CN109019676A - A kind of method that the precipitation method prepare high-purity Nano-class barium titanate - Google Patents

A kind of method that the precipitation method prepare high-purity Nano-class barium titanate Download PDF

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CN109019676A
CN109019676A CN201811176552.2A CN201811176552A CN109019676A CN 109019676 A CN109019676 A CN 109019676A CN 201811176552 A CN201811176552 A CN 201811176552A CN 109019676 A CN109019676 A CN 109019676A
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temperature
solution
barium
barium titanate
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CN109019676B (en
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资美勇
万亚锋
吴浩
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Hubei Tianci Electronic Materials Co Ltd
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Hubei Tianci Electronic Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/003Titanates
    • C01G23/006Alkaline earth titanates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention discloses a kind of methods that precipitation method prepare high-purity Nano-class barium titanate, are prepared for a kind of high-purity Nano-class barium titanate by the precipitation method, specifically include that (1) is dissolved;(2) it is co-precipitated;(3) filtration washing;(4) it is sanded spraying;(5) it calcines.Barium titanate prepared by the present invention has the features such as at low cost, crystal grain is small, purity is high, good dispersion.

Description

A kind of method that the precipitation method prepare high-purity Nano-class barium titanate
Technical field
The invention belongs to field of electronic materials, are related to a kind of method that the precipitation method prepare high-purity Nano-class barium titanate.
Background technique
With electronic component miniature requirement, MLCC etc. requires to fine grain, high dispersive barium titanate raw material, high-purity Degree, inexpensive direction is developed.Existing market major demands be 500nm and 300nm and hereinafter, and solid phase method prepare 300nm and with Lower complex process, higher cost and dispersion are unevenly;Hydro-thermal method barium titanate granularity is small, is uniformly dispersed, but at high cost.The present invention is logical The barium titanate for crossing precipitation method preparation is at low cost, and crystal grain is small, is uniformly dispersed, and purity is high fully meets market to 300nm and following crystalline substance Grain barium titanate demand.
Summary of the invention
Present invention aims to prepare a kind of high-purity Nano-class barium titanate with the precipitation method.
A kind of method that the precipitation method prepare high-purity barium titanate, its step are as follows:
(1) it dissolves: electronic grade barium carbonate powder being added in the dichloro oxygen titanium solution of 1.0 ~ 2.5mol/L under agitation, instead Barium titanium mixed solution a should be generated, wherein Ba/Ti ratio (molar ratio) is 0.995 ~ 1.005.
(2) it precipitates: using ammonium bicarbonate as precipitating reagent, 2.5 ~ 3.5mol/L ammonium bicarbonate solution being added to by barium with 25-35mL/min flow velocity In titanium mixed solution in a, the Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea of gross mass 5 ~ 8% are added into barium titanium mixed solution a, Stop charging when pH >=7, stirs 30min, reaction process is controlled at 35 ~ 42 DEG C;
(3) filtration washing: adding pure water that washing is filtered for multiple times, and chloride ion is detected with silver nitrate, until chloride ion≤10ppm(colorimetric Method);
(4) it is sanded spraying: slurry being sanded by sand mill, makes to detect granularity D50≤400nm;With inlet temperature for 250 ~ 300 DEG C, 100 DEG C of outlet temperature spray drying;
(5) calcine: calcination temperature 950 ~ 1000,3 DEG C/min of heating rate keep the temperature 2 ~ 3 hours.
The present invention is reacted with dichloro oxygen titanium solution using solid electronic grade barium carbonate powder, Japanese rock paddy carbon point is added simultaneously Son sieve and urea, reduce ammonium bicarbonate usage amount, are good for the environment, and slurry with surface there is the rock paddy carbon molecular sieve of porous structure to make To deposit core, pulp particle is uniformly arranged in rock paddy carbon molecular sieve surface, with regard to shape after pulp particle growth to a certain extent At the presoma that uniform particle sizes, particle size range are unified, finally calcining removal carbon molecular sieve obtains nano barium phthalate of the present invention.This hair It is bright to play the role of improving barium carbonate pattern, and the addition of urea has combustion-supporting effect, promotes carbon molecular sieve, ammonium bicarbonate high temperature point Solution, and it is higher than the common product purity prepared using technical grade barium chloride as the raw material precipitation method to produce product purity;Use sand milling Technique, the dispersion of product precipitate slurry is more uniform, and spraying rear product Ba/Ti is than more uniform stabilization, and mobility and dispersibility are more It is good.
Detailed description of the invention
Fig. 1 is the barium carbonate electromicroscopic photograph that embodiment 1 ~ 11 obtains;
Fig. 2 is the barium carbonate electromicroscopic photograph that comparative example 5 obtains.
Specific embodiment
Embodiment 1 ~ 7
By 99.67g(0.5025mol, calcination and the dichloro oxygen titanium that the total 0.5%) barium carbonate of moisture is added slowly to 2.0mol/L are molten In liquid (250mL) (Ba/Ti=1.005), it is stirred to react until solution is as clear as crystal.Then 3.5mol/L ammonium bicarbonate solution is distinguished It is gone in above-mentioned barium titanium mixed solution with 25,30,35mL/min flow velocitys, gross mass 5 ~ 8% is added into barium titanium mixed solution a Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea, until pH is 7 end, control reaction temperature is respectively 37 ± 2,40 ± 2, heat preservation 30 Minute.Using pure water, until chloride ion≤10ppm;After granularity≤300nm is sanded, with 250 DEG C of inlet temperatures, 100 DEG C go out Mouth temperature spray drying;Start to calcine after drying, 1000 DEG C of calcination temperature, keeps the temperature 2.5 hours.Using nano measurer1.2 Calculate partial size
In comparative example 1,2, be different from embodiment 1 ~ 7: ammonium bicarbonate solution flow velocity is 40 ~ 45mL/min, and reaction temperature is 45 ± 2 DEG C, test result is as follows:
Conclusion: 1-embodiment of embodiment 7 shows Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea that gross mass 5 ~ 8% is added, reaction Process control temp is 35 ~ 42 DEG C, and 25-35mL/min flow velocity can obtain that crystal grain is small, and be uniformly dispersed good, environmentally friendly effect.
Embodiment 8 ~ 13
By 99.17g(0.5mol, calcination is added slowly to the dichloro oxygen titanium solution of 1.0mol/L with the total 0.5%) barium carbonate of moisture In (500mL) (Ba/Ti=1.000), it is stirred to react until solution is as clear as crystal.Then by 2.5mol/L ammonium bicarbonate solution with 25mL/ Min flow velocity is gone in above-mentioned barium titanium mixed solution, and the Japanese rock paddy carbon point of gross mass 5 ~ 8% is added into barium titanium mixed solution a Sub- sieve and 2 ~ 3% urea, until pH is 7 end, 40 ± 2 DEG C of reaction temperature of control keeps the temperature 30 minutes.Using pure water, until Chloride ion≤10ppm;After granularity≤300nm is sanded, with 300 DEG C of inlet temperatures, 100 DEG C of outlet temperature spray drying;After drying Start to calcine, 950 ~ 1000 DEG C of calcination temperature, keeps the temperature 2 ~ 3 hours.Partial size is calculated using nano measurer1.2.
In comparative example 3,4, it is different from embodiment 8 ~ 13: does not add Japanese rock paddy carbon molecular sieve and urea, calcining temperature At 1020 ~ 1080 DEG C, other are same as embodiment 1 ~ 7 for degree control.
Comparative example 5:
By 99.67g(0.5025mol, calcination and the dichloro oxygen titanium that the total 0.5%) barium carbonate of moisture is added slowly to 2.6mol/L are molten In liquid (500mL) (Ba/Ti=1.005), it is stirred to react until solution is as clear as crystal.Then by 4.0mol/L ammonium bicarbonate solution with 30mL/min flow velocity is gone in above-mentioned barium titanium mixed solution, until pH is 7 end, 40 ± 2 DEG C of reaction temperature of control, heat preservation 30 Minute.Using a large amount of pure waters, until chloride ion≤10ppm;After granularity≤300nm is sanded, with 280 DEG C of inlet temperatures, 100 The spray drying of DEG C outlet temperature;Start to calcine after drying, 1000 DEG C of calcination temperature, keeps the temperature 2.5 hours.Test b a/Ti=1.002, Partial size 140nm is calculated using nano measurer1.2, electromicroscopic photograph display is reunited serious.
Test result is as follows:
Conclusion: 8-embodiment of embodiment 13 shows the Japanese rock paddy carbon molecules that gross mass 5 ~ 8% is added into barium titanium mixed solution a Sieve and 2 ~ 3% urea, calcination temperature control between 950 ~ 1000 DEG C, and it is small to obtain crystal grain, are uniformly dispersed good, environmentally friendly Effect.In addition, this patent is as follows through cost accounting:
1. this patent raw material barium carbonate and titanium tetrachloride, ammonium bicarbonate or urea are tetragonal phase finished product after reaction filtration washing sintering, 20000 yuan/ton of cost;
2. using conventional high-tension hydro-thermal method technique, with barium hydroxide, metatitanic acid is raw material, and one-pot production capacity is low;Reaction product is Cubic phase need to wash calcining and prepare tetragonal phase;And the tetragonal phase Electronic Speculum granularity > 300nm being typically prepared, cost is 30000 Yuan/ton;300nm uses water and alcohol or other organic matters to be molten with nanometer grade tetragonal-phase barium titanate prepared by hydro-thermal next time Agent, preparation cost is at 50000 yuan/ton.

Claims (3)

1. a kind of method that precipitation method prepare high-purity Nano-class barium titanate, it is characterised in that following steps:
(1) it dissolves: electronic grade barium carbonate powder is added in the dichloro oxygen titanium solution of 1.0 ~ 2.5mol/L, it is mixed that reaction generates barium titanium Close solution a;
(2) it precipitates: using ammonium bicarbonate as precipitating reagent, 2.5 ~ 3.5mol/L ammonium bicarbonate solution being added to by barium titanium with 25-35mL/min flow velocity and is mixed It closes in solution a, the Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea of gross mass 5 ~ 8%, pH >=7 is added into barium titanium mixed solution a When stop charging, stir 30min, be made slurry b;
(3) filtration washing: adding pure water that washing is filtered for multiple times, and chloride ion is detected with silver nitrate, until chloride ion≤10ppm;
(4) it is sanded spraying: slurry being sanded by sand mill, makes to detect D50 granularity≤400nm;With inlet temperature for 250 ~ 300 DEG C, 100 DEG C of outlet temperature spray drying;
(5) it calcines:, temperature 950 ~ 1000,3 DEG C/min of heating rate keeps the temperature 2 ~ 3 hours.
2. solution temperature≤45 DEG C according to claim 1, are guaranteed using cooling water temperature in step (1) course of dissolution, and Ba/Ti ratio (molar ratio) is 0.995 ~ 1.005.
3. according to claim 1, step (2) precipitating reagent ammonium bicarbonate solution temperature is 30 ~ 40 DEG C, concentration is 2.5 ~ 4.0mol/ L, reaction temperature are controlled at 35 ~ 42 DEG C.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772743A (en) * 2021-09-30 2021-12-10 青岛天尧新材料有限公司 Preparation method of manganese cobalt composite oxide powder

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1948152A (en) * 2006-11-10 2007-04-18 清华大学 High purity ultra fine zirconium biboride powder and its preparation method
KR20130017190A (en) * 2011-08-10 2013-02-20 삼성정밀화학 주식회사 Methods of coating the surface of barium titanic oxide and barium titanic oxide prepared by the same
CN103979600A (en) * 2014-05-30 2014-08-13 上海沃凯生物技术有限公司 Preparation method of ultrathin copper oxide powder
CN106966426A (en) * 2017-04-21 2017-07-21 常州市好利莱光电科技有限公司 A kind of preparation method of nanoporous stannous oxide
CN107555473A (en) * 2017-09-28 2018-01-09 洛阳理工学院 A kind of nanometer BaTiO3Raw powder's production technology
CN108046794A (en) * 2017-12-08 2018-05-18 中国科学院上海硅酸盐研究所 The method that metatitanic acid yttrium crystalline ceramics is prepared using Co deposited synthesis powder
CN108579715A (en) * 2018-05-15 2018-09-28 徐靖才 A kind of preparation method of porous easily separated nano titania catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1948152A (en) * 2006-11-10 2007-04-18 清华大学 High purity ultra fine zirconium biboride powder and its preparation method
KR20130017190A (en) * 2011-08-10 2013-02-20 삼성정밀화학 주식회사 Methods of coating the surface of barium titanic oxide and barium titanic oxide prepared by the same
CN103979600A (en) * 2014-05-30 2014-08-13 上海沃凯生物技术有限公司 Preparation method of ultrathin copper oxide powder
CN106966426A (en) * 2017-04-21 2017-07-21 常州市好利莱光电科技有限公司 A kind of preparation method of nanoporous stannous oxide
CN107555473A (en) * 2017-09-28 2018-01-09 洛阳理工学院 A kind of nanometer BaTiO3Raw powder's production technology
CN108046794A (en) * 2017-12-08 2018-05-18 中国科学院上海硅酸盐研究所 The method that metatitanic acid yttrium crystalline ceramics is prepared using Co deposited synthesis powder
CN108579715A (en) * 2018-05-15 2018-09-28 徐靖才 A kind of preparation method of porous easily separated nano titania catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772743A (en) * 2021-09-30 2021-12-10 青岛天尧新材料有限公司 Preparation method of manganese cobalt composite oxide powder

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