectively1/2Ti1/2)O3Clear gel and (Sr, Ca) TiO3Nanometer powder is received by clear gel cladding
The approach at rice flour end obtains the Nd (Zn that two-phase is evenly distributed, has " core-shell structure copolymer " structure1/2Ti1/2)O3—(Sr,Ca)TiO3Neodymium zinc
Titanium-strontium calcium titanium-based complex media ceramic nano-powder body, while micro sintering aid B is added in a manner of solution2O3And CuO, so as to real
Existing two-phase is uniformly distributed, can be under different sintering temperatures（900~1200 DEG C）Sintering has high dielectric constant（εrIt is worth for 42
~58）, ultra high quality factor（Q × f values are 60000~100000GHz）Neodymium zinc titanium-strontium calcium titanium-based composite microwave medium pottery
Porcelain.So as to, the present invention can reduce sintering temperature during neodymium zinc titanium-strontium calcium titanium-based complex media ceramic material is prepared,
The performance of the material is improved simultaneously, effectively reduces the industrial energy consumption and production cost of the material system.
Embodiment three
The present embodiment main material material formula uses [0.55Nd (Zn1/2Ti1/2)O3+0.45(Sr0.8Ca0.2)TiO3] it is chemical group
Into using the neodymium nitrate of purity more than 99%, zinc nitrate, strontium nitrate, calcium nitrate, butyl titanate and citric acid as starting material, and leading to
Following processing step is crossed to realize.
1）With the neodymium nitrate of purity more than 99%（Nd(NO3)3·5H2O）, zinc nitrate（Zn(NO3)2·6H2O）, butyl titanate
（C16H36O4Ti）And citric acid（C6H8O7·H2O）For starting material.By chemical expression 0.55Nd (Zn1/2Ti1/2)O3It will be certain
Neodymium nitrate, zinc nitrate, butyl titanate and the citric acid of ratio are dissolved in a certain amount of deionized water, form solution.Wherein, add
The total moles ratio of the citric acid entered and metal ion nitrate is 1.5:1.Then, ammonium hydroxide is slowly added to prepared solution
In, until pH value reaches 5.
2）With the strontium nitrate of purity more than 99%（Sr(NO3)2）, calcium nitrate（Ca(NO3)2）, butyl titanate（C16H36O4Ti）
And citric acid（C6H8O7·H2O）For starting material.By 0.45 (Sr of chemical expression0.8Ca0.2)TiO3By a certain proportion of nitric acid
Strontium, calcium nitrate, butyl titanate and citric acid are dissolved in a certain amount of deionized water, solution are formed, wherein the citric acid added in
Total moles ratio with metal ion nitrate is 1.5:1.Ammonium hydroxide is slowly added in prepared solution, until pH value reaches 5,
It is added at 80 DEG C and continues to stir, form vitreosol.Colloidal sol is placed in 150 DEG C of baking oven and dries, until forming xerogel；It will
The xerogel of acquisition is calcined at 800 DEG C, when calcination time is 1 small, obtains (Sr0.8Ca0.2)TiO3Nanometer powder（d50=50~
100nm）.
3）By 0.45 (Sr made from step 20.8Ca0.2)TiO3Nanometer powder is dispersed in absolute ethyl alcohol, stirs simultaneously strength
Ultrasound.In whipping process, 0.55Nd (Zn that step 1 is prepared1/2Ti1/2)O3Citric acid solution is added dropwise at 80 DEG C
0.45(Sr0.8Ca0.2)TiO3Suspension in, until formed even suspension nanometer powder colloidal sol.Colloidal sol is dried in 150 DEG C,
Form the presoma of xerogel cladding nanometer powder.The presoma powder of acquisition is calcined at 680 DEG C, calcination time is small for 1
When, obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body（d50=50~200nm）.
4）The complex media ceramic powder that step 3 is synthesized adds in the uniformly mixing such as bonding agent, plasticiser and organic solvent
Stirring, and using the compression moulding of traditional handicraft progress granulation for powders and blank, then in high temperature kiln roasting, firing temperature is
1200 DEG C, firing time 2h, that is, neodymium zinc titanium-strontium calcium titanium-based composite microwave medium ceramic is made（0.55Nd(Zn1/2Ti1/2)O3+
0.45(Sr0.8Ca0.2)TiO3）.
The relative dielectric constant ε of the composite microwave medium ceramic after testedrFor 57.7, quality factor（Q×f）It is worth and is
98000GHz, temperature coefficient of resonance frequency τfFor -8ppm/ DEG C.
Example IV
The present embodiment main material material formula uses [0.45Nd (Zn1/2Ti1/2)O3+0.55(Sr0.1Ca0.9)TiO3] it is chemical group
Into using the neodymium nitrate of purity more than 99%, zinc nitrate, strontium nitrate, calcium nitrate, butyl titanate and citric acid as starting material, and leading to
Following processing step is crossed to realize.
1）With the neodymium nitrate of purity more than 99%（Nd(NO3)3·5H2O）, zinc nitrate（Zn(NO3)2·6H2O）, butyl titanate
（C16H36O4Ti）And citric acid（C6H8O7·H2O）For starting material.By chemical expression 0.45Nd (Zn1/2Ti1/2)O3It will be certain
Neodymium nitrate, zinc nitrate, butyl titanate and the citric acid of ratio, which are dissolved in a certain amount of deionized water, forms solution.Wherein, add
The total moles ratio of the citric acid entered and metal ion nitrate is 2:1.Then, ammonium hydroxide is slowly added in prepared solution,
Until pH value reaches 8.
2）With the strontium nitrate of purity more than 99%（Sr(NO3)2）, calcium nitrate（Ca(NO3)2）, butyl titanate（C16H36O4Ti）
And citric acid（C6H8O7·H2O）For starting material.By chemical expression (Sr0.1Ca0.9)TiO3By a certain proportion of strontium nitrate, nitre
Sour calcium, butyl titanate and citric acid are dissolved in a certain amount of deionized water, solution are formed, wherein the citric acid and metal that add in
The total moles ratio of ion nitrate is 2:1.Ammonium hydroxide is slowly added in prepared solution, until pH value reaches 8, at 60 DEG C plus
Enter and continue to stir, form vitreosol.Colloidal sol is placed in 100 DEG C of baking oven and dries, until forming xerogel；By the dry of acquisition
Gel is calcined at 600 DEG C, when calcination time is 2 small, obtains (Sr0.1Ca0.9)TiO3Nanometer powder（d50=50~100nm）.
3）By 0.55 (Sr made from step 20.1Ca0.9)TiO3Nanometer powder is dispersed in absolute ethyl alcohol, stirs simultaneously strength
Ultrasound.In whipping process, 0.45Nd (Zn that step 1 is prepared1/2Ti1/2)O3Citric acid solution is added dropwise at 60 DEG C
0.55(Sr0.1Ca0.9)TiO3Suspension in, until formed even suspension nanometer powder colloidal sol.Colloidal sol is dried in 100 DEG C,
Form the presoma of xerogel cladding nanometer powder.The presoma powder of acquisition is calcined at 600 DEG C, calcination time is small for 2
When, obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body（d50=50~200nm）.
4）The complex media ceramic powder that step 3 is synthesized adds in the uniformly mixing such as bonding agent, plasticiser and organic solvent
Stirring, and using the compression moulding of traditional handicraft progress granulation for powders and blank, then in high temperature kiln roasting, firing temperature is
1150 DEG C, firing time 4h, that is, neodymium zinc titanium-strontium calcium titanium-based composite microwave medium ceramic is made（0.45Nd(Zn1/2Ti1/2)O3+
0.55(Sr0.1Ca0.9)TiO3）.
The relative dielectric constant ε of the composite microwave medium ceramic after testedrFor 42.5, quality factor（Q×f）It is worth and is
71500GHz, temperature coefficient of resonance frequency τfFor+7ppm/ DEG C.
The SEM figures of the neodymium zinc titanium that present embodiment is prepared-strontium calcium titanium-based complex media ceramic nano-powder body refer to
Fig. 3, it can be seen that nano-powder shows good island pattern, the average diameter of nano-powder is 50nm, grain shape
Close to spherical.The SEM that microwave-medium ceramics are prepared in present embodiment is schemed referring to Fig. 4, it can be seen that composite ceramic
Porcelain has high consistency, average grain size 500nm.
Embodiment five
The present embodiment main material material formula uses chemical formula：[0.5Nd(Zn1/2Ti1/2)O3+0.5SrTiO3]+0.5mol%B2O3
It is former by starting of the neodymium nitrate of purity more than 99%, zinc nitrate, strontium nitrate, butyl titanate, citric acid and boric acid for chemical composition
Material, and pass through following processing step and realize.
1）With the neodymium nitrate of purity more than 99%（Nd(NO3)3·5H2O）, zinc nitrate（Zn(NO3)2·6H2O）, butyl titanate
（C16H36O4Ti）, citric acid（C6H8O7·H2O）And boric acid（H3BO3）For starting material.By chemical expression 0.5Nd (Zn1/ 2Ti1/2)O3+0.5mol%B2O3A certain proportion of neodymium nitrate, zinc nitrate, butyl titanate and citric acid are dissolved in a certain amount of go
Solution is formed in ionized water.Wherein, the total moles ratio of the citric acid of addition and metal ion nitrate is 1.8:1.Then, by boron
Acid adds in solution dissolving by a certain percentage.Finally, ammonium hydroxide is slowly added in above-mentioned mixed solution, until pH value reaches 7.
2）With the strontium nitrate of purity more than 99%（Sr(NO3)2）, butyl titanate（C16H36O4Ti）And citric acid（C6H8O7·
H2O）For starting material.By chemical expression 0.5SrTiO3A certain proportion of strontium nitrate, butyl titanate and citric acid are dissolved in
In a certain amount of deionized water, solution is formed, wherein the total moles ratio of the citric acid added in and metal ion nitrate is 1.8:
1.Ammonium hydroxide is slowly added in prepared solution, until pH value reaches 7, is added at 70 DEG C and continues to stir, formed transparent molten
Glue.Colloidal sol is placed in 120 DEG C of baking oven and dries, until forming xerogel；The xerogel of acquisition at 700 DEG C is calcined, is calcined
When time is 1.5 small, SrTiO is obtained3Nanometer powder（d50=50~100nm）.
3）By 0.5SrTiO made from step 23Nanometer powder is dispersed in absolute ethyl alcohol, stirs and strength is ultrasonic.It is stirring
During mixing, 0.5Nd (Zn that step 1 is prepared1/2Ti1/2)O3+0.5mol%B2O3Citric acid solution is added dropwise at 70 DEG C
0.5SrTiO3Suspension in, until formed even suspension nanometer powder colloidal sol.Colloidal sol forms xerogel in 120 DEG C of drying
Coat the presoma of nanometer powder.The presoma powder of acquisition at 700 DEG C is calcined, when calcination time is 1.5 small, obtains neodymium
Zinc titanium-based complex media ceramic nano-powder body（0.5Nd(Zn1/2Ti1/2)O3+0.5SrTiO3, d50=50~200nm）.
4）The complex media ceramic powder that step 3 is synthesized adds in the uniformly mixing such as bonding agent, plasticiser and organic solvent
Stirring, and using the compression moulding of traditional handicraft progress granulation for powders and blank, then in high temperature kiln roasting, firing temperature is
1000 DEG C, firing time 3h, that is, neodymium zinc titanium-based composite microwave medium ceramic is made（0.5Nd(Zn1/2Ti1/2)O3+
0.5SrTiO3）.
The relative dielectric constant ε of the composite microwave medium ceramic after testedrFor 53, quality factor（Q×f）It is worth and is
87100GHz, temperature coefficient of resonance frequency τfFor -2ppm/ DEG C.
Embodiment six
The present embodiment main material material formula uses chemical formula：[0.5Nd(Zn1/2Ti1/2)O3+0.5CaTiO3]+0.5mol%B2O3
+ 1.0mol%CuO is chemical composition, with the neodymium nitrate of purity more than 99%, zinc nitrate, calcium nitrate, butyl titanate, citric acid, boron
Acid and copper nitrate are starting material, and pass through following processing step and realize.
1）With the neodymium nitrate of purity more than 99%（Nd(NO3)3·5H2O）, zinc nitrate（Zn(NO3)2·6H2O）, butyl titanate
（C16H36O4Ti）, citric acid（C6H8O7·H2O）, boric acid（H3BO3）And copper nitrate（Cu(NO3)2·6H2O）For starting material.It presses
Chemical expression 0.5Nd (Zn1/2Ti1/2)O3+0.5mol%B2O3+ 1.0mol%CuO is by a certain proportion of neodymium nitrate, zinc nitrate, titanium
Acid butyl ester and citric acid are dissolved in a certain amount of deionized water, form solution.Wherein, the citric acid of addition and metal ion nitre
The total moles ratio of hydrochlorate is 1.5:1.Then, boric acid and copper nitrate are added in into solution dissolving by a certain percentage.Finally, by ammonium hydroxide
It is slowly added in above-mentioned mixed solution, until pH value reaches 7.
2）With the calcium nitrate of purity more than 99%（Ca(NO3)2）, butyl titanate（C16H36O4Ti）And citric acid（C6H8O7·
H2O）For starting material.By chemical expression 0.5CaTiO3A certain proportion of calcium nitrate, butyl titanate and citric acid are dissolved in
Solution is formed in a certain amount of deionized water.Wherein, the total moles ratio of the citric acid of addition and metal ion nitrate is 1.5:
1.Then, ammonium hydroxide is slowly added in above-mentioned mixed solution, until pH value reaches 7, is added at 80 DEG C and continue to stir, formed saturating
Bright colloidal sol.The colloidal sol is placed in 120 DEG C of baking oven and is dried, until forming xerogel；The xerogel of acquisition is forged at 650 DEG C
It burns, when calcination time is 2 small, obtains CaTiO3Nanometer powder（d50=50~100nm）.
3）By 0.5CaTiO made from step 23Nanometer powder is dispersed in absolute ethyl alcohol, stirs and strength is ultrasonic.It is stirring
During mixing, 0.5Nd (Zn that step 1 is prepared1/2Ti1/2)O3+0.5mol%B2O3+ 1.0mol%CuO citric acid solutions are at 80 DEG C
It is added dropwise to 0.5CaTiO3Suspension in, until formed even suspension nanometer powder colloidal sol.By the colloidal sol in 120 DEG C
Drying forms the presoma of xerogel cladding nanometer powder.The presoma powder of acquisition is calcined at 650 DEG C, calcination time
For 2 it is small when, obtain neodymium zinc titanium-based complex media ceramic nano-powder body（d50=50~200nm）.
4）The complex media ceramic powder that step 3 is synthesized adds in the uniformly mixing such as bonding agent, plasticiser and organic solvent
Stirring, and using the compression moulding of traditional handicraft progress granulation for powders and blank, then in high temperature kiln roasting, firing temperature is
910 DEG C, firing time 3h, that is, neodymium zinc titanium-based composite microwave medium ceramic is made（0.5Nd(Zn1/2Ti1/2)O3+0.5CaTiO3]
+0.5mol%B2O3+1.0mol%CuO）.
The relative dielectric constant ε of the composite microwave medium ceramic after testedrFor 47, quality factor（Q×f）It is worth and is
62000GHz, temperature coefficient of resonance frequency τfFor 0ppm/ DEG C.
Pass through the elaboration of the above embodiment, it will be understood that nitrate, alcohol of the present invention with Nd, Zn, Sr, Ca, Ti element
Salt and citrate are raw material, prepare Nd (Zn respectively using sol-gel technology1/2Ti1/2)O3Clear gel and (Sr, Ca)
TiO3Nanometer powder is evenly distributed by the approach acquisition two-phase of clear gel cladding nanometer powder, has " core-shell structure copolymer " structure
Nd(Zn1/2Ti1/2)O3—(Sr,Ca)TiO3Neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body, while in a manner of solution
Add micro sintering aid B2O3And CuO, it is uniformly distributed so as to fulfill two-phase, it can be under different sintering temperatures（900~1200 DEG C）
Sintering has high dielectric constant（εrIt is worth for 42~58）, ultra high quality factor（Q × f values are 60000~100000GHz）'s
Neodymium zinc titanium-strontium calcium titanium-based composite microwave medium ceramic.So as to which the present invention can prepare neodymium zinc titanium-strontium calcium titanium-based complex media
During ceramic material, sintering temperature is reduced, while improves the performance of the material, effectively reduces the industrial energy of the material system
Consumption and production cost.
The foregoing is merely embodiments of the present invention, are not intended to limit the scope of the invention, every to utilize this
It is relevant to be directly or indirectly used in other for the equivalent structure or equivalent flow shift that description of the invention and accompanying drawing content are made
Technical field is included within the scope of the present invention.
Claims (13)
1. a kind of preparation method of microwave dielectric ceramic materials, which is characterized in that including：
Neodymium, zinc, the salt of titanium and citric acid are dissolved in aqueous solution and form the first mixed solution；
Strontium, calcium, the salt of titanium and citric acid are dissolved in aqueous solution and form the second mixed solution；
Ammonia spirit is added in into second mixed solution until forming vitreosol；
By vitreosol drying and obtain nanometer powder through calcining；
The nanometer powder is scattered in absolute ethyl alcohol, obtains suspension；
First mixed solution is added in the suspension until forming the colloidal sol of suspended powder；
The colloidal sol of the suspended powder is dried to the presoma to form xerogel cladding nanometer powder, and the presoma is calcined
There is the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body of " core-shell structure copolymer " structure.
2. according to the method described in claim 1, it is characterized in that, it is described neodymium, zinc, the salt of titanium and citric acid are dissolved in it is water-soluble
The step of liquid the first mixed solution of formation, includes：Neodymium nitrate, zinc nitrate, butyl titanate and citric acid are dissolved in deionized water
The first mixed solution is formed, wherein the total moles ratio of the citric acid added in and metal ion nitrate is 1.5~2.0:1.
3. according to the method described in claim 1, it is characterized in that, it is described strontium, calcium, the salt of titanium and citric acid are dissolved in it is water-soluble
The step of liquid the second mixed solution of formation, includes：Strontium nitrate, calcium nitrate, butyl titanate and citric acid are dissolved in deionized water
The second mixed solution is formed, wherein the total moles ratio of the citric acid added in and metal ion nitrate is 1.5~2.0:1.
4. according to the method described in claim 1, it is characterized in that, described obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramics
After the step of nano-powder, further include：
Bonding agent, plasticiser and organic solution are added in the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body, is led to
It crosses granulation for powders and powder granule is made in the neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.
5. according to the method described in claim 4, it is characterized in that, it is described by granulation for powders by the neodymium zinc titanium-strontium calcium titanium
After the step of powder granule is made in based composite dielectric ceramic nano-powder body, further include：Required shape is made in the powder granule
The blank of shape.
6. the according to the method described in claim 5, it is characterized in that, step of the blank that powder granule is made to required shape
After rapid, further include：The blank is obtained into microwave-medium ceramics through sintering.
7. the according to the method described in claim 6, it is characterized in that, the step of blank obtains microwave-medium ceramics through sintering
Including：
The blank at 900~1200 DEG C is sintered, when sintering time is 2~4 small, obtains microwave-medium ceramics.
8. according to the method described in claim 1, it is characterized in that, the salt and citric acid of the neodymium, zinc, titanium are dissolved in aqueous solution
The step of forming the first mixed solution includes：Neodymium, zinc, the salt of titanium and citric acid are dissolved in deionized water, and add in ammonium hydroxide
Solution is until pH forms the first mixed solution for 5~8.
9. according to the method described in claim 1, it is characterized in that, it is described into the second mixed solution add in ammonia spirit until
The step of forming vitreosol includes：
At 60~80 DEG C, ammonium hydroxide is added in into second mixed solution and is stirred continuously, until forming vitreosol.
It is 10. according to the method described in claim 1, it is characterized in that, described that vitreosol is dry and obtain nanometer through calcining
The step of powder, includes：The vitreosol is dried to obtain xerogel, the xerogel calcines 1~2 at 600~800 DEG C
Hour, obtain nanometer powder.
11. according to the method described in claim 1, it is characterized in that, described add in the first mixed solution in the suspension
Until the step of forming the colloidal sol of suspended powder includes：
In the case where 60~80 DEG C are stirred, first mixed solution is added dropwise in the suspension until being formed outstanding
The colloidal sol of floating powder.
12. according to the method described in claim 1, it is characterized in that, described dry to form xerogel by the colloidal sol of suspended powder
The presoma of nanometer powder is coated, and the presoma calcined to obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano powder
The step of body, includes：
The colloidal sol of suspended powder is dried to obtain to the presoma of xerogel cladding nanometer powder at 100~150 DEG C；Before described
Drive body calcined at 600~800 DEG C 1~2 it is small when obtain neodymium zinc titanium-strontium calcium titanium-based complex media ceramic nano-powder body.
13. according to the method described in claim 1, it is characterized in that, the salt of the neodymium, zinc, titanium is according to chemical formula：(1-x)Nd
(Zn1/2Ti1/2)O3+aB2O3The mol ratio of+bCuO feeds intake, and according to 0≤a≤0.5mol%, 0≤b≤1.0mol%'s rubs
You match at least one for adding boric acid and copper oxide into first mixed solution；The strontium, calcium, the salt of titanium are according to change
Formula：x(Sr1-yCay)TiO3Mol ratio feed intake, wherein 0.45≤x≤0.55,0<y<1.0.
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| RU2593271C1 (en) * | 2015-06-30 | 2016-08-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю. А." | Liquid composite dielectric |
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| CN111470861B (en) * | 2020-04-22 | 2022-03-01 | 吴坚强 | Microwave dielectric ceramic material and method for preparing microwave ceramic filter device by using same |
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