CN1803709A - Nanometer bismuth titanate aqueous casting slurry and preparation method thereof - Google Patents
Nanometer bismuth titanate aqueous casting slurry and preparation method thereof Download PDFInfo
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- CN1803709A CN1803709A CN 200510112112 CN200510112112A CN1803709A CN 1803709 A CN1803709 A CN 1803709A CN 200510112112 CN200510112112 CN 200510112112 CN 200510112112 A CN200510112112 A CN 200510112112A CN 1803709 A CN1803709 A CN 1803709A
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Abstract
The invention relates to the dispersion in water of nano bismuth titanate powder and its water-based casting slurry. Wherein, using water-soluble AA-acrylate copolymer as dispersant to disperse the nano bismuth titanate powder with size less than 180nm in water and prepare the suspension with high solid content and low viscosity and well stability; then obtaining the final slurry by adding adhensive and plasticizer from AA-acrylate copolymer, polyvinyl alcohol ,glycerin and ether. Wherein, the final content in slurry comprises: 60-80wt% solid, 0.3-4.0wt% copolymer, 4-10wt% polyvinyl alcohol, 2.5-7.0wt% glycerin and 1.25-3.5wt% ether. The final product has well property and even distribution of powder size and air pore.
Description
Technical field
The present invention relates to a kind of nanometer bismuth titanate (Bi
4Ti
3O
12) aqueous casting slurry and preparation method.More precisely providing a kind of is that dispersion agent, polyvinyl alcohol are that binding agent, low-molecular-weight alcohols are that softening agent, low-molecular-weight ethers are the water-base nano bismuth titanates slurry that is applicable to curtain coating of defoamer with the acrylic acid and acrylic ester copolymers.This slurry solid load height, favorable dispersity, stable can be used for preparing the casting films of 60-300 μ m.This invention belongs to the field that water-based tape casting prepares stupalith.
Background technology
Bismuth titanates is to have low-k, high curie point and big spontaneous polarization, and at electrical condenser, aspects such as high-temperature piezoelectric transmitter and photoelectric device have wide practical use.In addition, the bismuth titanates advantage that do not contain lead element makes it become the potential surrogate of the Pb-based lanthanumdoped zirconate titanates base piezoelectric ceramic of present widespread use.Yet the sheet structure characteristics determined of bismuth titanates its tender stupid electric field height, be difficult for polarization.The method that solves mainly contains two kinds: the one, and adopt design of components to carry out doping vario-property, the 2nd, preparation texturing pottery.Different with design of components, what preparation texturing pottery adopted is the method for microstructure design, promptly adopts certain technology that the crystal grain orienting in the material is lined up, and the most general method is the template grain growth technology at present.And in the template grain growth technology, raw materials usedly usually form by a large amount of nano level fine powder bodies and the template that has the anisotropic grain pattern on a small quantity, as relative simple technology, curtain coating often is used to make template crystal grain to align in base substrate, and this moment, the character of casting slurry just seemed particularly important.
From present bibliographical information, what adopt at the curtain coating of bismuth titanates great majority is organic curtain coating.Yet organic curtain coating needs to use a large amount of organic solvents in the slurry process for preparation, and most organic solvent not only has toxicity, can cause detrimentally affect to environment and human body in exclusion process, and cost is higher, is not suitable for producing in enormous quantities.Consider the needs of environment protection and Sustainable development, water-based flow casting technique just progressively comes into one's own.Compare with organic curtain coating, the kind of the selectable dispersion agent of aqueous casting slurry, binding agent and softening agent is all fewer, because the surface tension of water is bigger, slurry can produce a large amount of bubbles in mechanical milling process again, will produce detrimentally affect to the density of casting films.Therefore, water-based tape casting will be taken all factors into consideration Zeta-potential, the ionic strength of solution and the factors such as selection of pH value and dispersion agent and binding agent etc. of powder in water solvent.In addition, flow casting molding is based on the stable slurry of high solid loading, modest viscosity, and the particle diameter of used powder mostly is nano level or submicron order greatly in the high-performance ceramic, because ultrafine particle surface energy height, trend with spontaneous reunion, the coacervate gravitate easily sinks, and this will directly influence stability of slurry.Therefore, the dispersion of superfine powder in solution is most important.
Summary of the invention
The object of the present invention is to provide a kind of nanometer bismuth titanate aqueous casting slurry, described slurry is to be that dispersion agent, polyvinyl alcohol are that binding agent, low-molecular-weight alcohols are that softening agent, low-molecular-weight ethers are defoamer, are applicable to the water-base nano bismuth titanates slurry of curtain coating with the acrylic acid and acrylic ester copolymers.At first based on the scattering problem of bismuth titanates nano-powder in the aqueous solution, select water miscible acrylic acid and acrylic ester copolymers to replace polyacrylic ionogen commonly used as dispersion agent, utilize acrylic acid and acrylic ester copolymers to be adsorbed on Coulomb repulsion effect and the sterically hindered effect that powder surface produces and realize the good distribution of bismuth titanates nano-powder in the aqueous solution, select suitable binding agent and softening agent to obtain solid load height, favorable dispersity, stable aqueous casting slurry again.
The objective of the invention is to implement by following manner: with the nanometer bismuth titanate is starting raw material, adds deionized water and dispersion agent in proportion, uses NH
3H
2O regulates the pH value to 8-10, is obtaining Bi behind the ball milling 15-24h on the multi-directional ball grinding machine
4Ti
3O
12Suspension.Add binding agent and softening agent (content of additive is the weight percent of solid load) again, continue ball milling 15-24h on the multi-directional ball grinding machine.Slurry is poured out, added defoamer at last, obtain the aqueous casting slurry of bismuth titanates after the vacuum outgas.
Specifically
(1) take by weighing the bismuth titanates nano-powder of 60-80% by weight, add deionized water and dispersion agent in proportion, dispersant is 0.1-4.0wt% (content of dispersion agent is the weight percent of solid load).Use NH
3H
2O regulates the pH value and has the high Zeta-potential of absolute value to guarantee slurry to 8-10, gives full play to intergranular Coulomb repulsion effect, is obtaining Bi behind the ball milling 15-24h on the multi-directional ball grinding machine
4Ti
3O
12Suspension.The particle diameter of used bismuth titanate powder is less than 180nm.
(2) add the binding agent polyvinyl alcohol of 4-10%, the softening agent of 2.5-7.0% in above-mentioned suspension, (content of binding agent and softening agent is the weight percent of solid load) continues ball milling 15-24h on the multi-directional ball grinding machine.
(3) slurry is poured out, added the defoamer of 1.25-3.5%, (content of defoamer also be the weight percent of solid load) is the aqueous casting slurry that obtains bismuth titanates after outgasing under the condition of 0.05-0.08MPa in vacuum tightness.
In sum according to water-based slurry provided by the present invention, it is characterized in that with acrylic acid and acrylic ester copolymers as dispersion agent, polyvinyl alcohol is a binding agent, low-molecular-weight glycerol is that softening agent, low-molecular-weight ether are defoamer, with the solid load is benchmark, the content of acrylic acid and acrylic ester copolymers is 0.1-4.0%, the content of polyvinyl alcohol is 4-10%, the content of glycerol is 2.5-7.0%, the content of ether is 1.25-3.5%, and the nanometer bismuth titanate powder solid load in the slurry accounts for 60-80wt%; Above content is weight percentage; The particle diameter of employed bismuth titanate powder is less than 180nm.
Advantage of the present invention is conspicuous
(1) blank preparation technics is simple, and cost is low, and is almost pollution-free to environment.
(2) the solid load height of slurry, favorable dispersity, stable are suitable for curtain coating.
(3) use the casting films surfacing of this pulp preparation, powder granule and even air hole distribution, the intensity height, workability is good.
Description of drawings
Preparation technology's schema of Fig. 1 casting slurry
Fig. 2 solid load is the flow curve of the bismuth titanates slurry of 78wt%
Fig. 3 is different, and the acrylic acid and acrylic ester copolymers dispersant is the influence of the bismuth titanates slurry rheological property of 67wt% to solid load
The Zeta-potential of bismuth titanates suspension and the relation of pH value under the different acrylic acid and acrylic ester copolymers dispersant concentrations of Fig. 4
SEM photo (a) upper surface of casting films upper and lower surface behind Fig. 5 binder removal; (b) lower surface
Embodiment
Further illustrate substantive distinguishing features of the present invention and obvious improvement by following embodiment description, but the present invention only is confined to embodiment by no means.
Solid load in the design slurry is 78wt%, the content of dispersion agent acrylic acid and acrylic ester copolymers is 1.0wt%, the content of binding agent polyvinyl alcohol is 5.0wt%, the content of softening agent glycerol is 2.5wt%, the content of defoamer ether is 1.3wt% (content of additive is the weight percent of solid load), the pH value is 9, prepares slurry according to the technical process of Fig. 1, and rheological property as shown in Figure 2.The microstructure of gained casting films upper and lower surface is as shown in Figure 5 behind the binder removal after the curtain coating.This casting films upper and lower surface structures is similar, surfacing, powder granule and even air hole distribution.
Solid load in the design slurry is 60wt%, the content of dispersion agent acrylic acid and acrylic ester copolymers is 3wt%, the content of binding agent polyvinyl alcohol is 8wt%, the content of softening agent glycerol is 2.5wt%, the content of defoamer ether is 1.3wt% (above-mentioned content is the weight percent of solid load), the pH value is 10, prepares slurry according to the technical process of Fig. 1, and rheological property is similar shown in Figure 2.
The content of acrylic acid and acrylic ester copolymers is 0.5wt% in the design slurry, the relation that records the Zeta-potential of slurry and pH value as shown in Figure 4, solid load be 67wt% slurry rheological property as shown in Figure 3.Compare with the slurry that does not add acrylic acid and acrylic ester copolymers, the iso-electric point that adds the slurry of acrylic acid and acrylic ester copolymers obviously is offset to low pH value direction, when the pH value greater than 3 the time, Zeta-potential descends significantly, helps improving stability of slurry.Because being the slurry of 67wt%, solid load under the situation of not adding acrylic acid and acrylic ester copolymers, can't prepare, therefore for to contrast, having prepared acrylic acid and acrylic ester copolymers content is the slurry of 0.1wt%, after finding to add the acrylic acid and acrylic ester copolymers of 0.5wt%, the viscosity of slurry reduces, and flowability is able to obvious improvement.
The content of dispersion agent acrylic acid and acrylic ester copolymers is 1.0wt% in the design slurry, the relation that records the Zeta-potential of slurry and pH value as shown in Figure 4, solid load be 67wt% slurry rheological property as shown in Figure 3.
The content of dispersion agent acrylic acid and acrylic ester copolymers is 2.0wt% in the design slurry, the relation that records the Zeta-potential of slurry and pH value as shown in Figure 4, solid load be 67wt% slurry rheological property as shown in Figure 3.
The content of dispersion agent acrylic acid and acrylic ester copolymers is 4.0wt% in the design slurry, and solid load is 67wt%, and the rheological property that records slurry behind the ball milling 24h as shown in Figure 3.
Claims (4)
1. nanometer bismuth titanate powder aqueous casting slurry, it is characterized in that with acrylic acid and acrylic ester copolymers as dispersion agent, polyvinyl alcohol is a binding agent, low-molecular-weight glycerol is that softening agent, low-molecular-weight ether are defoamer, with the solid load is benchmark, the content of acrylic acid and acrylic ester copolymers is 0.1-4.0%, the content of polyvinyl alcohol is 4-10%, the content of glycerol is 2.5-7.0%, the content of ether is 1.25-3.5%, and the nanometer bismuth titanate powder solid load in the slurry accounts for 60-80wt%; Above content is weight percentage.
2. by the described nanometer bismuth titanate powder of claim 1 aqueous casting slurry, the particle diameter that it is characterized in that employed bismuth titanate powder is less than 180nm.
3. the method for preparing the described nanometer bismuth titanate powder of claim 1 aqueous casting slurry is characterized in that concrete processing step is:
(a) take by weighing a certain amount of Bi
4Ti
3O
12Powder adds deionized water and dispersion agent in proportion, and dispersant is the weight percent 0.1-4.0wt% of solid load; And use NH
3H
2O regulates pH value of slurry to 8-10, is obtaining Bi behind the ball milling 15-24h on the multi-directional ball grinding machine
4Ti
3O
12Suspension;
(b) in above-mentioned suspension, add binding agent, softening agent, continue ball milling 15-24h on the multi-directional ball grinding machine;
(c) slurry is poured out, added defoamer at last, obtain the aqueous casting slurry of bismuth titanates after the vacuum outgas.
4. by the preparation method of the described nanometer bismuth titanate powder of claim 3 aqueous casting slurry, the vacuum tightness that it is characterized in that described vacuum outgas is 0.05-0.08MPa.
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| CNB2005101121127A CN100347129C (en) | 2005-12-27 | 2005-12-27 | Nanometer bismuth titanate aqueous casting slurry and preparation method thereof |
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| CN100347129C CN100347129C (en) | 2007-11-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100551874C (en) * | 2007-04-27 | 2009-10-21 | 中国科学院上海硅酸盐研究所 | A kind of method of in type water-based tape casting film being carried out again flow casting molding |
| CN102267812A (en) * | 2011-04-11 | 2011-12-07 | 山东女子学院 | Method for preparing thick membrane by using polycrystal Ca0.4Sr0.6Bi4Ti4O15 nano powder with perovskite structure |
| CN103056958A (en) * | 2012-12-29 | 2013-04-24 | 贵州振华红云电子有限公司 | Method for preparing piezoelectric ceramic piece green compact by using aqueous tape casting |
| CN102101772B (en) * | 2009-12-16 | 2013-08-21 | 佛山市华南精细陶瓷技术研究开发中心 | Water-based casting dielectric ceramic raw belt |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171369A (en) * | 1997-06-26 | 1998-01-28 | 中国科学院固体物理研究所 | Process for preparing nm-class bismuth titanate and its sosoloid |
| US6379813B1 (en) * | 1999-09-17 | 2002-04-30 | S. C. Johnson Commercial Markets, Inc. | Pigmented compositions and articles of manufacture containing same |
| JP2002091313A (en) * | 2000-09-13 | 2002-03-27 | Nitto Denko Corp | Printing sheet and printed sheet |
| CN1290796C (en) * | 2003-11-07 | 2006-12-20 | 四川大学 | Sodium bismuth titanate base nonleaded piezoelectric ceramic |
-
2005
- 2005-12-27 CN CNB2005101121127A patent/CN100347129C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100551874C (en) * | 2007-04-27 | 2009-10-21 | 中国科学院上海硅酸盐研究所 | A kind of method of in type water-based tape casting film being carried out again flow casting molding |
| CN102101772B (en) * | 2009-12-16 | 2013-08-21 | 佛山市华南精细陶瓷技术研究开发中心 | Water-based casting dielectric ceramic raw belt |
| CN102267812A (en) * | 2011-04-11 | 2011-12-07 | 山东女子学院 | Method for preparing thick membrane by using polycrystal Ca0.4Sr0.6Bi4Ti4O15 nano powder with perovskite structure |
| CN103056958A (en) * | 2012-12-29 | 2013-04-24 | 贵州振华红云电子有限公司 | Method for preparing piezoelectric ceramic piece green compact by using aqueous tape casting |
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| CN100347129C (en) | 2007-11-07 |
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Granted publication date: 20071107 Termination date: 20101227 |