CN102030364A - Preparation method of low-temperature sintering nano-sized magnesium titanate powder - Google Patents
Preparation method of low-temperature sintering nano-sized magnesium titanate powder Download PDFInfo
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Abstract
The invention discloses a preparation method of low-temperature sintering nano-sized magnesium titanate powder, comprising the following steps of: dissolving a magnesium compound into absolute ethyl alcohol; then adding and dissolving a proper quantity of boric acid, lithium nitrate and ammonium metavanadate in the absolute ethyl alcohol, and meanwhile, dissolving a titanium compound into acetic acid; mixing the above two solutions and simultaneously adding a proper quantity of surfactant; after the above mixed solution is evenly stirred, putting the solution into water bath to obtain gel; drying the gel; and calcining at the temperature of 600-1000 DEG C to obtain the magnesium titanate powder disclosed in the invention. The method has simple process, and a low-temperature sintering accessory ingredient precursor is introduced into the solution of magnesium and titanium compound, so that an accessory ingredient component is evenly mixed with a magnesium titanate matrix component at the atom scale. The prepared magnesium titanate powder can simultaneously satisfy dual requirements on nano-sized particles and lower sintering temperature, and can be used for preparing minitype lamellar multilayer microwave devices.
Description
Technical field
The present invention relates to a kind of preparation method, belong to materials science field with nano barium titanate magnesium powder of low-temperature sintering characteristic.
Background technology
Along with the modern information technologies high speed development of mobile communication technology particularly, directions such as the microminiaturization of electronic devices and components forward, high frequencyization, integrated, modularization, multifunction and cost degradation develop, and microminiaturized and high frequencyization have become the essential characteristic of present advanced electronic devices and components.Under the effort of researcher, the miniaturization of chip multilayer components and parts has obtained develop rapidly; As 0603 main product that has become chip ceramic capacitor, 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), present forward 1.0 * 0.8 * 0.6 (mm
3) even littler dimensional directions development.The key problem in technology that promotes chip device miniaturization, microminiaturization is the development of powder technology and thick film technology, with submicron even nano level powder is raw material, prepare the ceramic diaphragm of thickness at 1～5 μ m, be to realize chip device miniaturization and microminiaturized key problem in technology, the nanometer of powder granule has become the research emphasis of present electronic ceramic fields.
Magnesium titanate ceramics has characteristics such as dielectric loss is low, frequency-temperature coefficient is little, add its abundant raw material, with low cost, become one of at present most widely used microwave dielectric ceramic materials, with it is high frequency heat compensating condenser, laminated ceramic capacitor, gps antenna, the dielectric filter that dielectric material is made, and resonator etc. has obtained using widely in the communications industry.Yet the sintering temperature of magnesium titanate ceramics is up to more than 1400 ℃, and low temperature co-fired for realization and copper, silver or 30Pd-70Ag electrode must reduce its sintering temperature.Huang etc. (Mater Res Bull, 2001,36:2741) by adding a spot of B
2O
3The sintering temperature of pottery is reduced to 1200 ℃.Bernard etc. (J Eur Ceram Soc, 2004,24:1877) at MgTi
0.975O
3In add LiF, the sintering temperature of pottery is reduced to 1000 ℃.Jantunen etc. (J Eur Ceram Soc, 2000,20:2331) with the MgTiO of 30wt%
3-CaTiO
3The RO-B of base-material and 70wt%
2O
3-SiO
2(R=Zn, Ba) glass has been realized low-temperature sintering at 900 ℃, the dielectric properties of acquisition are: ε
r=8.5, Q * f=8800 (8GHz).Chen etc. (Mater ChemPhys, 2003,79:129) press MgCaTiO
3/ BaBSiO glass is 50/50 proportioning, has also obtained the pottery at 900 ℃ of densified sintering products, and its dielectric properties are: ε
r=13.2, Q * f=10000.Though above-mentioned low sintering magnesium titanate ceramics can be used for the preparation of chip device, but because the powder granule of the traditional solid-phase synthesis of employing is at micron order, can't prepare the ceramic diaphragm of thickness below 5 μ m, thus limited to promoting the chip multilayer miniaturization of devices with microminiaturized effect.
For obtaining the tiny nano level metatitanic acid magnesium powder of particle diameter, (J Alloys Compd such as Li, 2010,492:564) inquired into magnesium titanate gel phase transition after treatment in detail, Miao etc. (Mater Sci Eng B, 2006,128:103) adopt sol-gel method to synthesize the magnesium titanate powder of 10-30nm, and realized ceramic dense sintering at 1200 ℃, obtained good microwave dielectric property: ε
r=16.6, Q * f=42,600, τ
f=-41ppm/ ℃.Yet the sintering temperature of above-mentioned nano barium titanate magnesium powder is difficult to the low temperature co-fired of realization and metal electrode up to 1200 ℃, does not possess actual application value in chip multilayer electronic devices and components field.Thereby, prepare and to realize low temperature co-fired, particle dia nano barium titanate magnesium powder with electrodes such as copper, silver or 30Pd-70Ag less than 100nm, can effectively promote the microminiaturization of chip multilayer microwave device, the development of modern mobile communication technology will be had important promoter action.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with nano barium titanate magnesium powder of low-temperature sintering characteristic, the magnesium titanate powder for preparing by the inventive method can satisfy the double requirements of nano-scale particle and lower sintering temperature simultaneously.
The preparation method of a kind of low-temperature sintering nano barium titanate magnesium powder that the present invention proposes may further comprise the steps:
(1) with the compound dissolution of magnesium in dehydrated alcohol, form the solution of 0.5～3.0mol/l, the amount of pressing magnesium elements then adds 0.01%～12% boric acid, 0.01%～10% lithium nitrate, 0.01%～3% ammonium meta-vanadate, mixes to stir each solute is dissolved fully; As preferably, the compound dissolution of magnesium forms the solution of 1.5～3.0mol/l in dehydrated alcohol; When the compound dissolution of magnesium in dehydrated alcohol, best results when forming the solution of 2.5mol/l.
(2) with the compound dissolution of titanium in acetic acid, form the solution of 1.0～2.5mol/l;
(3) by titanium elements and magnesium elements be 1: 1 mol ratio, the solution of above-mentioned steps (2) is joined in the solution of step (1), add tensio-active agent, mixing and stirring by 1%～5% of whole solution quality simultaneously; As preferably, 2～2.5% of the whole solution quality of surfactant comprise of adding;
(4) above-mentioned mixing solutions is placed 40～60 ℃ water-bath, until obtaining transparent gel;
(5) with above-mentioned gel in 80～100 ℃ baking oven dry 10～24 hours, put into the high alumina crucible then, calcine, promptly get nano barium titanate magnesium powder at 600～1000 ℃.
In the technique scheme, the compound of described magnesium is one or more in magnesium nitrate, magnesium acetate, the magnesium chloride, the compound of described titanium is one or more in tetraethyl titanate, tetrabutyl titanate, the titanium tetrachloride, and described tensio-active agent is one or more in oleic acid, polyoxyethylene glycol, polyvinyl alcohol and the polyvinyl butyral acetal.
The present invention compared with prior art, has following beneficial features: by in the solution of magnesium titanium compound, introducing low-temperature sintering auxiliary agent precursor, realize auxiliary agent constituent element and magnesium titanate matrix constituent element uniform mixing in the atom level level, obtain the uniform magnesium titanate powder of component by sol-gel transition and after calcining then, this powder can satisfy the double requirements of nano-scale particle and lower sintering temperature simultaneously; The magnesium titanate powder of the present invention's preparation is compared with existing low-temperature sintering magnesium titanate powder, except having lower sintering temperature, also has less powder granule diameter; The magnesium titanate powder of the present invention's preparation is compared with existing nano barium titanate magnesium powder, except having less powder granule diameter, also has lower sintering temperature, can satisfy the preparation requirement of miniature chip multilayer device fully.
Embodiment
Below in conjunction with example the present invention is further described.
Embodiment 1:
Take by weighing the 1mol magnesium nitrate and be dissolved in the dehydrated alcohol, form the solution of 3.0mol/l, in above-mentioned solution, add 0.12mol boric acid, 0.0001mol lithium nitrate, 0.0001mol ammonium meta-vanadate then, mix to stir that each solute is dissolved fully; Take by weighing the 1mol tetrabutyl titanate and be dissolved in the acetic acid, form the solution of 1.0mol/l.The acetum of tetrabutyl titanate is slowly joined in the ethanol solution of magnesium nitrate, add 25 gram oleic acid simultaneously as tensio-active agent, mixing and stirring.Above-mentioned mixing solutions is placed 60 ℃ water-bath, obtain transparent gel after for some time,, put into the high alumina crucible then,, promptly get nano barium titanate magnesium powder of the present invention 750 ℃ of calcinings 2 hours with above-mentioned gel in 80 ℃ baking oven dry 24 hours.
Above-mentioned powder detects through X-ray electron diffraction, and principal crystalline phase is MgTiO
3Phase, through scanning electron microscopic observation, the particle diameter of powder is between 40-60nm.The polyvinyl alcohol water solution that adds 15wt% in above-mentioned powder is as tackiness agent, through behind granulation, moulding, the binder removal 1100 ℃ of sintering 2 hours, can obtain the magnesium titanate ceramics of dense structure, and have good microwave dielectric property: ε
r=17.63, Q * f=33,768GHz.This nano barium titanate magnesium powder can be realized low temperature co-fired with the 30Pd-70Ag electrode can be used for the preparation of miniature chip multilayer device.
Embodiment 2:
Take by weighing the 1mol magnesium acetate and be dissolved in the dehydrated alcohol, form the solution of 2.0mol/l, in above-mentioned solution, add 0.0001mol boric acid, 0.1mol lithium nitrate, 0.01mol ammonium meta-vanadate then, mix to stir that each solute is dissolved fully; Take by weighing the 1mol tetraethyl titanate and be dissolved in the acetic acid, form the solution of 2.0mol/l.The acetum of tetraethyl titanate is slowly joined in the ethanol solution of magnesium acetate, add 40 gram polyoxyethylene glycol simultaneously as tensio-active agent, mixing and stirring.Above-mentioned mixing solutions is placed 55 ℃ water-bath, obtain transparent gel after for some time,, put into the high alumina crucible then,, promptly get nano barium titanate magnesium powder of the present invention 700 ℃ of calcinings 3 hours with above-mentioned gel in 90 ℃ baking oven dry 20 hours.
Above-mentioned powder detects through X-ray electron diffraction, and principal crystalline phase is MgTiO
3Phase, through scanning electron microscopic observation, the particle diameter of powder is between 30-40nm.The polyvinyl alcohol water solution that adds 15wt% in above-mentioned powder is as tackiness agent, through behind granulation, moulding, the binder removal 1100 ℃ of sintering 2 hours, can obtain the magnesium titanate ceramics of dense structure, and have good microwave dielectric property: ε
r=17.56, Q * f=33,243GHz.This nano barium titanate magnesium powder can be realized low temperature co-fired with the 30Pd-70Ag electrode can be used for the preparation of miniature chip multilayer device.
Embodiment 3:
Taking by weighing 0.5mol magnesium nitrate, 0.4mol magnesium acetate, 0.1mol magnesium chloride is dissolved in the dehydrated alcohol, form the solution of 2.5mol/l, in above-mentioned solution, add the boric acid of 0.1mol, the lithium nitrate of 0.05mol, the ammonium meta-vanadate of 0.003mol then, mix to stir that each solute is dissolved fully; Take by weighing 0.5mol tetrabutyl titanate, 0.3mol tetraethyl titanate, 0.2mol titanium tetrachloride and be dissolved in the acetic acid, form the solution of 1.5mol/l.The acetum of titanium compound is slowly joined in the ethanol solution of magnesium compound, add 10 gram polyoxyethylene glycol and 10 gram polyvinyl alcohol simultaneously as tensio-active agent, mixing and stirring.Above-mentioned mixing solutions is placed 50 ℃ water-bath, obtain transparent gel after for some time,, put into the high alumina crucible then,, promptly get nano barium titanate magnesium powder of the present invention 800 ℃ of calcinings 1 hour with above-mentioned gel in 95 ℃ baking oven dry 18 hours.Above-mentioned powder detects through X-ray electron diffraction, and principal crystalline phase is MgTiO
3Phase, through scanning electron microscopic observation, the particle diameter of powder is between 60-90nm.The polyvinyl alcohol water solution that adds 15wt% in above-mentioned powder is as tackiness agent, through behind granulation, moulding, the binder removal 1100 ℃ of sintering 2 hours, can obtain the magnesium titanate ceramics of dense structure, and have good microwave dielectric property: ε
r=17.51, Q * f=34,437GHz.This nano barium titanate magnesium powder can be realized low temperature co-fired with the 30Pd-70Ag electrode can be used for the preparation of miniature chip multilayer device.
Claims (4)
1. the preparation method of a low-temperature sintering nano barium titanate magnesium powder is characterized in that, may further comprise the steps:
(1) with the compound dissolution of magnesium in dehydrated alcohol, form the solution of 0.5～3.0mol/l, the quality of pressing magnesium elements then adds 0.01%～12% boric acid, 0.01%～10% lithium nitrate, 0.01%～3% ammonium meta-vanadate, mixes to stir each solute is dissolved fully;
(2) with the compound dissolution of titanium in acetic acid, form the solution of 1.0～2.5mol/l;
(3) by titanium elements and magnesium elements be 1: 1 mol ratio, the solution of above-mentioned steps (2) is joined in the solution of step (1), add tensio-active agent, mixing and stirring by 1%～5% of whole solution quality simultaneously;
(4) above-mentioned mixing solutions is placed 40～60 ℃ water-bath, until obtaining transparent gel;
(5) with above-mentioned gel in 80～100 ℃ baking oven dry 10～24 hours, put into the high alumina crucible then, calcine at 600～1000 ℃, nano barium titanate magnesium powder;
The compound of described magnesium is one or more in magnesium nitrate, magnesium acetate or the magnesium chloride; The compound of described titanium is one or more in tetraethyl titanate, tetrabutyl titanate or the titanium tetrachloride; Described tensio-active agent is one or more in oleic acid, polyoxyethylene glycol, polyvinyl alcohol and the polyvinyl butyral acetal.
2. preparation method according to claim 1, the compound dissolution that it is characterized in that described magnesium forms the solution of 1.5～3.0mol/l in dehydrated alcohol.
3. preparation method according to claim 2, the compound dissolution that it is characterized in that described magnesium forms the solution of 2.5mol/l in dehydrated alcohol.
4. preparation method according to claim 1 is characterized in that 2～2.5% of the middle whole solution quality of surfactant comprise that adds of described step (3).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195510A (en) * | 2021-12-28 | 2022-03-18 | 元颉新材料科技(浙江)有限公司 | Pure crystalline phase high-quality factor nano-size magnesium calcium titanate ceramic powder and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 《Materials Science and Engineering B》 20061231 Ya-Mei Miao et al. Low-temperature synthesis of nano-crystalline magnesium titanate materials by the sol-gel method pp.103-106 1-4 第128卷, 2 * |
| 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 20060715 缪亚美 溶胶-凝胶法低温制备纳米钛酸镁粉体 第26页 1-4 , 第07期 2 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195510A (en) * | 2021-12-28 | 2022-03-18 | 元颉新材料科技(浙江)有限公司 | Pure crystalline phase high-quality factor nano-size magnesium calcium titanate ceramic powder and preparation method thereof |
| CN114195510B (en) * | 2021-12-28 | 2024-04-23 | 元颉新材料科技(浙江)有限公司 | Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof |
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