CN1903733A - Preparation method of single phase nano-CaTiO3 powder using collosol-gel low temperature synthesis - Google Patents
Preparation method of single phase nano-CaTiO3 powder using collosol-gel low temperature synthesis Download PDFInfo
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- CN1903733A CN1903733A CN 200610052790 CN200610052790A CN1903733A CN 1903733 A CN1903733 A CN 1903733A CN 200610052790 CN200610052790 CN 200610052790 CN 200610052790 A CN200610052790 A CN 200610052790A CN 1903733 A CN1903733 A CN 1903733A
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Abstract
The present invention discloses a preparation method of low-temperature synthetic single-phase nano CaTiO3 ceramic powder body by using sol-gel process. Said method includes the following steps: dissolving inorganic salt of calcium in anhydrous ethyl alcohol; dissolving butyl titanate in the mixed solution of anhydrous ethyl alcohol and acetic acid; drop-adding nitric acid and acrylic acid to regulate pH value; according to mole ratio of 1:1 of calcium: titanium mixing the above-mentioned two solutions, adding proper quantity of dispersing agent; uniformly stirring the obtained solution, sealing and standing still to obtain gel, drying and grinding said gel, calcining so as to obtain the invented nano ceramic powder body.
Description
Technical field
The present invention relates to nanometer CaTiO
3The preparation method of powder especially relates to the synthetic single phase nano CaTiO of sol-gel method low temperature
3The method of powder belongs to materials science field.
Background technology
CaTiO
3Be a kind of important titanate, it has higher dielectric constant, can make the radio ceramics electrical condenser of miniaturized high capacity, as coupling, bypass, energy storage, blocking capacitor etc.; At present, CaTiO
3Pottery is widely used in the dielectric materials of preparation electronic industry, the basic conducting element of high frequency instrument etc. as raw material.As far back as twentieth century seventies, people such as Kell have announced CaTiO first on " J.Am.Ceram.Soc. " 56 (1973) the 352nd pages
3The microwave dielectric property of pottery: ε
r=170, Qf=3500GHz, τ
f=+800ppm/ ℃.Owing to have bigger positive frequency temperature factor, high specific inductivity, people are to CaTiO
3Pottery has carried out broad research with the compound of other negative frequency temperature factor system with this microwave-medium ceramics that obtains good dielectric properties.For example, C.L.Huang etc. is at " Mat.Chem.Phy. " 78 (2002): 111-115 has studied CaTiO
3Regulate MgTiO
3Low-temperature sintering problem after the frequency-temperature coefficient system; Kucheiko etc. have studied CaTiO at " J.Am.Ceram.Soc. " 1996 the 10th phase 2739-2743 pages or leaves
3To Ca (Al
1/2Ta
1/2) O
3The adjusting of pottery frequency-temperature coefficient; P.Liu etc. are at " J.European Ceramic Society " 2003, and 23:2417-2421 has studied CaTiO
3Regulate Ca (Li
1/3Ta
2/3) O
3The frequency-temperature coefficient of pottery.
CaTiO
3In the preparation of nano-powder, reported mechanical ball milling method, hydrothermal synthesis method, the chemical coprecipitation etc. of mainly containing.The Manik of the Mi of " Powder Technology " the 104th phase 75-79 page or leaf in 1999 and " Materials Chemistry and Physics " the 86th phase 284-292 page or leaf in 2004, and the people such as Wu Qisheng of domestic " silicate journal " the 5th phase of calendar year 2001 479-483 page or leaf adopt solid phase CaO and TiO respectively
2Powder is a raw material, by mixing and ball milling, utilizes mechanical force and chemical to synthesize CaTiO
3Nanocrystalline, but remaining more TiO
2Influenced CaTiO mutually
3Nanocrystalline purity.People such as Lee pass through mechanical ball milling earlier in " J.Ceram.Proc.Res. " 2004 the 3rd phases 223-226 beginning of the page method obtains CaTiO
3Nanocrystalline, utilize the dissolving of inorganics in organic solvent again, final product has been obtained nano level CaTiO 800 ℃ of calcinings
3Powder, but two steps of this arts demand finish, comparatively complicated." functional materials " 1996 the 5th phase 429-430 pages or leaves, people such as Peng Zifei adopt chemical coprecipitation to prepare nano level CaO-TiO
2Powder about 50nm, but is not done detailed report to its phase composite through the median size of 650 ℃ of thermal treatments powder after two hours.More than about nanometer CaTiO
3The preparation method of powder exists a common difficult point to be: be difficult to obtain single-phase pure nanometer CaTiO
3Powder; And up to the present, do not see nanometer CaTiO
3The relevant report of microwave dielectric property.
Summary of the invention
The present invention breaks through single-phase pure nanometer CaTiO
3The difficult point of powder preparing, the inorganic salt that adopt low-cost calcium are raw material, utilize sol-gel method, sterically hindered effect by gelation process and dispersion agent, and the process heating and calcining decomposes organism and inorganic ion generation oxidizing reaction forms crystalline phase, thereby obtain single phase nano CaTiO at a lower temperature
3Ceramic powder, and to nanometer CaTiO
3Microwave dielectric property behind the sintering is done reported first.
Sol-gel method low temperature synthesizes single phase nano CaTiO
3The preparation method of powder may further comprise the steps:
(1) inorganic salt with calcium are dissolved in the dehydrated alcohol, form the inorganic salt ethanol solution of calcium;
(2) butyl (tetra) titanate is dissolved in the mixing solutions of dehydrated alcohol and acetate, forms the dehydrated alcohol and the acetic acid mixed solution of butyl (tetra) titanate, at least a pH value with mixing solutions that drips in nitric acid and the vinylformic acid transfers to 1～3;
(3) with the dehydrated alcohol of the inorganic salt ethanol solution of calcium and butyl (tetra) titanate and acetic acid mixed solution by calcium: the mol ratio of titanium is 1: 1 a mixed, add dehydrated alcohol and acetate, the concentration of calcium in the mixing solutions or titanium is transferred to 0.5～2mol/l, and the volume ratio of acetate and dehydrated alcohol is 0～1; Add at least a in nitric acid and the vinylformic acid mixing solutions pH value is transferred to 1～3; Weight in mixing solutions is 100%, adds 1～10% dispersion agent;
(4) the above-mentioned mixing solutions that makes is stirred, seals, place 20～60 ℃ of environment, obtain the gel of homogeneous transparent; Gel is dry in 80～120 ℃ baking oven, obtain crisp material;
(5) above-mentioned crisp material is ground, put into the high alumina crucible,, obtain the CaTiO of white 600～900 ℃ of calcinings
3Nano-powder.
The inorganic salt of described calcium can be Ca (NO
3)
24H
2O, CaCl
2, Ca (CH
3COOH)
2H
2O.
Described dispersion agent can be one or more in polyoxyethylene glycol (PEG), Viscotrol C, oleic acid, the stearic acid.
Above-mentioned sol-gel method low temperature synthesizes single phase nano CaTiO
3The preparation method of powder prepares single phase nano CaTiO
3Powder.
Adopt the technology of the invention described above, can obtain particle diameter at 20～100nm and finely disseminated single-phase CaTiO
3Nano-ceramic powder, this nano-powder have higher Qf value after sintering porcelain into, compare with the Qf value after the synthetic micro-powder of conventional solid-state method sinters porcelain into, are significantly improved; And its sintering temperature is with respect to CaTiO
3The sintering temperature of micro-powder has descended 200 ℃.CaTiO
3The nano powder of nano powder and other negative frequency temperature factor is compound, can be used for preparing small-sized chip multiplayer microwave devices such as 0402,0201 laminated ceramic capacitor, has great industrial application value.Preparation method of the present invention has following characteristics:
1. adopt Ca (NO
3)
24H
2O, CaCl
2, Ca (CH
3COOH)
2H
2The inorganic salt of calcium such as O are raw material, and low price and raw material are easy to get;
2. adopt wet chemical method that calcium, titanium elements 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. the CaTiO that obtains
3The ceramic powder particle diameter is adjustable between 20～100nm, and good dispersion; And can after 700 ℃ of calcinings, obtain the single-phase pure CaTiO of particle diameter about 20nm
3Ceramic powder greatly reduces single-phase CaTiO
3Synthesis temperature;
4. the pure nanometer CaTiO of this method synthetic
3Powder can sinter porcelain at 1200 ℃, than the synthetic micron of conventional solid-state method CaTiO
3The sintering temperature of powder (1400 ℃) has descended about 200 ℃; This nano-powder has higher Qf value after sintering porcelain into, sinters Qf value raising 20% behind the porcelain into than the synthetic micro-powder of conventional solid-state method.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
Take by weighing the Ca (NO of 1mol
3)
24H
2O is dissolved in 470 milliliters of dehydrated alcohols, forms the nitrocalcite ethanol solution that concentration is about 2mol/l; The butyl (tetra) titanate of 1mol is mixed with the 200ml dehydrated alcohol, add the acetate of 100ml then, dripping 3 gram concentration simultaneously is 65～68% concentrated nitric acid; Above-mentioned two solution are mixed, stir, add 100ml acetate, 2 gram concentration again and be 65～68% concentrated nitric acid, 20 gram PEG400.
After above-mentioned mixing solutions stirred, be statically placed in 60 ℃ the water-bath, obtain the gel of yellow transparent, 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 white powder, be nano material of the present invention 800 ℃ of calcinings 1 hour.
This material is through TEM Electronic Speculum and laser particle size analysis, and the powder median size is between 60～70nm, and dispersion of particles is good; XRD analysis shows that this nano-powder is single-phase pure CaTiO
3Powder.
With the above-mentioned single-phase pure CaTiO that obtains 800 ℃ of calcinings
3Nano-powder grinding, granulation, be pressed into diameter 18mm, the height 8～9mm nahlock, at 1200～1250 ℃ of sintering, its microwave dielectric property is: ε
r=171, Qf=4239GHz.
Embodiment 2:
Take by weighing the Ca (CH of 1mol
3COOH)
2H
2O is dissolved in 220 milliliters of dehydrated alcohols, forms the lime acetate ethanol solution that concentration is about 4mol/l; The butyl (tetra) titanate of 1mol is mixed with 250ml acetate, add the dehydrated alcohol of 150ml then, dripping 2 gram concentration simultaneously is 65～68% concentrated nitric acid; Above-mentioned two solution are mixed, stir, add 50ml acetate, 100ml dehydrated alcohol, 2 gram concentration again and be 65～68% concentrated nitric acid, 30 gram oleic acid.
After above-mentioned mixing solutions stirred, be statically placed in 40 ℃ the water-bath, obtain the gel of yellow transparent, gel is taken out put into pallet, 120 ℃ dry 12 hours down, obtain the crisp material of garnet.
Above-mentioned crisp garnet material is ground, put into the high alumina crucible,, obtain white powder, be nano material of the present invention 700 ℃ of calcinings 1 hour.
This material is through the TEM electronic microscope photos, and the powder median size is about 20nm; XRD analysis shows that this nano-powder is single-phase pure CaTiO
3Powder.
With the above-mentioned single-phase pure CaTiO that obtains 700 ℃ of calcinings
3Nano-powder grinding, granulation, be pressed into diameter 18mm, the height 8～9mm nahlock, at 1200～1250 ℃ of sintering, its microwave dielectric property is: ε
r=171, Qf=4013GHz.
Embodiment 3:
Take by weighing the Ca (NO of 0.5mol
3)
24H
2O is dissolved in 80 milliliters of dehydrated alcohols, forms the nitrocalcite ethanol solution that concentration is about 5mol/l; The butyl (tetra) titanate of 0.5mol is mixed with 100ml acetate, add the dehydrated alcohol of 150ml then, dripping 4 gram concentration simultaneously is that 65～68% concentrated nitric acid restrains vinylformic acid with 5; Above-mentioned two solution are mixed, stir, add 100ml acetate, 30 gram PEG2000 again.
After above-mentioned mixing solutions stirred, be statically placed in 50 ℃ the water-bath, obtain the gel of yellow transparent, take out and put into pallet, 100 ℃ dry 12 hours down, obtain crisp material.
Above-mentioned crisp material is ground, put into the high alumina crucible,, obtain white powder, be nano material of the present invention 750 ℃ of calcinings 1 hour.
This material is through the TEM electronic microscope photos, and the powder median size is between 40～50nm; XRD analysis shows that this nano-powder is single-phase pure CaTiO
3Powder.
With the above-mentioned single-phase pure CaTiO that obtains 750 ℃ of calcinings
3Nano-powder grinding, granulation, be pressed into diameter 18mm, the height 8～9mm nahlock, at 1200～1250 ℃ of sintering, its microwave dielectric property is: ε
r=171, Qf=4362GHz.
Claims (4)
1, the synthetic single phase nano CaTiO of a kind of sol-gel method low temperature
3The preparation method of powder may further comprise the steps:
(1) inorganic salt with calcium are dissolved in the dehydrated alcohol, form the inorganic salt ethanol solution of calcium;
(2) butyl (tetra) titanate is dissolved in the mixing solutions of dehydrated alcohol and acetate, forms the dehydrated alcohol and the acetic acid mixed solution of butyl (tetra) titanate, at least a pH value with mixing solutions that drips in nitric acid, the vinylformic acid transfers to 1～3;
(3) with the dehydrated alcohol of the inorganic salt ethanol solution of calcium and butyl (tetra) titanate and acetic acid mixed solution by calcium: the mol ratio of titanium is 1: 1 a mixed, add dehydrated alcohol and acetate, the concentration of calcium in the mixing solutions or titanium is transferred to 0.5～2mol/l, and the volume ratio of acetate and dehydrated alcohol is 0～1; Add at least a in nitric acid and the vinylformic acid mixing solutions pH value is transferred to 1～3; Weight in mixing solutions is 100%, adds 1～10% dispersion agent;
(4) the above-mentioned mixing solutions that makes is stirred, seals, place 20～60 ℃ of environment, obtain the gel of homogeneous transparent; Gel is dry in 80～120 ℃ baking oven, obtain crisp material;
(5) above-mentioned crisp material is ground, put into the high alumina crucible,, obtain the CaTiO of white 600～900 ℃ of calcinings
3Nano-powder.
2, preparation method according to claim 1 is characterized in that: the inorganic salt of described calcium can be Ca (NO
3)
24H
2O, CaCl
2, Ca (CH
3COOH)
2H
2O.
3. preparation method according to claim 1 is characterized in that: described dispersion agent can be one or more in polyoxyethylene glycol, Viscotrol C, oleic acid, the stearic acid.
4. the single phase nano CaTiO of preparation method's preparation according to claim 1
3Powder.
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| CN102502797A (en) * | 2011-10-08 | 2012-06-20 | 哈尔滨工程大学 | Method for preparing calcium titanate with eggshells as raw material |
| CN103736476A (en) * | 2014-01-23 | 2014-04-23 | 云南大学 | Calcium titanate/calcium oxide composite photocatalyst as well as preparation method and application thereof |
| CN103922393A (en) * | 2014-03-29 | 2014-07-16 | 山东玉皇化工有限公司 | Method for preparing nanometer flake calcium titanate through supercritical ethyl alcohol fluid |
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| CN101224984B (en) * | 2008-01-30 | 2010-06-02 | 浙江大学 | Low temperature synthesis of ultra-fine ZnO-SiO2 microwave dielectric ceramic powder by sol-gel method |
| CN102502797A (en) * | 2011-10-08 | 2012-06-20 | 哈尔滨工程大学 | Method for preparing calcium titanate with eggshells as raw material |
| CN103736476A (en) * | 2014-01-23 | 2014-04-23 | 云南大学 | Calcium titanate/calcium oxide composite photocatalyst as well as preparation method and application thereof |
| CN103736476B (en) * | 2014-01-23 | 2015-09-30 | 云南大学 | A kind of calcium titanate/calcium oxide composite photo-catalyst and method for making thereof and purposes |
| CN103922393A (en) * | 2014-03-29 | 2014-07-16 | 山东玉皇化工有限公司 | Method for preparing nanometer flake calcium titanate through supercritical ethyl alcohol fluid |
| CN103922393B (en) * | 2014-03-29 | 2015-07-15 | 山东玉皇盛世化工股份有限公司 | Method for preparing nanometer flake calcium titanate through supercritical ethyl alcohol fluid |
| CN106745212A (en) * | 2017-01-09 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts |
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| CN107180916A (en) * | 2017-06-15 | 2017-09-19 | 绍兴文理学院 | A kind of flexible infiltration perovskite photovoltaic material |
| CN108004682A (en) * | 2017-12-08 | 2018-05-08 | 西安理工大学 | A kind of method that electrostatic spinning prepares lotus positive electricity hybridized fiber film |
| CN108004682B (en) * | 2017-12-08 | 2020-08-18 | 西安理工大学 | Method for preparing positively charged hybrid fiber membrane by electrostatic spinning |
| CN108530057A (en) * | 2018-05-15 | 2018-09-14 | 浙江大学 | Sol-gel method application and preparation is in the morphology controllable CaTiO of energy storage3The method of ceramics |
| CN108530057B (en) * | 2018-05-15 | 2020-09-15 | 浙江大学 | Preparation of morphology-controllable CaTiO applied to energy storage by sol-gel method3Method for producing ceramic |
| CN110407548A (en) * | 2019-06-21 | 2019-11-05 | 邓道美 | A kind of preparation method of electromagnetic wave absorbability composite gypsum material |
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| CN110937627A (en) * | 2019-12-12 | 2020-03-31 | 吉林师范大学 | Preparation method of defective calcium titanate nanoparticles |
| 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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