CN104803412B - Hydro-thermal method prepares the method for two Barium metatitanate .s - Google Patents
Hydro-thermal method prepares the method for two Barium metatitanate .s Download PDFInfo
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- CN104803412B CN104803412B CN201510226049.3A CN201510226049A CN104803412B CN 104803412 B CN104803412 B CN 104803412B CN 201510226049 A CN201510226049 A CN 201510226049A CN 104803412 B CN104803412 B CN 104803412B
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Abstract
The present invention relates to the hydrothermal preparing process of ferroelectric material two Barium metatitanate., include following steps: 1) dried barium hydroxide. and sodium hydroxide are mixed in deionized water, obtain mixed solution after being sufficiently stirred for；2) in vacuum glove box, titanium tetrachloride is added drop-wise to step 1) described in mixed solution in obtain reaction solution；3) reaction solution that described configuration is good is joined in polytetrafluoroethyllining lining, then liner is put into hydrothermal reaction kettle react；4) by the product eccentric cleaning obtained after described reaction, it is dried, obtains presoma；5) by described presoma heat treatment in Muffle furnace, two Barium metatitanate .s are obtained.The invention has the beneficial effects as follows: two purer barium carbonate powders can be obtained, and barium dititanate can be prepared by sintering further with this.The present invention is not required to the highest pressure, and device therefor is simple, lower cost.
Description
Technical field
The present invention relates to ferroelectric material technical field, particularly relate to a kind of ferroelectric material at b direction of principal axis with bigger dielectric constant
The hydrothermal preparing process of two Barium metatitanate .s.
Background technology
Ferroelectricity is nineteen twenty, Frenchman Valasek cease salt (sodium potassium tartrate tetrahydrate, NaKC at sieve4H4O6·4H2O) send out in
Existing.There is the crystal structure of ferroelectric material just there is when being not added with external electric field spontaneous polarization phenomenon, and its polarised direction
Can change along with the change in external electrical field direction.The crystal structure of ferroelectric material can change in certain temperature, by ferroelectric phase
It is changed into paraelectric phase, therefore can apply in Ferroelectric Random Access Memory, dynamic RAM, make the temperature that structure is undergone mutation
Degree is referred to as Curie temperature.
Study the most highly developed BaTiO3Based leadless piezoelectric ceramics is BaO-TiO2A kind of compound in system, to environment
Friendly and there is higher dielectric constant, but its low Curie temperature limits its application.The ferroelectricity of two Barium metatitanate .s is closely
Within several years, being found, its space group is the C of low-symmetry2, it is BaTiO at the axial dielectric constant of b32～3 times, and
Curie temperature is 380-470 DEG C, has a good application prospect.But two Barium metatitanate .s are Thermodynamically stables at 1220-1230 DEG C
, it is all metastable condition at a temperature of other, therefore prepares the two pure phases of Barium metatitanate. and there is certain difficulty.
In the method for current known preparation two Barium metatitanate., there are molten-salt growth method, solid reaction process, sol-gal process, laser chemistry
Vapour deposition, discharge plasma sintering, float-zone method etc..The document utilizing two one-step hydrothermals to prepare two Barium metatitanate .s delivered for 2006
Wang L, Li G, Zhang Z.Synthesis of nanobelts [J] .Materials Research Bulletin, 2006,41 (4):
The preparation-obtained material of 842-846 is not two Barium metatitanate .s according to X ray diffracting spectrum reality shown in this article.The most so far
Hydro-thermal method is not the most utilized to be successfully prepared the relevant report of two Barium metatitanate. phases.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of new preparation method utilizing hydro-thermal method to prepare two Barium metatitanate .s.This is prepared
Method is with Hydrothermal Synthesis as key step, and device therefor is simple, and lower cost can synthesize two barium carbonate powders, and with this
Two barium titanate ferroelectric ceramicses can be sintered further into.
The present invention solves the method that the technical scheme is that hydro-thermal method of above-mentioned technical problem prepares two Barium metatitanate .s, include with
Lower step:
1) dried barium hydroxide. and sodium hydroxide are mixed in deionized water, after being sufficiently stirred for, obtain mixed solution；Described one
The mol ratio of hydronium(ion) Barium monoxide and sodium hydroxide is 1:6～10；
2) in vacuum glove box, titanium tetrachloride is added drop-wise to step 1) described in mixed solution in obtain reaction solution；Described
The mol ratio of dried barium hydroxide. and titanium tetrachloride is 1:1.8～2.1；
3) reaction solution that described configuration is good is joined in polytetrafluoroethyllining lining, then liner is put into hydrothermal reaction kettle carry out
Reaction；
4) by the product eccentric cleaning obtained after described reaction, it is dried, obtains presoma；
5) by described presoma heat treatment in Muffle furnace, ferroelectric material two Barium metatitanate. with relatively high-curie temperature is obtained.
By such scheme, step 2) pH value that regulates described reaction solution is 11-14.
By such scheme, step 3) compactedness in described polytetrafluoroethyllining lining is 70%-80%.
By such scheme, the temperature of described hydro-thermal reaction is 160～240 DEG C, and the time of described hydro-thermal reaction is 18～72 hours.
By such scheme, the temperature of described heat treatment is 900～1200 DEG C, and the time of described heat treatment is 3～6 hours.
The present invention prepares the technological process of two Barium metatitanate .s and mainly includes hydro-thermal reaction and heat treatment, in hydrothermal reaction process, titanium from
Son (Ti4+), barium ions (Ba2+) and solution in hydroxide ion (OH-) react, generate the amorphous phase of rich titanium.
Owing to barium/titanium mol ratio controls near 1:2, the nucleus of two Barium metatitanate .s therefore can be formed.In heat treatment process subsequently, two
The nucleus of Barium metatitanate., through forming core and growth process, crystallizes into two Barium metatitanate. crystalline phases.
The invention has the beneficial effects as follows: provide a kind of new preparation method utilizing hydro-thermal method to prepare two Barium metatitanate .s, can obtain relatively
Two pure barium carbonate powders, and barium dititanate can be prepared by sintering further with this.The present invention is not required to the highest pressure,
Device therefor is simple, lower cost, can be applicable to two barium carbonate powders and the preparation of pottery.
Accompanying drawing explanation
The X-ray diffractogram of the ferroelectric material that Fig. 1 provides for the embodiment of the present invention 1；
The dielectric properties test figure of the ferroelectric material that Fig. 2 provides for the embodiment of the present invention 1；
The scanning electron microscope (SEM) photograph of the ferroelectric material that Fig. 3 provides for the embodiment of the present invention 1；
The X-ray diffractogram of the ferroelectric material that Fig. 4 provides for the embodiment of the present invention 2；
The X-ray diffractogram of the ferroelectric material that Fig. 5 provides for the embodiment of the present invention 3；
The X-ray diffractogram of the ferroelectric material that Fig. 6 provides for the embodiment of the present invention 4.
Detailed description of the invention
In the present invention, chemical raw material used is street drug, the present invention first by dried barium hydroxide. and sodium hydroxide go from
Mixing in sub-water, the mol ratio of described dried barium hydroxide. and sodium hydroxide is 1:x, and described x meets following condition: 6 < x < 10,
It is preferably 7≤x≤9.In above-mentioned solution, add titanium tetrachloride, obtain reaction solution.In the present invention, described
Titanium tetrachloride measures in vacuum glove box, drips and stirs, and then inhibits the hydrolysis of titanium tetrachloride.This
In invention, the mol ratio of described dried barium hydroxide. and titanium tetrachloride is preferably 1:1.8～2.1.After obtaining reaction solution, will
It joins in polytetrafluoroethyllining lining, and compactedness is preferably 70%～80%.Described reaction solution need to regulate pH with sodium hydroxide
Value, preferably 11～14.Described polytetrafluoroethyllining lining being put into and carry out hydro-thermal reaction in hydrothermal reaction kettle, described hydro-thermal is anti-
The temperature answered is preferably 160～240 DEG C, more preferably 170～230 DEG C, most preferably 180～220 DEG C, described hydro-thermal reaction time
Between be preferably 18～72 hours, more preferably 30～48 hours.After hydro-thermal reaction terminates, by product eccentric cleaning 6～8 times, so
After be dried to obtain presoma.Hydro-thermal reaction device is not particularly limited by the present invention, can be thermostatic drying chamber.Obtain presoma
After, by its heat treatment, ferroelectric material two Barium metatitanate. with relatively high-curie temperature i.e. can be obtained, the temperature of described heat treatment is preferred
Being 900～1200 DEG C, more preferably 920～1120 DEG C, most preferably 940～1100 DEG C, described heat treatment time is preferably 3～6
Hour.Annealing device is not particularly limited by the present invention, can be chamber type electric resistance furnace.
The ferroelectric material providing the present invention carries out performance detection, and result shows, ferroelectric material prepared by the present invention is purer two
Barium metatitanate., and there is higher Curie temperature, its Curie temperature is 389 DEG C.
In order to further illustrate the present invention, below in conjunction with example prepared by the hydro-thermal method that the present invention provides the preparation method of two Barium metatitanate .s
It is described in detail.
Embodiment 1
By the dried barium hydroxide. (Ba (OH) that purity is 99%2·H2O) 0.00248mol and purity are the sodium hydroxide of 98%
(NaOH) 0.01984mol (mol ratio 1:8) mixes in deionized water, obtains mixed solution.By purity in vacuum glove box
It is the titanium tetrachloride (TiCl of 99.5%4) 0.00496mol (barium/titanium mol ratio 1:2) is added drop-wise in described mixed solution, after stirring
To reaction solution.Pouring in polytetrafluoroethyllining lining by described reaction solution, regulation compactedness is 80% and pH value is 12～13
Put in hydrothermal reaction kettle after (regulating with sodium hydroxide).Utilize thermostatic drying chamber, described hydrothermal reaction kettle is heated to 180
DEG C reaction 36 hours, then by product eccentric cleaning 6 times, obtains presoma after drying；By presoma at chamber type electric resistance furnace
In 1050 DEG C of heat treatments 4 hours, obtain material, described material is two purer Barium metatitanate .s.
Being that Germany's Bruker company D8 type X-ray ff diffractometer material to obtaining carries out component analysis by model, result sees
Fig. 1.Fig. 1 is the X ray picture of material prepared by the embodiment of the present invention.As shown in Figure 1, the material that prepared by the present embodiment is for relatively
Two pure Barium metatitanate .s, its molecular formula is BaTi2O5。
It is that Britain's Wayne Kerr 6500B precise impedance analyser material to obtaining carries out dielectric properties test, result by model
See Fig. 2.Fig. 2 is the dielectric properties figure of material prepared by the embodiment of the present invention.As shown in Figure 2, the material that prepared by the present embodiment
The Curie temperature of material is 389 DEG C.
Being that Japan's JSM-5510LV scanning electron microscope material to obtaining carries out pattern test by model, result sees Fig. 3.
Fig. 3 is the scanning electron microscope (SEM) photograph of material prepared by inventive embodiments.From the figure 3, it may be seen that material prepared by the present embodiment is elementary cell
In the most bar-shaped, micro-meter scale size.
Embodiment 2
By the dried barium hydroxide. (Ba (OH) that purity is 99%2·H2O) 0.00248mol and purity are the sodium hydroxide of 98%
(NaOH) 0.0248mol (mol ratio 1:10) mixes in deionized water, obtains mixed solution.By purity in vacuum glove box
It is the titanium tetrachloride (TiCl of 99.5%4) 0.005208mol (barium/titanium mol ratio 1:2.1) is added drop-wise in described mixed solution, after stirring
Obtain reaction solution.Pouring in polytetrafluoroethyllining lining by described reaction solution, regulation compactedness is 80% and pH value is 13～14
Put in hydrothermal reaction kettle after (regulating with sodium hydroxide).Utilize thermostatic drying chamber, described hydrothermal reaction kettle is heated to 180
DEG C reaction 50 hours, then by product eccentric cleaning 6 times, obtains presoma after drying；By presoma at chamber type electric resistance furnace
In 1050 DEG C of heat treatments 4 hours, obtain material, described material principal phase is two Barium metatitanate .s.
Being that Germany's Bruker company D8 type X-ray diffractometer material to obtaining carries out component analysis by model, result sees figure
4.Fig. 4 is the X ray picture of material prepared by the embodiment of the present invention.As shown in Figure 4, the material that prepared by the present embodiment is two titaniums
Acid barium, but contain a small amount of rutile and a small amount of ferroelectric material Barium metatitanate. (BaTiO the most simultaneously3).The change of preparation technology parameter causes
Obtained material purity relatively embodiment 1 decreases.
Embodiment 3
By the dried barium hydroxide. (Ba (OH) that purity is 99%2·H2O) 0.00248mol and purity are the sodium hydroxide of 98%
(NaOH) 0.01488mol (mol ratio 1:6) mixes in deionized water, obtains mixed solution.By purity in vacuum glove box
It is the titanium tetrachloride (TiCl of 99.5%4) 0.004464mol (barium/titanium mol ratio 1:1.8) is added drop-wise in described mixed solution, after stirring
Obtain reaction solution.Pouring in polytetrafluoroethyllining lining by described reaction solution, regulation compactedness is 80% and pH value is 11～12
After put in hydrothermal reaction kettle.Utilize thermostatic drying chamber, described hydrothermal reaction kettle is heated to 160 DEG C of reactions 24 hours, then
By product eccentric cleaning 6 times, obtain presoma after drying；By little for presoma 950 DEG C of heat treatments 4 in chamber type electric resistance furnace
Time.Finally give based on the product of two Barium metatitanate .s.
Being that Germany's Bruker company D8 type X-ray diffractometer material to obtaining carries out component analysis by model, result sees figure
5.Fig. 5 is the X ray picture of material prepared by the embodiment of the present invention.As shown in Figure 5, the material principal phase that prepared by the present embodiment is
Two Barium metatitanate .s, but occur in that content Barium metatitanate. (BaTiO more more than embodiment 2 simultaneously3) and a small amount of microwave dielectric material
Ba4Ti13O30.The change of preparation technology parameter causes obtained material purity relatively embodiment 1 to decrease.
Embodiment 4
By the dried barium hydroxide. (Ba (OH) that purity is 99%2·H2O) 0.00248mol and purity are the sodium hydroxide of 98%
(NaOH) 0.01984mol (mol ratio 1:8) mixes in deionized water, obtains mixed solution.By purity in vacuum glove box
It is the titanium tetrachloride (TiCl of 99.5%4) 0.00496mol (barium/titanium mol ratio 1:2) is added drop-wise in described mixed solution, after stirring
To reaction solution.Pouring in polytetrafluoroethyllining lining by described reaction solution, regulation compactedness is 70% and pH value is 12～13
After put in hydrothermal reaction kettle.Utilize thermostatic drying chamber, described hydrothermal reaction kettle is heated to 240 DEG C of reactions 72 hours, then
By product eccentric cleaning 6 times, obtain presoma after drying；By little for presoma 1100 DEG C of heat treatments 6 in chamber type electric resistance furnace
Time.The thing finally given is mainly two Barium metatitanate .s mutually.
Being that Germany's Bruker company D8 type X-ray diffractometer material to obtaining carries out component analysis by model, result sees figure
6.Fig. 6 is the X ray picture of material prepared by the embodiment of the present invention.It will be appreciated from fig. 6 that material principal phase prepared by the present embodiment is
Two Barium metatitanate .s, but contain a small amount of ferroelectric material Barium metatitanate. (BaTiO simultaneously3) and Ba6Ti17O40.The change of preparation technology parameter
Obtained material purity relatively embodiment 1 is caused to decrease.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for this skill
For the those of ordinary skill in art field, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement
And modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (2)
1. the method that hydro-thermal method prepares two Barium metatitanate .s, includes following steps:
1) dried barium hydroxide. and sodium hydroxide are mixed in deionized water, after being sufficiently stirred for, obtain mixed solution；Described one
The mol ratio of hydronium(ion) Barium monoxide and sodium hydroxide is 1:6～10；
2) in vacuum glove box, titanium tetrachloride is added drop-wise to step 1) described in mixed solution in obtain reaction solution；Regulation
The pH value of described reaction solution is 11-14；The mol ratio of described dried barium hydroxide. and titanium tetrachloride is 1:1.8～2.1；
3) reaction solution that described configuration is good is joined in polytetrafluoroethyllining lining, then liner is put into hydrothermal reaction kettle carry out
Reaction；The temperature of hydro-thermal reaction is 160～240 DEG C, and the time of described hydro-thermal reaction is 18～72 hours；
4) by the product eccentric cleaning obtained after described reaction, it is dried, obtains presoma；
5) by described presoma heat treatment in Muffle furnace, the temperature of described heat treatment is 900～1200 DEG C, described heat treatment
Time be 3～6 hours；Obtain ferroelectric material two Barium metatitanate. with relatively high-curie temperature.
Hydro-thermal method the most according to claim 1 prepares the method for two Barium metatitanate .s, it is characterised in that step 3) described poly-four
Compactedness in fluorothene liner is 70%-80%.
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| CN110129772B (en) * | 2019-04-10 | 2021-06-22 | 广东省医疗器械研究所 | Preparation method of barium titanate in-situ coating |
| CN113788494A (en) * | 2021-10-27 | 2021-12-14 | 上海大学(浙江·嘉兴)新兴产业研究院 | Preparation method of barium dititanate |
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