CN102898147A - Environment-coordinating method for preparing titanate piezoelectric ceramic powder - Google Patents
Environment-coordinating method for preparing titanate piezoelectric ceramic powder Download PDFInfo
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- CN102898147A CN102898147A CN2012104362801A CN201210436280A CN102898147A CN 102898147 A CN102898147 A CN 102898147A CN 2012104362801 A CN2012104362801 A CN 2012104362801A CN 201210436280 A CN201210436280 A CN 201210436280A CN 102898147 A CN102898147 A CN 102898147A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003980 solgel method Methods 0.000 claims abstract description 31
- 239000004310 lactic acid Substances 0.000 claims abstract description 20
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000011858 nanopowder Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000007613 environmental effect Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 8
- 230000008961 swelling Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000010936 titanium Substances 0.000 claims description 19
- 241001427617 Pyrophorus Species 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003352 sequestering agent Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 230000033228 biological regulation Effects 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- -1 titanate compound Chemical class 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 11
- 238000010532 solid phase synthesis reaction Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical class [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 238000002076 thermal analysis method Methods 0.000 description 1
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical class [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an environment-coordinating method for preparing titanate piezoelectric ceramic powder, and the method is characterized in that lactic acid is chelating agent, swelling agent and pore-forming agent, sol is prepared under the normal temperature by utilizing a sol-gel method, after the pH value is adjusted, the sol is vacuum concentrated or removed with solvent under constant pressure to obtain gel, the gel is processed through unique swelling process and spontaneous combustion way under the temperature of 180 DEG C to 200 DEG C to obtain a nano pyrophoric material, and the pyrophoric material is pre-burned to obtain nano powder under the temperature of 550DEG C to 600DEG C; and the powder is processed through procedures such as granulating, tabletting, plastic releasing and the like to obtain a green sheet, the green sheet is sintered for 1 to 2h under the condition of 950DEG C to 1025DEG C to obtain a ceramic sheet, and the ceramic sheet is polarized in normal-temperature silicon oil to obtain the titanate piezoelectric ceramic powder after standing. The method has important practical significance for traditional piezoelectric ceramic production process to realize high quality, low energy consumption, low cost and environmental friendliness; and meanwhile, an important innovation effect for the titanate compound application field seeking no conglobation and having ultra-large specific surface area can be achieved.
Description
Technical field
The present invention relates to a kind of technology of preparing of titanate piezoelectric ceramic powder, relate in particular to the technology that a kind of water base sol-gel method prepares titanate compound no-agglomeration nano powder.The field that belongs to functional materials and adopt greenization environmental harmony type technology to produce nano-powder.
Background technology
Be found to so far from the titanate piezoceramic material, industrial production adopts traditional solid-phase synthesis always, but its technique has the drawback that is difficult to overcome: component is difficult to homogeneous, ball milling also introduces impurity and the structure deteriorate rate is higher, coarse micron particles, 850 ℃ ~ 900 ℃ powder calcined temperature, 1100 ℃ ~ 1300 ℃ pyroceramic sintering, and all need 2 ~ 5 hours long-time insulation, rigid index request to equipment is higher, during consumption energy consumption, the inaccurate grade of metering that the while high temperature sintering causes the serious volatilization of metal ion to cause is all seriously restricting the quality and performance of finished product piezoelectric ceramics, although the investigator carries out modification and compound to the piezoelectric ceramics of all kinds of systems, but the backwardness of production technology level is determining product index and is not reaching design requirements far away, so seek the standby technology of a kind of new system of all drawbacks that can overcome traditional technology, become focus and the difficult point of this area research.
It is exactly one of focus that sol-gel method prepares piezoelectric ceramic technology, it is as a kind of research technology early, and possess: technique is simple, accurate measurement, the component homogeneous, low-temperature sintering (1050 ℃ ~ 1140 ℃, 2 ~ 3 hours) can be prepared nano-powder, the advantages such as product performance are good, make it become a large focus of research, have potentiality practical, realize the industrialization transition of global piezoelectric ceramics production technology.But in decades, traditional sol-gel method is confined to the experimental phase always, fluctuate, fail to have breakthrough, be difficult to industrialization, tracing it to its cause is: 1. traditional sol-gel method mostly is the alcohol radical sol-gel method, it has adopted a large amount of organic solvent (as: ethanol, ethylene glycol, ethylene glycol monomethyl ether, glycerol etc.) and expensive organic raw material (being mainly carboxylate salt), low cost can't truly be realized, greenization, environment compatibility; 2. colloidal sol desolventizes process and causes serious environmental pollution, the unstable poor operability that causes of colloidal sol of preparation is difficult to practicality, can only be confined to experimental study, but can not large-scale industrialization, cause the production of piezoelectric ceramics so far still to adopt traditional solid-phase synthesis.Therefore explore one and have important Research Significance and using value take green solvent and green material as main sol-gel technology route, especially adopt green resource water to replace the solvent of organic, the environmental harmony of global piezoelectric ceramics production technology is had revolutionary meaning transition.For many years, the related process of sol-gel method of greenization that only had in the world few document and patent report, greenization mainly is that to change organic solvent into single pure water be solvent, organic raw material changes oxide compound and inorganic salt into, but in only minority report, its technique all contains the organic solvent of a great deal of, and water has just served as a kind of medium, fully the realization greenization on the meaning.
Water base sol-the gel process of greenization, mainly refer to: except sequestrant and special material, do not introduce any organic solvent, thereby under single aqueous conditions, prepare stable colloidal sol, colloidal sol can keep stable state in the process that desolventizes, have the characteristics such as easy to operate, easy industrialization.But because water is the stronger material of a kind of polarity, most of organic sequestering agents and water insoluble perhaps are difficult to effectively finish the complexing to metal ion in the solvent of strong polarity, also or the sequestrant costliness impracticable; Although the Citrate trianion method of finding can be under aqueous conditions effective complexation of metal ions, the powder prepared of its technique, more coarse, easy caking etc., the sol-gel method of effect and alcohol radical differs greatly, even if therefore it has researching value, but do not possess practical value.In addition, the titanium source of titanate compound is mainly titanium dioxide, titanyl sulfate, titanium chloride, tetrabutyl titanate etc., although it is balanced that price occupy, they otherwise water insoluble, or meeting water is fast hydrolyzing, generate titanium hydroxide, and then be hydrolyzed to titanium dioxide, be difficult to prepare colloidal sol.Therefore the key that breaks through water base sol-gel process is to seek a kind of special sequestrant, it need possess simultaneously: wetting ability, close titanium source, the directed titanium source that suppresses of energy are hydrolyzed, effectively finish the complexing to many kinds of metal ions, cheap practicality, environmental harmony type, easy to operate, quality product high, this selection to water base sequestrant is to be difficult to together the barrier gone beyond, make a general survey of many in the world achievements in research, do not obtain any breakthrough progress to water base sol-gel process recent decades.
Therefore find a kind of novel water base sequestrant, explore a brand-new water base sol-gel method technology of preparing route, can overcome the critical defect that solid-phase synthesis brings fully, can overcome again the various disadvantages that causes of traditional sol-gel method, and can realize the water base sol-gel process of the greenization on the complete meaning, just become the in the world utmost point difficult point of research.
Summary of the invention
Purpose of the present invention: overcome the defective of traditional solid-phase synthesis and traditional Sol-Gel Preparation Technique, provide a kind of environmental harmony type to prepare the method for titanate piezoelectric ceramic powder.Truly realized the greenization of technique, the environmental harmony type, low cost, low power consuming, excellent operability, practical; Realize the qualitative leap of piezoelectric ceramics technology of preparing, for laying the foundation transition of piezoelectric ceramics industry production technology.
Technical scheme of the present invention is as follows:
A kind of environmental harmony type method for preparing the titanate piezoelectric ceramic powder may further comprise the steps:
(1) adopt the green resource pure water as unique solvent, metal oxide and carbonate are raw material, perhaps metal oxide replaces with nitrate, select hydrofluoric acid or the vitriol oil or nitric acid as solvating agent depending on the difference in titanium source, ammoniacal liquor or urea are neutralizing agent, ammonium nitrate is ignition dope, this ammonium nitrate is introduced by ammoniacal liquor and nitric acid or is added separately, the titanium source is tetrabutyl titanate or metatitanic acid, titanyl sulfate, titanium sulfate, titanium dioxide, titanium tetrachloride one or a combination set of, lactic acid is sequestrant, swelling agent, pore-forming material, adopt water base sol-gel method, prepare at normal temperatures colloidal sol, after colloidal sol is transferred pH, after 80 ℃ ~ 160 ℃ lower vacuum concentration or normal pressure desolventize gel, gel lower obtains the nanometer pyrophorus after through unique bulking process and spontaneous combustion approach at 180 ℃ ~ 200 ℃, pyrophorus gets nano-powder 550 ℃ ~ 600 ℃ lower pre-burnings after 0.5 ~ 1 hour, powder is thin layer micropore shape without reunion, thickness of thin layer＜10nm has larger specific surface area;
(2) get above-mentioned powder, through after the granulation, compressing tablet, plastic removal operation, green sheet was finished sintering in 1 ~ 2 hour under 950 ℃ ~ 1025 ℃ conditions of very low temperature, namely get the ceramic plate that phase composite is single, microtexture is extremely fine and close, grain size is 300nm ~ 800nm approximately, the ceramic plate process is coated with silver, behind the silver ink firing, in normal temperature silicone oil, apply the DC electric field of 1.5 ~ 3.5kV/mm, polarized 10 ~ 20 minutes, the polarization temperature is normal temperature ~ 80 ℃, namely obtains titanate piezoelectric ceramics finished product after leaving standstill.
The present invention has following technique effect:
(1) solvent and raw material are the simplest reagent, have realized greenization, and low cost has overcome the most fatal defective of traditional sol-gel method.
(2) a kind of novel water-based sequestrant-lactic acid of invention, it possesses: wetting ability, close titanium source, Complexation Efficiency is high, cheapness is practical, environmental harmony type, easy to operate, quality product high, has broken through the key obstacle of water base sol-gel process;
(3) adopting lactic acid is sequestrant, makes extremely stable colloidal sol, has overcome traditional colloidal sol factors of instability;
(4) adopting lactic acid is swelling agent and unique bulking process, has realized that the nothing of powder is reunited, and has overcome the serious phenomenon of powder reuniting of solid-phase synthesis and traditional sol-gel method;
(5) adopting lactic acid is pore-forming material and two sections special boring techniques, has realized lamelliform, many micropores effect of powder, has increased greatly the specific surface area of powder;
(6) invented the Trinitarian technology of preparing that lactic acid serves as sequestrant, swelling agent, pore-forming material simultaneously;
(7) powder adopts the ultralow temperature short period of time to finish pre-burning, has overcome the long-time pre-burning of high temperature of solid-phase synthesis, effectively reduces energy consumption; And the fineness of powder crystal grain has surpassed traditional sol-gel method;
(8) sintering temperature and the time of pottery reduce greatly, come from not the reuniting of its powder, thin layer microporous, nanometer, larger specific surface area etc., not only are lower than solid-phase synthesis, also are lower than traditional sol-gel method, fall energy consumption obvious; Also effectively avoid the volatilization problem of metal ion under the high temperature;
(9) density of pottery is high, is higher than solid-phase synthesis; The size of ceramic crystalline grain is less than traditional sol-gel method, and tiny its electric property that makes of the raising of density and crystal grain is excellent;
(10) normal temperature of polarization, has more advantage with respect to solid-phase synthesis and traditional sol-gel method at the low voltage short period of time.
Description of drawings
Fig. 1 is the infrared spectra (IR) of the gel of embodiment 1;
Fig. 2 is the X-diffraction (XRD) of the gel of embodiment 1
Fig. 3 is the XRD of the nanometer pyrophorus of embodiment 1;
Fig. 4, common digital according to (GPJ) for the nanometer pyrophorus of embodiment 1
Fig. 5 is the gel simultaneous thermal analysis instrument (TG-DSC) of embodiment 1;
Fig. 6 is the XRD of 1 hour the powder of 600 ℃ of pre-burnings of embodiment 1;
Fig. 7 is the scanning electron microscope (SEM) of 600 ℃ of powders of embodiment 1,7a-b;
Fig. 8 is traditional sol-gel method BNKLT, the SEM of 600 ℃ of powders, 8a-b;
Fig. 9 is the powder of embodiment 1 XRD at 1 hour pottery of 1000 ℃ of sintering;
Figure 10 is the SEM on the surface of the pottery of embodiment 1,10a-b;
Figure 11 is the SEM of the cross section of the pottery of embodiment 1;
Figure 12 is the IR of the gel of embodiment 2;
Figure 13 is the GPJ of the nanometer pyrophorus of embodiment 2;
Figure 14 is the gel TG-DSC of embodiment 2;
Figure 15 is the XRD of 1 hour the powder of 600 ℃ of pre-burnings of embodiment 2;
Figure 16 is the SEM of 600 ℃ of powders of embodiment 2,16a-b;
Figure 17 is the powder of embodiment 2 XRD at 1 hour pottery of 1000 ℃ of sintering;
Figure 18 is the SEM on the surface of the pottery of embodiment 2,18a-b;
Figure 19 is the SEM of the cross section of the pottery of embodiment 2;
Figure 20 is the GPJ of the nanometer pyrophorus of embodiment 3;
Figure 21 is the SEM of 600 ℃ of powders of embodiment 3,21a-b;
Figure 22 is the gel TG-DSC of embodiment 4;
Figure 23 is the XRD of 1 hour the powder of 550 ℃ of pre-burnings of embodiment 4;
Figure 24 is the SEM of 550 ℃ of powders of embodiment 4,24a-b;
Figure 25 is the powder of embodiment 4 XRD at 1 hour pottery of 1000 ℃ of sintering;
Because being all titanate compound, preparation technology is identical, embodiment 3, embodiment 4 and embodiment 1, embodiment 2 many similar parts, and concrete data plot is not enumerated one by one, but does not represent content of the present invention is done any restriction.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The chelating of lactic acid, Trinitarian technology of preparing expanded, pore-creating are applied to the preparation of other compound, with being considered as in the scope of the present invention.
Raw material of the present invention can be that oxide compound and nitrate and carbonate etc. are multiple, swelling agent lactic acid is necessary, gel must be through obtaining the nano-powder without reunion after unique bulking process pre-burning, powder can go out pottery by sintering through subsequent technique between low-temperature short-time.
Below be to the present invention is directed to several titanate piezoelectrics, adopt water base sol-gel method, the example that the process bulking process is prepared.
Embodiment 1
Specific embodiments of the invention 1, water base sol-gel method prepares Bi
0.5(Na
0.7K
0.2Li
0.1)
0.5TiO
3The step of (writing a Chinese character in simplified form BNKLT) nano-powder and piezoelectric ceramics is as follows:
(1) collosol concentration is C
Sol-gel-Ti 4+=0.15 ~ 0.25mol/L, 20 gram samples (in the quality of the finished product BNKLT);
(2) after the accurate stoichiometry, get 10.98 gram Bi
2O
3(purity 99.8%) is dissolved in the 45ml concentrated nitric acid also short molten, to the transparent rear cooling of achromaticity and clarification, again with 1.75 gram Na
2CO
3(purity 99.8%), 0.66 gram K
2CO
3(purity 99.0%), 0.18 gram Li
2CO
3The aqueous solution of (purity 97.0%) adds wherein, obtains A liquid;
(3) ratio by lactic acid and the amount of substance of tetrabutyl titanate is 2.0 ~ 6.0, get 50ml lactic acid (purity 85 ~ 90%) and be added on 32.49 gram tetrabutyl titanate (purity 98.5%, density ≈ 1.0) in, after fully stirring, add again 50 ~ 100ml water, stir to yellow clear, obtain B liquid;
(4) under the normal temperature, B liquid is added behind the A liquid to get mixed solution (can select to add 2 ~ 5 gram ammonium nitrate or do not add), transfer pH=3.0 ~ 5.0 with ammoniacal liquor, and mend that to add water to the colloidal sol cumulative volume be 500ml, mixed solution can be yellow clear after continuous heating stirred, get water base stable sol after the of short duration ageing, Tyndall effect is obvious;
(5) under 140 ℃, after normal pressure desolventizes, get the opaque gel of milk yellow, IR shows that the gel space reticulated structure is completed into.
(6) gel was placed under 180 ℃ the environment pre-treatment 30 minutes, make the expanded rear spontaneous combustion of its rear rapid large volume of being heated, namely get huge skeleton shape and the nanometer pyrophorus of grey black of the homogeneous of metalluster is arranged;
(7) get pyrophorus, 600 ℃ of pre-burnings 1 hour, obtain the BNKLT powder, SEM shows that it does not reunite, is thin layer micropore shape, bed thickness＜10nm, has larger specific surface area; XRD shows that it is single perovskite structure, is 10 ~ 18nm by the grain size of its powder of figure spectrum estimation;
(8) get the powder granulation, make green sheet under the pressure of 12MPa ~ 14MPa, the base sheet was 950 ℃ ~ 1025 ℃ sintering 1 ~ 2 hour, and the XRD figure spectrum shows to get the single ceramic plate of phase composite; SEM shows that its ceramic crystalline grain size is 300nm ~ 800nm, possesses perfect how much patterns, and cross section SEM figure shows that its density is very high;
(9) ceramic plate behind the silver ink firing, in the normal temperature silicone oil, leaves standstill to get the finished product piezoelectric ceramics through being coated with silver after polarizing under the volts DS of 1.5 ~ 3.5kV/mm 10 ~ 20 minutes, according to ieee standard test electric property.
Specific embodiments of the invention 2, water base sol-gel method prepares CeO
2-[0.998Bi
0.5(Na
0.7K
0.2Li
0.1)
0.5TiO
3-0.002BiFeO
3] (write a Chinese character in simplified form: C-BNKLT-BF) step of nano-powder and piezoelectric ceramics is as follows:
(1) collosol concentration is C
Sol-gel-Ti 4+=0.15 ~ 0.25mol/L, 20 gram samples (in the quality of the finished product C-BNKLT-BF);
(2) after the accurate stoichiometry, with 0.20 gram CeO
2(purity 99.0%) and 10.88 gram Bi
2O
3(purity 99.8%) is dissolved in respectively in 10ml and the 45ml concentrated nitric acid also hot short molten, to CeO
2The hydrogen peroxide of middle dropping denier, and fully boil, all to the transparent rear cooling of achromaticity and clarification, again with 0.08 gram nine water iron nitrates (purity 98.5%), 1.73 gram Na
2CO
3(purity 99.8%), 0.65 gram K
2CO
3(purity 99.0%), 0.18 gram Li
2CO
3The aqueous solution of (purity 97.0%) adds wherein, obtains A liquid;
(3) ratio by lactic acid and the amount of substance of tetrabutyl titanate is 2.0 ~ 6.0, get 50ml lactic acid (purity 85 ~ 90%) and be added on 32.07 gram tetrabutyl titanate (purity 98.5%, density ≈ 1.0) in, after fully stirring, add again 50 ~ 100ml water, stir to yellow clear, obtain B liquid;
(4) under the normal temperature, B liquid is added behind the A liquid to get mixed solution (selectivity adds 2 ~ 5 gram ammonium nitrate or do not add), transfer pH=3.0 ~ 5.0 with ammoniacal liquor, and mend that to add water to the colloidal sol cumulative volume be 500ml, lasting stirring is yellow clear to mixed solution afterwards, gets colloidal sol after the ageing;
Under (5) 140 ℃, after normal pressure desolventizes, get gel;
(6) gel was placed under 180 ℃ the environment pre-treatment 30 minutes, after the expanded spontaneous combustion, namely get huge skeleton shape and the nanometer pyrophorus of grey black of the homogeneous of metalluster is arranged;
(7) get pyrophorus, 600 ℃ of pre-burnings 1 hour, obtain C-BNKLT-BF without the nano-powder of reuniting;
(8) get the powder granulation, compressing tablet etc., base sheet get single, the fine and close ceramic plate of phase composite 950 ℃ ~ 1025 ℃ sintering 1 ~ 2 hour;
(9) ceramic plate behind the silver ink firing, in the normal temperature silicone oil, leaves standstill to get the finished product piezoelectric ceramics through being coated with silver after polarizing under the volts DS of 1.5 ~ 3.5kV/mm 10 ~ 20 minutes, the test electric property.
Embodiment 3
Specific embodiments of the invention 3, water base sol-gel method preparation [0.94 Bi
0.5(Na
0.7K
0.2Li
0.1)
0.5TiO
3-0.06BaTiO
3]-BiFeO
3The step of (writing a Chinese character in simplified form 0.94BNKLT-0.06BT-BF) is as follows:
(1) collosol concentration is C
Sol-gel-Ti 4+=0.15 ~ 0.25mol/L, 20 gram samples (in the quality of the finished product 0.94BNKLT-0.06BT-BF);
(2) after the accurate stoichiometry, to 1.11 gram BaCO
3Add 5ml water in (purity 99.8%), and then to wherein dripping concentrated nitric acid till just clarify water white transparency, get 10.27 gram Bi
2O
3(purity 99.8%) is dissolved in the 45ml concentrated nitric acid also hot short molten, to the transparent rear cooling of achromaticity and clarification, mixes above-mentioned two liquid, again with 0.08 gram nine water iron nitrates (purity 98.5%), and 1.60 gram Na
2CO
3(purity 99.8%), 0.61 gram K
2CO
3(purity 99.0%), 0.17 gram Li
2CO
3The aqueous solution of (purity 97.0%) adds wherein, obtains A liquid;
(3) ratio by lactic acid and the amount of substance of tetrabutyl titanate is 2.0 ~ 6.0, get 50ml lactic acid (purity 85 ~ 90%) and be added on 32.21 gram tetrabutyl titanate (purity 98.5%, density ≈ 1.0) in, after the stirring, add 50 ~ 100ml water, stir to yellow clear, obtain B liquid;
(4) under the normal temperature, B liquid is added behind the A liquid to get mixed solution, transfers pH=3.0 ~ 5.0 with ammoniacal liquor, and mend that to add water to the colloidal sol cumulative volume be 500ml, be yellow clear to mixed solution after continuing to stir, after the ageing colloidal sol;
(5) under 140 ℃, after normal pressure desolventizes, get gel;
(6) gel is placed under 200 ℃ the environment pre-treatment 30 minutes, after the expanded spontaneous combustion, namely get the nanometer pyrophorus;
(7) get pyrophorus, 600 ℃ of pre-burnings 1 hour, obtain 0.94BNKLT-0.06BT-BF without the nano-powder of reuniting;
(8) get the powder granulation, compressing tablet etc., base sheet get single, the fine and close ceramic plate of phase composite 950 ℃ ~ 1025 ℃ sintering 1 ~ 2 hour;
(9) ceramic plate behind the silver ink firing, in the normal temperature silicone oil, leaves standstill to get the finished product piezoelectric ceramics through being coated with silver after polarizing under the volts DS of 1.5 ~ 3.5kV/mm 10 ~ 20 minutes, the test electric property.
Specific embodiments of the invention 4, water base sol-gel method prepare Pb (Zr
0.52Ti
0.48) O
3The step of (writing a Chinese character in simplified form PZT) is as follows:
(1) collosol concentration is C
Sol-gel-Ti 4+=0.15 ~ 0.25mol/L, 20 gram samples (in the quality of the finished product PZT);
(2) behind the accurate-metering, 14.78 gram tri-lead tetroxides (purity 95.0%) are dissolved in the 45ml concentrated nitric acid, short molten, and drip the hydrogen peroxide of 1.2 ~ 1.5ml, fully boil 30min, cool off to clear, the aqueous solution with 13.85 grams, five water zirconium nitrates (99.0%) adds wherein again, obtains A liquid;
(3) ratio by lactic acid and the amount of substance of tetrabutyl titanate is 2.0 ~ 6.0, get 50ml lactic acid (purity 85 ~ 90%) and be added on 10.19 gram tetrabutyl titanate (purity 98.5%, density ≈ 1.0) in, after the stirring, add 50 ~ 100ml water, stir to yellow clear, obtain B liquid;
(4) under the normal temperature, B liquid is added behind the A liquid to get mixed solution, transfers pH=3.0 ~ 5.0 with ammoniacal liquor, and mend that to add water to the colloidal sol cumulative volume be 500ml, be yellow clear to mixed solution after continuing to stir, after the ageing colloidal sol;
(5) under 140 ℃, after normal pressure desolventizes, get gel;
(6) gel is placed under the air ambient, slowly heat up (if adopt rapidly thermal treatment, may cause confined explosion, cause pyrophorus to flash) after the expanded spontaneous combustion, namely gets the nanometer pyrophorus to 200 ℃ of lower pre-treatment 30 minutes;
(7) get pyrophorus, 550 ℃ of pre-burnings 1 hour, namely get PZT without the nano-powder of reuniting;
(8) get the powder granulation, compressing tablet etc., base sheet get single, the fine and close ceramic plate of phase composite 950 ℃ ~ 1025 ℃ sintering 1 ~ 2 hour;
(9) ceramic plate is through being coated with silver, behind the silver ink firing, under 60 ~ 80 ℃, in the silicone oil, leaves standstill to get the finished product piezoelectric ceramics after polarizing under the volts DS of 1.5 ~ 3.5kV/mm 10 ~ 20 minutes, the test electric property.
The present invention, obtain experimental data and measuring result and experimental phenomena by above four embodiment, show and to compare traditional solid-phase synthesis and traditional sol-gel method by water base sol-gel method the two has more: low cost, low temperature is synthetic, excellent operability, greenization, environment compatibility, the advantages such as low condition polarization.
Electrical performance testing
Following table is for adopting the partial-titanium hydrochlorate piezoelectric ceramics performance table of the present invention's preparation:
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (6)
1. an environmental harmony type method for preparing the titanate piezoelectric ceramic powder is characterized in that, may further comprise the steps:
(1) adopt the green resource pure water as unique solvent, metal oxide and carbonate are raw material, perhaps metal oxide replaces with nitrate, select hydrofluoric acid or the vitriol oil or nitric acid as solvating agent depending on the difference in titanium source, ammoniacal liquor or urea are neutralizing agent, ammonium nitrate is ignition dope, this ammonium nitrate is introduced by ammoniacal liquor and nitric acid or is added separately, the titanium source is tetrabutyl titanate or metatitanic acid, titanyl sulfate, titanium sulfate, titanium dioxide, titanium tetrachloride one or a combination set of, lactic acid is sequestrant, swelling agent, pore-forming material, adopt water base sol-gel method, prepare at normal temperatures colloidal sol, after colloidal sol is transferred pH, after 80 ℃ ~ 160 ℃ lower vacuum concentration or normal pressure desolventize gel, gel lower obtains the nanometer pyrophorus after through unique bulking process and spontaneous combustion approach at 180 ℃ ~ 200 ℃, pyrophorus gets nano-powder 550 ℃ ~ 600 ℃ lower pre-burnings after 0.5 ~ 1 hour, powder is thin layer micropore shape without reunion, thickness of thin layer＜10nm has larger specific surface area;
(2) get above-mentioned powder, through after the granulation, compressing tablet, plastic removal operation, green sheet was finished sintering in 1 ~ 2 hour under 950 ℃ ~ 1025 ℃ conditions of very low temperature, namely get the ceramic plate that phase composite is single, microtexture is extremely fine and close, grain size is 300nm ~ 800nm approximately, the ceramic plate process is coated with silver, behind the silver ink firing, in normal temperature silicone oil, apply the DC electric field of 1.5 ~ 3.5kV/mm, polarized 10 ~ 20 minutes, the polarization temperature is normal temperature ~ 80 ℃, namely obtains titanate piezoelectric ceramics finished product after leaving standstill.
2. method claimed in claim 1 is characterized in that, lactic acid and Ti
4+The ratio of amount of substance be 2.0 ~ 6.0, the pH=3.0 of colloidal sol ~ 5.0.
3. method claimed in claim 1 is characterized in that, the water content of water base sol-gel process has larger regulation range, V(water, volumeter): V (lactic acid, volumeter) 〉=1.0, amount of water is not established the upper limit.
4. method claimed in claim 1, it is characterized in that, the bulking process that adopts is: its gel is 180 ℃ ~ 200 ℃ lower pre-treatment after 30 minutes, make it obtain moment spontaneous combustion behind decades of times and the larger expanded volume, generate huge skeleton shape and the nanometer pyrophorus of grey black of the homogeneous of metalluster is arranged; Gel adopts to be done or wet two states.
5. method claimed in claim 1 is characterized in that, described titanate is MTiO
3, M be can with TiO
3 2-Salify and have the metal ion of perovskite structure, M is single metal ion, or the complex body of two kinds and two or more metal ions, the source of its metallic element can be oxide compound, carbonate, nitrate.
6. method claimed in claim 1, it is characterized in that, described method is applicable to prepare multiple titanate nano-ceramic powder without reuniting, perhaps be used for the compound of compound, the tungsten bronze structure of the base metal niobate structure of other non-titanate structure, the preparation of bismuth laminated compound powder, be used for Bi
0.5Na
0.5TiO
3, Bi
0.5K
0.5TiO
3, Bi
0.5Na
0.5TiO
3-Bi
0.5K
0.5TiO
3, Bi
0.5Na
0.5TiO
3-Bi
0.5K
0.5TiO
3-BaTiO
3, Bi
0.5(Na
1-x-yK
yLi
x)
0.5TiO
3, Pb (Zr
xTi
1-x) O
3, BaTiO
3, (Ba, Sr) TiO
3, (Ba, Ca) (Ti, Zr) O
3, Na
0.5K
0.5NbO
3, (Na
0.5K
0.5)
0.94Li
0.06NbO
3, Na
0.52K
0.48NbO
3(Na
0.52K
0.48)
0.94Li
0.06NbO
3, Bi
4Ti
3O
12, SrBi
4Ti
4O
15, Sr
0.5Ba
0.5Nb
2O
6, (Sr
0.5Ba
0.5)
2NaNb
5O
15, Sr
1.9Ca
0.1NaNb
5O
15, Sr
1.8Ca
0.1(Bi
0.5Na
0.5)
0.1NaNb
5O
15, Sr
1.8Ca
0.1(Bi
0.5K
0.5)
0.1NaNb
5O
15, Sr
1.8Ca
0.1(Bi
0.5Li
0.5)
0.1NaNb
5O
15The preparation of compound nano powder comprises for the preparation of one or more of its replacement, doping, modification and compound system.
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| CN111348924A (en) * | 2018-12-20 | 2020-06-30 | 攀枝花学院 | Refractory and corrosion-resistant material for resisting titanium melt and preparation method and application thereof |
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