CN101224984B - Low temperature synthesis of ultra-fine ZnO-SiO2 microwave dielectric ceramic powder by sol-gel method - Google Patents
Low temperature synthesis of ultra-fine ZnO-SiO2 microwave dielectric ceramic powder by sol-gel method Download PDFInfo
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- CN101224984B CN101224984B CN2008100596315A CN200810059631A CN101224984B CN 101224984 B CN101224984 B CN 101224984B CN 2008100596315 A CN2008100596315 A CN 2008100596315A CN 200810059631 A CN200810059631 A CN 200810059631A CN 101224984 B CN101224984 B CN 101224984B
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Abstract
The invention discloses a preparation method of sol-gel to synthesize the ultrafine microwave dielectric ceramic powder of ZnO-SiO2 in the low temperature, which comprises the steps that: the zinc salt and the tetraethyl orthosilicate are respectively dissolved in the anhydrous ethanol to form the ethanol solution of zinc salt and the ethanol solution of tetraethyl orthosilicate; the two solutionsare stirred and mixed with the mole ratio of Zn to Si being 2 : 1, then proper anhydrous ethanol is added to control the density of the zinc salt in the mixed solution within a range of 0.5 to 1 mol/l; deionized water is added to promote hydrolytic polymerization; at least one of nitric acid and acrylic acid is added dropwise to adjust the pH value; proper dispersing agent is added to overcome the powder agglomeration; and the gel is obtained after even stirring, sealing and standing of the obtained solution, and then the obtained gel is dried and calcined to obtain the ultrafine microwave dielectric ceramic powder of ZnO-SiO2. The preparation method has the advantages that the ultrafine powder with an adjustable particle size of 80 to 200 nm can be calcined and synthesized under the lowtemperature condition of 800 to 850 DEG C; and the powder has good microwave property after sintering.
Description
Technical field
The present invention relates to ultra-fine ZnO-SiO
2The preparation method of microwave dielectric ceramic powder especially relates to sol-gel method low temperature synthesizing superfine ZnO-SiO
2The method of microwave dielectric ceramic powder belongs to materials science field.
Background technology
Along with the high speed development of information technology, high frequencyization and the microminiaturized essential characteristic that has become present advanced electronic devices and components.Along with further dwindling of ceramic components volume, the medium layer in the chip multilayer device architecture is also more and more thinner, and an important channel of therefore following preparation ultra-thin medium layer is adopted superfine powder even nanometer grade powder exactly.
Guo.Y etc. are at " J.Eur.Ceram.Soc ", and 2006,26:16-18 " Characterization anddielectric behavior of willemite and TiO
2-doped willemite ceramics atmillimeter-wave frequency " literary composition discloses ZnO-SiO first
2The isostatic cool pressing preparation method of microwave-medium ceramics and microwave property are because its excellent microwave performance causes the concern of vast researcher.Subsequently, " J.Am.Ceram.Soc ", 2007, people such as 90:3127-3130.Nguyen N.H are at " Effect of Zn/Si ratio on the microstructural and microwave dielectrics pro-perties of Zn
2SiO
4Ceramics " literary grace prepares Zn with solid phase method and non-stoichiometric
2SiO
4Pottery and microwave property, non-stoichiometric can be eliminated excessive ZnO to Zn
2SiO
4The ceramic microwave Effect on Performance has obviously been improved quality factor q * f.But up to now, Shang Weijian has employing wet chemical method (containing sol-gel method) to prepare ultra-fine Zn
2SiO
4Pottery is to satisfy the report of ceramic component miniaturization.Sol-gel method is a kind of wet chemical method of comparatively extensive and sophisticated preparation superfine powder of application, can access big, the active big high pure and ultra-fine powder of specific surface area, has been widely used in the preparation of all kinds of electronic ceramics powders.
Summary of the invention
The invention provides a kind ofly, utilize sol-gel method to prepare ultra-fine ZnO-SiO from the requirement of microwave device miniaturization to microwave dielectric ceramic materials powder super-refinement
2The method of microwave dielectric ceramic powder, by the sterically hindered effect of gelation process and dispersion agent, and the process heating and calcining decomposes organism and zinc salt ion generation oxidizing reaction forms crystalline phase, thereby obtains ultra-fine ZnO-SiO at a lower temperature
2Microwave dielectric ceramic powder.
Sol-gel method low temperature synthesizing superfine ZnO-SiO
2The preparation method of microwave dielectric ceramic powder may further comprise the steps:
(1) zinc salt is dissolved in the dehydrated alcohol, forms the zinc salt ethanol solution;
(2) tetraethoxy is dissolved in the ethanol solution, forms the tetraethoxy ethanolic soln;
(3) with zinc salt ethanol solution and tetraethoxy ethanolic soln in zinc: the mol ratio of silicon is that 2: 1 ratio mixes, and adds an amount of dehydrated alcohol, makes that the concentration of zinc salt is controlled at 0.5～1mol/l in the mixing solutions; Add deionized water again, promote hydrolytic process, deionized water: the mol ratio of tetraethoxy transfers to 0～8; Add at least a in nitric acid or the vinylformic acid mixing solutions pH value is transferred to 1～3; Weight in mixing solutions is 100%, adds 1～10% dispersion agent polyoxyethylene glycol PEG;
(4) the above-mentioned mixing solutions that makes is stirred, sealing places 10～40 ℃ of environment, obtains even water white gel; Gel oven dry under 80～100 ℃ is become crisp xerogel;
(5) above-mentioned crisp xerogel is ground, put into the high alumina crucible,, obtain the ZnO-SiO of white 600～1000 ℃ of calcinings
2Microwave dielectric ceramic powder.
Described zinc salt is Zn (NO
3)
26H
2O, Zn (CH
3COOH)
22H
2O, ZnCl
2
Adopt above-mentioned technology, can obtain particle diameter at 100～200nm and finely disseminated ultra-fine ZnO-SiO
2Microwave dielectric ceramic powder, this superfine powder have higher Q * f value after sintering porcelain into, compare, are significantly improved with the Q * f value after the synthetic micro-powder of conventional solid-state method sinters porcelain into; And its sintering temperature has descended 100～150 ℃ with respect to the sintering temperature of solid phase method gained micro-powder.Can be used for preparing ultra-thin cast film and miniature chip multiplayer microwave device, have great industrial application value.Preparation method of the present invention has following characteristics:
(1) adopts Zn (NO
3)
26H
2O, Zn (CH
3COOH)
22H
2O, ZnCl
2Deng zinc salt is raw material, and low price and raw material are easy to get;
(2) adopt wet chemical method that zinc, element silicon are evenly distributed in the colloidal sol, utilize the sterically hindered effect of gelation process and dispersion agent, the Chemical Composition that makes final product evenly and also the diameter of particle that obtains after the calcining tiny;
(3) can after 800 ℃ of calcinings, obtain ultra-fine ZnO-SiO
2Microwave dielectric ceramic powder greatly reduces ZnO-SiO
2The synthesis temperature of powder, the superfine powder particle diameter that obtains is adjustable between 100～200nm, and good dispersion;
(4) the ultra-fine ZnO-SiO of this method synthetic
2Microwave-medium ceramics can sinter porcelain at 1250 ℃, than the synthetic micron ZnO-SiO of conventional solid-state method
2The sintering temperature of powder (1400 ℃) has descended about 150 ℃; This nano-powder has higher Q * f value after sintering porcelain into, and the Q * f value of synthesizing after micro-powder sinters porcelain into than conventional solid-state method improves 20%.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
Take by weighing the Zn (NO of 1mol
3)
2.6H
2O is dissolved in 475 milliliters of dehydrated alcohols, forms the zinc nitrate ethanol solution that concentration is about 2.0mol/l; The tetraethoxy of 0.5mol is mixed with 110 milliliters of dehydrated alcohols, form the tetraethoxy ethanolic soln; Above-mentioned two solution are mixed, stir, add 550 milliliters of dehydrated alcohols, making zinc concentration is 0.8mol/l.Add the 3mol deionized water then, 8 gram concentration are 65～68% concentrated nitric acid, 20 gram PEG400, the pH value of solution is 1.5.
After above-mentioned mixing solutions stirred, be statically placed in 30 ℃ the water-bath, obtain water white gel, gel is taken out put into pallet, 80 ℃ dry 24 hours down, obtain crisp material.
Above-mentioned crisp material is ground, put into the high alumina crucible,, obtain the ZnO-SiO of white 800 ℃ of calcinings 1 hour
2Microwave dielectric ceramic powder.
This material is through TEM Electronic Speculum and laser particle size analysis, and the powder median size is between 100～200nm, and dispersion of particles is good; XRD analysis shows that the principal crystalline phase of this nano-powder is Zn
2SiO
4
With above-mentioned nano-powder grinding, the granulation that obtains 800 ℃ of calcinings, be pressed into the nahlock of diameter 18mm, height 8～9mm, at 1250 ℃ of sintering 30min, its microwave dielectric property is: ε
r=6.14, Qf=67500GHz.
Embodiment 2:
Take by weighing the Zn (CH of 0.5mol
3COOH)
22H
2O is dissolved in 320 milliliters of dehydrated alcohols, forms the zinc acetate ethanol solution that concentration is about 1.5mol/l; The tetraethoxy of 0.25mol is mixed with 115 milliliters of dehydrated alcohols, form the tetraethoxy ethanolic soln; Above-mentioned two solution are mixed, stir, add 400 milliliters of dehydrated alcohols, making zinc concentration is 0.6mol/l.Add 2mol deionized water, 3 gram concentration then and be 65～68% concentrated nitric acid and 4 gram vinylformic acid, 10 gram PEG1000, the pH value of solution is 2.
After above-mentioned mixing solutions stirred, be statically placed in 35 ℃ the water-bath, obtain water white gel, gel is taken out put into pallet, 90 ℃ dry 24 hours down, obtain crisp material.
Above-mentioned crisp material is ground, put into the high alumina crucible,, obtain the ZnO-SiO of white 850 ℃ of calcinings 1 hour
2Microwave dielectric ceramic powder.
This material is through TEM Electronic Speculum and laser particle size analysis, and the powder median size is between 120～180nm, and dispersion of particles is good; XRD analysis shows that the principal crystalline phase of this nano-powder is Zn
2SiO
4
With above-mentioned nano-powder grinding, the granulation that obtains 850 ℃ of calcinings, be pressed into the nahlock of diameter 18mm, height 8～9mm, at 1250 ℃ of sintering 30min, its microwave dielectric property is: ε
r=6.32, Qf=70300GHz.
Embodiment 3:
The Zncl2 that takes by weighing 0.5mol is dissolved in 115 milliliters of dehydrated alcohols, forms the zinc nitrate ethanol solution that concentration is about 4mol/l; The tetraethoxy of 0.25mol is mixed with 110 milliliters of dehydrated alcohols, form the tetraethoxy ethanolic soln; Above-mentioned two solution are mixed, stir, add 250 milliliters of dehydrated alcohols, making zinc concentration is 1.0mol/l.Add the 1mol deionized water then, 2.5 gram concentration are 65～68% concentrated nitric acid, 8 gram PEG1000, the pH value of solution is 2.5.
After above-mentioned mixing solutions stirred, be statically placed in 30 ℃ the water-bath, obtain water white gel, gel is taken out put into pallet, 80 ℃ dry 24 hours down, obtain crisp material.
Above-mentioned crisp material is ground, put into the high alumina crucible,, obtain the ZnO-SiO of white 800 ℃ of calcinings 1 hour
2Microwave dielectric ceramic powder.
This material is through TEM Electronic Speculum and laser particle size analysis, and the powder median size is between 150～280nm, and dispersion of particles is good; XRD analysis shows that the principal crystalline phase of this nano-powder is Zn
2SiO
4
With above-mentioned nano-powder grinding, the granulation that obtains 800 ℃ of calcinings, be pressed into the nahlock of diameter 18mm, height 8～9mm, at 1250 ℃ of sintering 30min, its microwave dielectric property is: ε
r=6.25, Qf=65300GHz.
Claims (1)
1. one kind is utilized sol-gel method low temperature synthesizing superfine ZnO-SiO
2The preparation method of microwave dielectric ceramic powder may further comprise the steps:
(1) zinc salt is dissolved in the dehydrated alcohol, forms the zinc salt ethanol solution;
Described zinc salt is Zn (NO
3)
26H
2O or Zn (CH
3COOH)
22H
2O or ZnCl
2
(2) tetraethoxy is dissolved in the dehydrated alcohol, forms the tetraethoxy ethanolic soln;
(3) with zinc salt ethanol solution and tetraethoxy ethanolic soln by zinc: the mol ratio of silicon is 2: 1 a mixed, adds dehydrated alcohol, makes that the concentration of zinc salt is controlled at 0.5～1mol/l in the mixing solutions; Add deionized water again, promote hydrolytic process, deionized water: the mol ratio of tetraethoxy transfers to 0～8; Add at least a in nitric acid or the vinylformic acid mixing solutions pH value is transferred to 1～3; Weight in mixing solutions is 100%, adds 1～10% dispersion agent polyoxyethylene glycol PEG;
(4) the above-mentioned mixing solutions that makes is stirred, sealing places 10～40 ℃ of environment, obtains even water white gel; Gel oven dry under 80～100 ℃ is become crisp xerogel;
(5) above-mentioned crisp xerogel is ground, put into the high alumina crucible,, obtain the ZnO-SiO of white 600～1000 ℃ of calcinings
2Microwave dielectric ceramic powder.
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| CN104016671B (en) * | 2014-05-16 | 2015-12-02 | 西安工程大学 | The preparation method of ramie form ZnO Air-Sensitive Porcelain Materials |
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| CN107867841A (en) * | 2016-09-22 | 2018-04-03 | 施海月 | A kind of TiO2Adulterate ZnO/SiO2The preparation method of microwave-medium ceramics |
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| CN111302792B (en) * | 2020-03-25 | 2021-06-22 | 广东风华高新科技股份有限公司 | Dielectric constant series adjustable low-temperature co-fired dielectric material and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| CN1736944A (en) * | 2005-07-18 | 2006-02-22 | 浙江大学 | Method for low-temperature synthesis of nanometer CaO-SiO2 series nanometre microwave medium ceramic powder |
| CN1903733A (en) * | 2006-08-01 | 2007-01-31 | 浙江大学 | Preparation method of single phase nano-CaTiO3 powder using collosol-gel low temperature synthesis |
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| CN1736944A (en) * | 2005-07-18 | 2006-02-22 | 浙江大学 | Method for low-temperature synthesis of nanometer CaO-SiO2 series nanometre microwave medium ceramic powder |
| CN1903733A (en) * | 2006-08-01 | 2007-01-31 | 浙江大学 | Preparation method of single phase nano-CaTiO3 powder using collosol-gel low temperature synthesis |
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