CN102276252B - Method for preparing yttrium and manganese doped barium strontium calcium titanate nano powder - Google Patents
Method for preparing yttrium and manganese doped barium strontium calcium titanate nano powder Download PDFInfo
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- CN102276252B CN102276252B CN 201110138113 CN201110138113A CN102276252B CN 102276252 B CN102276252 B CN 102276252B CN 201110138113 CN201110138113 CN 201110138113 CN 201110138113 A CN201110138113 A CN 201110138113A CN 102276252 B CN102276252 B CN 102276252B
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Abstract
The invention discloses a method for preparing yttrium and manganese doped barium strontium calcium titanate (BSCT) nano powder, which comprises the following steps: preparing aqueous solution of an organic acid; slowly dripping titanium isopropoxide into prepared aqueous solution of the organic acid; stirring and regulating the pH value of the solution to 7.5 to 8.5; dissolving Ba(CH3COO)2, Sr(CH3COO)2.0.5H2O, Ca(NO3)2, Y(NO3)3 and Mn(NO3)2 according to a stoichiometric ratio, stirring to obtain clear solution, adding the clear solution into obtained solution of titanate, regulating the pH value of the solution till the solution is weakly acidic and obtaining solution of a precursor; and directly calcining the obtained solution of the precursor. The BSCT powder prepared by the method disclosed by the invention has the advantages of small particle size, low degree of aggregation, uniform particle size distribution and the like; the preparation method is simple, the preparation period is short, the used raw material is cheap and readily available, and special equipment is not required; and the method is suitable for large-scale production and is expected to be used in industry.
Description
Technical field
The present invention relates to a kind of method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder, belongs to the nano-ceramic powder preparing technical field.
Background technology
Ferroelectric barium strontium calcium (BSCT) and strontium-barium titanate (BST) stupalith are because its high-k, excellent performance such as Curie temperature is adjustable, be widely used in the various electronic ceramic devices, for example: various piezoelectric transducers, dynamic RAM and phase changer etc.Recently, the excellent properties that shows on the no-refrigeration infrared focal plane thermal imaging system of BSCT stupalith has caused the great interest of people again.Because it is worked, and does not need refrigeration unit, greatly reduced the cost of producing infrared eye near room temperature.Have under the room temperature advantage such as work, response spectrum is wide, but the fast all weather operations of response speed, low cost, reduce power consumption, long lifetime, miniaturization, high reliability, application have a large capacity and a wide range by the no-refrigeration infrared focal plane thermal imaging system that this class material is made, become in the current infrared focal plane imaging technology one of the most noticeable technological breakthrough.
In order to obtain the BSCT stupalith of excellent performances such as dielectric, pyroelectricity, the preparation of even, the ultra-fine BSCT powder of chemical constitution is one of factor of most critical.In recent years, people have adopted various liquid phase methods to prepare nanometer BSCT powder.Prepare powder with general solid reaction process and compare, liquid phase method has that each constituent element mixing uniformity is good, reactive behavior is high, obtain advantages such as fine powder body easily.But still there are some shortcomings that are difficult to overcome in present various liquid phase methods and have limited its practical application greatly, and for example: the powder reuniting of coprecipitation method preparation is comparatively serious, and is difficult to remove foreign ion; Hydrothermal method is difficult to obtain the powder of stoichiometric ratio; And general sol-gel method, the cycle is all long, and process is also complicated.Therefore, exploration can either reduce the powder granule degree, increase the powder homogeneity, can guarantee stoichiometric ratio again, and the technological process novel method of practical preparation BSCT nano-powder simply again just becomes one of gordian technique of being badly in need of solution.
Summary of the invention
For the BSCT powder that solves prior art for preparing exists that granularity is big, skewness, stoichiometric ratio are wayward, and problems such as preparation process complexity, cycle length, the invention provides a kind of method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder, to satisfy present microminiaturization, miniaturization and integrated device to the requirement of BSCT powder raw material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder comprises the steps:
A) water-soluble organic acid is soluble in water, stir to clarify;
B) titanium isopropylate is slowly splashed in the aqueous solutions of organic acids of step a) preparation dropping process control solution temperature≤65 ℃;
C) stir after 20～30 hours, the pH value of regulator solution is 7.5～8.5;
D) with Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water according to stoichiometric ratio, stir and make the formation settled solution;
E) solution of step d) preparation is joined in the solution that step c) obtains, stir and add water to be made into mass concentration be 10%～20% mixing solutions, the pH value of regulator solution is slightly acidic then, obtains precursor solution;
F) precursor solution that step e) is obtained is directly calcined, and namely gets the BSCT nano-powder that yttrium manganese mixes.
Described water-soluble organic acid is recommended as acetic acid or water-soluble alpha hydroxy acid.
Described water-soluble alpha hydroxy acid is recommended as lactic acid.
Water-soluble organic acid in the step a) and the mass ratio of water are 1: 1～3: 1.
Titanium isopropylate in the step b) and the mass ratio of water-soluble organic acid are 0.5: 1～1: 1.
The pH value of the precursor solution in the step e) is preferably 5.5～6.5.
Calcination condition in the step f) is recommended as at 550～800 ℃ and calcined 1～20 hour down, is preferably at 700～800 ℃ to calcine 1～2 hour down.
The chemical constitution of described yttrium manganese barium titanate doping strontium calcium is recommended as:
Ba
0.6(1-x)-(x-0.001)/2(Sr
0.3Ca
0.1)
1-xY
xTi
0.999Mn
0.001O
3，0.001≤x≤0.010。
Compared with prior art, adopt the nano-powder of method of the present invention preparation have particle diameter little (10～25nm), advantage such as low, the even particle size distribution of degree of aggregation, can satisfy present microminiaturization, miniaturization and integrated device to the requirement of BSCT powder raw material; And preparation method of the present invention is simple, and preparation cycle is short, and the raw material of use is cheap and easy to get, need not specific installation, is fit to large-scale production, is expected to obtain industrial applications.
Description of drawings
The XRD figure spectrum of the yttrium manganese barium titanate doping strontium calcium powder body that Fig. 1 makes for embodiment 1, wherein: a is the powder that obtained in 20 hours 550 ℃ of calcinings, and b is the powder that obtained in 2 hours 700 ℃ of calcinings, and c is the powder that obtained in 1 hour 800 ℃ of calcinings;
The TEM figure of the yttrium manganese barium titanate doping strontium calcium powder body that Fig. 2 makes for embodiment 1;
The TEM figure of the yttrium manganese barium titanate doping strontium calcium powder body that Fig. 3 makes for embodiment 2.
Embodiment
The present invention is described in further detail and completely below in conjunction with embodiment.
Embodiment 1
568 gram lactic acid are dissolved in the 395 gram deionized waters, stir to clarify; 568 gram titanium isopropylates are slowly splashed in the lactic acid aqueous solution, and vigorous stirring is also controlled temperature≤65 ℃ of solution simultaneously; Stirring after 24 hours, is that 28% strong aqua and the pH value of acetic acid regulator solution are 8.0 with mass concentration, makes solution-stabilized.
According to Formula B a
0.5928(Sr
0.3Ca
0.1)
0.993Y
0.007Ti
0.999Mn
0.001O
3Take by weighing the Ba (CH of stoichiometric ratio
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water, stir and make the formation settled solution; Join then in the metatitanic acid solution for preparing, fully stir, and adding water, to be made into mass concentration be 15% mixing solutions; Be that 28% strong aqua and the pH value of acetic acid regulator solution are 6.0 with mass concentration, obtain precursor solution.
Divide three equal parts with the precursor solution that obtains, portion was calcined 20 hours at 550 ℃, and a 700 ℃ of calcinings 2 hours, portion was calcined 1 hour under 800 ℃.
The BSCT powder that the yttrium manganese that different calcination conditions are obtained mixes carries out its material phase analysis with the RAX-10 diffractometer, and the XRD figure spectrum that obtains is seen shown in Figure 1.
As seen from Figure 1: just can obtain the BSCT powder that pure phase yttrium manganese mixes in 2 hours 700 ℃ of calcinings, if prolong calcination time, then can obtain the BSCT powder that pure phase yttrium manganese mixes at low temperature (550 ℃) more, than additive method, this synthesis temperature is very low.Simultaneously, from the broadening of diffraction peak as can be seen, the synthetic powder of method is thinner thus.
Fig. 2 schemes for the TEM of the yttrium manganese barium titanate doping strontium calcium powder body that present embodiment makes, and as seen from Figure 2: the particle diameter of prepared yttrium manganese barium titanate doping strontium calcium powder body is little, has only about 10nm, and is approaching with the calculation result of XRD, and even particle size distribution, and degree of aggregation is very low.
568 gram acetic acid are dissolved in the 190 gram deionized waters, stir to clarify; 284 gram titanium isopropylates are slowly splashed in the acetic acid aqueous solution, and vigorous stirring is also controlled temperature≤65 ℃ of solution simultaneously.
All the other contents are described with embodiment 1.
Fig. 3 schemes for the TEM of the yttrium manganese barium titanate doping strontium calcium powder body that present embodiment makes.As seen from Figure 3: the particle diameter of prepared yttrium manganese barium titanate doping strontium calcium powder body is less, is about 10～25nm, and is approaching with the calculation result of XRD, and even particle size distribution, and degree of aggregation is lower.
In sum, adopt the yttrium manganese barium titanate doping strontium calcium powder body of the inventive method preparation have particle diameter little (10～25nm), advantage such as low, the even particle size distribution of degree of aggregation.
Be necessary to be pointed out that at this: above embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (6)
1. a method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder is characterized in that, comprises the steps:
A) water-soluble organic acid is soluble in water, stir to clarify; Described water-soluble organic acid is acetic acid or lactic acid;
B) titanium isopropylate is slowly splashed in the aqueous solutions of organic acids of step a) preparation dropping process control solution temperature≤65 ℃;
C) stir after 20～30 hours, the pH value of regulator solution is 7.5～8.5;
D) with Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water according to stoichiometric ratio, stir and make the formation settled solution;
E) solution of step d) preparation is joined in the solution that step c) obtains, stir and add water to be made into mass concentration be 10%～20% mixing solutions, the pH value of regulator solution is slightly acidic then, obtains precursor solution;
F) precursor solution that step e) is obtained was directly calcined 1～20 hour down at 550～800 ℃, namely got the BSCT nano-powder that yttrium manganese mixes.
2. the method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder according to claim 1, it is characterized in that: the water-soluble organic acid in the step a) and the mass ratio of water are 1:1～3:1.
3. the method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder according to claim 1, it is characterized in that: the titanium isopropylate in the step b) and the mass ratio of water-soluble organic acid are 0.5:1～1:1.
4. the method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder according to claim 1, it is characterized in that: the pH value of the precursor solution in the step e) is 5.5～6.5.
5. the method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder according to claim 1 is characterized in that: the calcination condition in the step f) is for 700～800 ℃ of calcinings 1～2 hour down.
6. according to each described method for preparing yttrium manganese barium titanate doping strontium calcium nano-powder in the claim 1 to 5, it is characterized in that the chemical constitution of described yttrium manganese barium titanate doping strontium calcium is:
Ba
0.6(1-x)-(x-0.001)/2(Sr
0.3Ca
0.1)
1-xY
xTi
0.999Mn
0.001O
3，0.001≤x≤0.010。
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