CN1300060C - Preparation method of low permittivity nanometer microwave medium ceramic powder - Google Patents
Preparation method of low permittivity nanometer microwave medium ceramic powder Download PDFInfo
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- CN1300060C CN1300060C CNB2005100507892A CN200510050789A CN1300060C CN 1300060 C CN1300060 C CN 1300060C CN B2005100507892 A CNB2005100507892 A CN B2005100507892A CN 200510050789 A CN200510050789 A CN 200510050789A CN 1300060 C CN1300060 C CN 1300060C
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- magnesium
- ceramic powder
- microwave
- nanometer
- citric acid
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Abstract
The present invention discloses a preparation method of low permittivity nanometer microwave medium ceramic powder, which comprises: (1) magnesium inorganic brine is dissolved to form a magnesium inorganic brine solution, silica sol is added into the magnesium inorganic brine solution according to that the molar ratio of silicon to magnesium is 1:1, and a mixed solution of the magnesium inorganic brine solution and the silica sol is stirred; (2) a certain amount of citric acid is added into glycol, an obtained mixed solution is heated and dissolved; (3) the mixed solution of the magnesium inorganic brine solution and the silica sol and the mixed solution of the citric acid and the glycol are mixed according to a certain molar ratio and are heated to evaporate water. After evaporated, an obtained product is heated up to 125 to 135 DEG C, and temperature is kept for 2 to 4 hours. Then, the product is heated up to 180 to 220 DEG C, and temperature is kept for 2 to 4 hours to obtain a black material. After ground, the black material is calcined at 800 to 1000 DEG C, which can obtain MgSiO3 and Mg2SiO4 microwave dielectric ceramic powder of a nanometer level with good dispersion, and the particle diameter of the microwave dielectric ceramic powder is from 80 to 100 nm. Synthesis temperature is greatly reduced. After sintered into porcelain, the nanometer powder prepared by the present invention has good microwave dielectric properties and can be used for preparing small-scale sheet type multilayered microwave devices, such as 0402 and 0201 multilayered microwave ceramic capacitors, etc., and the nanometer powder prepared by the present invention has great industrial application value.
Description
Technical field
The preparation method of a kind of low permittivity nanometer microwave medium ceramic powder of the present invention belongs to materials science field.
Background technology
Along with electronics develops to miniaturization, the miniaturization of the various electronic packages of inevitable requirement, microminiaturization.Components and parts miniaturization has at present obtained develop rapidly; Aspect laminated ceramic capacitor, 0603 has become main product, and 0402 has appeared on the market, and 0201 has succeeded in developing; The chip multilayer microwave device progressively replaces cavity configuration, and miniaturization day by day, has been reduced to 2.0 * 1.25 * 1.0 (mm as the size of the multilayer ceramic filter of Japanese village field company
3), from now on will be to being of a size of 1.0 * 0.8 * 0.6 (mm
3) even littler direction develop.
The key problem in technology that promotes device miniaturization, microminiaturization is the development of powder technology and thin film technique.With the laminated ceramic capacitor is example, the capacitor C=kS/h of dielectric ceramic, and the best approach that improves the dielectric ceramic electrical capacity is the thickness that reduces medium layer; And for microwave filter, resonant frequency f
0=1/2 π (LC)
1/2, under certain resonant frequency, electrical capacity is a definite value, for structure of reducing device and the dielectric loss that reduces material, should adopt low-k as far as possible, and reduces thickness of dielectric layers.The laminated ceramic capacitor film has been reduced to below the 5um at present, and generally between 20～300um, development trend from now on is ceramic condenser film and the following microwave device film of 10um of 1～5um to the thickness of multilayer ceramic filter.Film to be of five storeys at least above particle packing become the dielectric ceramic layer could guarantee effectively to isolate in electrode, the particulate size has determined the minimum thickness of medium layer, nano-powder is undoubtedly the best terms of settlement of the problems referred to above.The nanometer of powder granule is a great development direction of world's electronic ceramics, who have nanometer commodity technology who just will dominate market, each main manufacturer of the world all spends huge sums to nanoelectronic ceramic powder expansion research as AVX/Kyocera Corporation, Philips Components, TDK Corporation, Samsung EMCO, TAM Ceramics etc.
When medium ceramic material was applied to microwave circuit, material behavior and wiring figure can influence transmission signal, and the specific inductivity of medium ceramic material is big more, and the time of lag of line signal can be long more; Therefore, the medium ceramic material of exploitation low-k, significant to the circuit microelectronics under the high frequency.MgSiO
3, Mg
2SiO
4Deng MgO-SiO
2System's pottery has good microwave property, and its specific inductivity is low, quality factor is high; But owing to utilize conventional solid phase method could synthesizing MgSiO more than 1300 ℃
3, Mg
2SiO
4Crystalline phase, and its sintering temperature is more than 1500 ℃, so relevant pure MgSiO
3, Mg
2SiO
4The research of crystalline phase pottery seldom.
Li Xiaotu etc. at " piezoelectricity and acousto-optic " 2004,26 (1) 48-51. " a kind of high frequency hangs down Jie MLC porcelain systematic research " literary composition to MgO-SiO
2-TiO
2System launches research, by adjusting Mg
2SiO
4With Mg
2TiO
4Ratio, obtain ε
r=12 ± 35.058 (1GHz), tg δ＜1 * 10
-4The low Jie's positive temperature coefficient ceramic material of high frequency that dielectric properties are good; Sun Jizhou etc. are at " XI AN JIAOTONG UNIVERSITY Subject Index " 2003,37 (6) 604-607. " MgO-SiO
2-TiO
2The research of system Co, Ca ion doping " studied Co, Ca to MgO-SiO
2-TiO
2The doping of system; Luo Linghong etc. have studied B in " Journal of Inorganic Materials " 2001,16 (5) 1009-1014. " high-frequency multilayer chip inductor dielectric material "
3O
3-P
2O
5-MgO-Al
2O
3-SiO
2The system devitrified glass is as the application of high-frequency multilayer chip inductor dielectric material.At MgO-SiO
2The superfine powder research aspect of system domesticly never sees that relevant report is arranged; The people such as Sei-ichi Suda of Japan are at " Journal ofNon-Crystalline Solids " 1999,255 178-184. " Synthesis of MgO-SiO
2AndCaO-SiO
2Amorphous powder by sol-gel process and ion exchange " in by in sol-gel process, carrying out ion-exchange, obtained the MgO-SiO of 0.3～0.4um
2Powder is with the MgO-SiO of this method preparation
2The granularity that is ceramic powder is bigger than normal, can not satisfy the requirement of ultrathin casting films of preparation and microdevice.
Summary of the invention
The present invention provides a kind of preparation method of dielectric constant microwave ceramic medium nano-powder from the requirement of microwave device miniaturization to microwave dielectric ceramic materials powder super-refinement, selects the good MgO-SiO of microwave property
2System is utilized the pechini method, and by bonding and the sterically hindered effect of ethylene glycol to metal ion, and the process heating and calcining decomposes organism and inorganic ion generation oxidizing reaction forms crystal grain, thereby obtains nano level MgO-SiO at a lower temperature
2Microwave dielectric ceramic powder.
The preparation method of a kind of low permittivity nanometer microwave medium ceramic powder that the present invention proposes may further comprise the steps:
(1) inorganic salt with magnesium are dissolved in the deionized water, are 1: 1 mol ratio adding silicon sol again by silicon and magnesium, fully stir to make it to mix;
(2) a certain amount of citric acid (CA) is joined in the ethylene glycol (EG), heating is dissolved citric acid in ethylene glycol, and the mol ratio of CA and EG is 1: 4～1: 8;
(3) be above-mentioned (1) to be mixed with the solution that makes of (2) in 1: 1～1: 4 by CA and the mol ratio of magnesium inorganic salt, stir; Slowly heating makes water evaporates; Be warmed up to 125 ℃～135 ℃ insulations 2～4 hours then, continue to be warmed up to 180 ℃～220 ℃ insulations 2～4 hours, obtain crisp atrament;
4. above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be dielectric constant microwave ceramic medium nano-powder of the present invention 800 ℃～1000 ℃ calcinings.
The inorganic salt of described magnesium are Mg (NO
3)
26H
2O, Mg (CH
3COOH)
24H
2O or MgCl
2
The present invention adopts Mg (NO
3)
26H
2O, Mg (CH
3COOH)
24H
2O, MgCl
2Inorganic salt and silicon sol in magnesium are raw material, and low price and raw material are easy to get; Utilize citric acid to bonding and the sterically hindered effect of the complexing action of metal ion, ethylene glycol, metal ion is evenly distributed in the polymkeric substance, thereby finally can obtains the compound of uniform ingredients metal ion.Adopt technology of the present invention, after 900 ℃ of calcinings, can obtain particle diameter at 80～100nm and finely disseminated MgSiO
3, Mg
2SiO
4The nano level microwave dielectric ceramic powder greatly reduces MgO-SiO
2The synthesis temperature of compound.The nano-powder that the present invention makes has excellent microwave dielectric properties (ε after sintering porcelain into
r=6.4 ± 0.1, Qf＞35000GHz), can be used for preparing small-sized chip multiplayer microwave devices such as 0402,0201 multiplayer microwave ceramic condenser has great industrial application value.
Embodiment
Below in conjunction with example the present invention is further described.
Embodiment 1:
Take by weighing the Mg (NO of 1mol
3)
26H
2O is dissolved in a certain amount of deionized water, forms the magnesium nitrate aqueous solution of 1mol/l; In this magnesium nitrate aqueous solution, be that the amount of 1mol adds silicon sol, stir it to be mixed in 3 hours by silicon.The citric acid (CA) of 1mol is joined in the ethylene glycol (EG) of 4mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the water evaporates in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 130 ℃ of insulations 3 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 210 ℃ of insulations 2 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano material of the present invention 900 ℃ of calcinings 2 hours.
This material is through tem analysis, and particle diameter is between 80～100nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is MgSiO
3, Mg
2SiO
4Mixed phase.
With the above-mentioned nanometer MgSiO that obtains 900 ℃ of calcinings
3, Mg
2SiO
4Grinding, granulation, be pressed into the nahlock of diameter 18mm height 8～9mm, at 1450 ℃ of sintering, its microwave dielectric property is: ε
r=6.43, Qf=38900GHz.
Embodiment 2:
Take by weighing the MgCl of 1mol
2Be dissolved in a certain amount of deionized water, form the magnesium chloride brine of 0.8mol/l; In this magnesium chloride brine, be that the amount of 1mol adds silicon sol, stir it to be mixed in 4 hours by silicon.The citric acid (CA) of 2mol is joined in the ethylene glycol (EG) of 9mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the water evaporates in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 130 ℃ of insulations 3 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 210 ℃ of insulations 2 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano material of the present invention 900 ℃ of calcinings 2 hours.
This material is through tem analysis, and particle diameter is between 80～95nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is MgSiO
3, Mg
2SiO
4Mixed phase.
With the above-mentioned nanometer MgSiO that obtains 900 ℃ of calcinings
3, Mg
2SiO
4Grinding, granulation, be pressed into the nahlock of diameter 18mm height 8～9mm, at 1450 ℃ of sintering, its microwave dielectric property is: ε
r=6.47, Qf=37000GHz.
Embodiment 3:
Take by weighing the Mg (CH of 1mol
3COOH)
24H
2O is dissolved in a certain amount of deionized water, forms the magnesium acetate aqueous solution of 1.5mol/l; In this magnesium acetate aqueous solution, be that the amount of 1mol adds silicon sol, stir it to be mixed in 4 hours by silicon.The citric acid (CA) of 1.5mol is joined in the ethylene glycol (EG) of 9mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the water evaporates in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 125 ℃ of insulations 4 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 220 ℃ of insulations 3 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano material of the present invention 900 ℃ of calcinings 2 hours.
This material is through tem analysis, and particle diameter is between 80～100nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is MgSiO
3, Mg
2SiO
4Mixed phase.
With the above-mentioned nanometer MgSiO that obtains 900 ℃ of calcinings
3, Mg
2SiO
4Grinding, granulation, be pressed into the nahlock of diameter 18mm height 8～9mm, at 1450 ℃ of sintering, its microwave dielectric property is: ε
r=6.48, Qf=39500GHz.
Claims (2)
1, a kind of preparation method of low permittivity nanometer microwave medium ceramic powder may further comprise the steps:
(1) inorganic salt with magnesium are dissolved in the deionized water, form the inorganic salt solution of 0.5～1.5mol/l magnesium; Be 1: 1 mol ratio adding silicon sol again by silicon and magnesium, stirred 1～5 hour;
(2) a certain amount of citric acid is joined in the ethylene glycol, heating is dissolved citric acid in ethylene glycol, and the mol ratio of citric acid and ethylene glycol is 1: 4～1: 8;
(3) be above-mentioned (1) to be mixed with (2) solution in 1: 1～1: 4 by the citric acid and the mol ratio of magnesium inorganic salt, stir; Slowly heating makes water evaporates; Be warmed up to 125 ℃～135 ℃ insulations 2～4 hours then, continue to be warmed up to 180 ℃～220 ℃ insulations 2～4 hours, obtain crisp atrament;
(4) above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white nano-ceramic powder 800 ℃～1000 ℃ calcinings.
2, the preparation method of low permittivity nanometer microwave medium ceramic powder according to claim 1 is characterized in that: the inorganic salt of described magnesium are Mg (NO
3)
26H
2O, MgCl
2Or Mg (CH
3COOH)
24H
2O.
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|---|---|---|---|
| CNB2005100507892A CN1300060C (en) | 2005-07-18 | 2005-07-18 | Preparation method of low permittivity nanometer microwave medium ceramic powder |
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|---|---|---|---|
| CNB2005100507892A CN1300060C (en) | 2005-07-18 | 2005-07-18 | Preparation method of low permittivity nanometer microwave medium ceramic powder |
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| CN103715408B (en) * | 2013-12-13 | 2016-03-16 | 天津大学 | The sol-gel process for preparing of lithium ion battery negative material zinc titanate lithium |
| CN112194483B (en) * | 2020-10-23 | 2022-07-26 | 厦门松元电子股份有限公司 | High-strength calcium-magnesium-titanium microwave dielectric ceramic material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513804A (en) * | 2003-06-30 | 2004-07-21 | 哈尔滨工业大学 | Preparation method of composite silicate containing aluminium and/or magnesium |
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Granted publication date: 20070214 Termination date: 20120718 |