CN105669193A - K-Na-Li niobate barium titanate-based lead-free piezoelectric ceramic and low-temperature sintering preparation method thereof - Google Patents
K-Na-Li niobate barium titanate-based lead-free piezoelectric ceramic and low-temperature sintering preparation method thereof Download PDFInfo
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Abstract
The invention discloses K-Na-Li niobate barium titanate-based lead-free piezoelectric ceramic and a low-temperature sintering preparation method thereof and belongs to the field of environment-friendly functional ceramic materials. The K-Na-Li niobate barium titanate-based lead-free piezoelectric ceramic is (1-x)(Na<a>K<b>Li<c>)NbO<3>-xBaTiO<3>-yMQ, wherein a, b, c, x and y are molar fractions, 0.30 <= a <= 0.80, 0.30 <= b <= 0.80, 0.00 <= c <= 0.30, 0.01 <= x <= 0.25, and 0.00 <= y <= 0.35. The preparation method includes the steps of weighting raw materials, ball-milling and mixing the raw materials, roasting the mixed raw materials, performing secondary ball milling, performing granulation and moulding, performing glue removal and sintering the piezoelectric ceramic. The K-Na-Li niobate barium titanate-based lead-free piezoelectric ceramic is prepared within a low temperature range of 900-1000 DEG C and has excellent performance.
Description
Technical field
The invention belongs to ceramic material field, in particular it relates to a kind of potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics and low-temperature melt producing method thereof.
Background technology
Piezoelectric ceramics is as a kind of important functional material, with the performance of its uniqueness, has obtained in fields such as electronic information, transducer, sensor, actuator, Non-Destructive Testing and mechanicss of communication and has been widely applied. That large-scale use is lead zirconate titanate Pb (Zr, Ti) O in the market3(being called for short PZT) base piezoelectric ceramic, owing to its lead tolerance reaches more than 60wt%, in preparation, uses, and in waste treatment process, environment and human health is brought very big infringement. Along with raising and the social sustainable development implementation of people's environmental consciousness, the piezoelectric ceramics of development environment friendly becomes the focus of piezoelectric research field.
Researching and developing field at leadless piezoelectric ceramics, countries in the world have all carried out substantial amounts of work, and achieve the progress of stage. At present, research reports that maximum leadless piezoelectric ceramics systems mainly has Barium metatitanate. (BT) base pottery, potassium-sodium niobate (NKN) base pottery, bismuth-sodium titanate (BNT) base pottery ceramic, bismuth laminated and tungsten bronze structure ceramic etc. In above-mentioned several leadless piezoelectric ceramics systems, NKN base and BT base piezoelectric ceramic have the piezoelectric property of excellence because of it, are subject to the extensive concern of domestic and international research worker, are acknowledged as most rising leadless piezoelectric ceramics. But up to now, the leadless piezoelectric ceramics of the unitary system of development is still within test chamber development, it is difficult to meet the needs of practical application.
Recently, in piezoelectric ceramics potassium-sodium niobate lithium barium titanate base piezoelectric ceramic solid solution research, also has certain development. NKN pottery and BT pottery are without any toxic element, and are all perovskite structure, and therefore NKN-BT potassium-sodium niobate lithium barium titanate base piezoelectric ceramic solid solution receives the concern of people. But the NKN-BT potassium-sodium niobate lithium barium titanate base piezoelectric ceramic sintering temperature of research is more than 1100 DEG C at present, at this temperature, K, Na volatilization is serious, the piezoelectric property of the potassium-sodium niobate lithium barium phthalate base solid solution of preparation is unsatisfactory, and therefore sintering preparation NKN-BT potassium-sodium niobate lithium barium titanate based ceramic solid solution is significant at low temperatures.And according to, in the Patents found, being showed no the report by carrying out doping reduction pressureless sintering temperature at NKN-BT potassium-sodium niobate lithium barium titanate based ceramic.
Summary of the invention
High for sintering temperature in current preparation method, component controls difficulty, material property is not good waits deficiency, the invention reside in a kind of potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics of offer and low-temperature melt producing method thereof, and the pottery prepared has good piezoelectric property.
The present invention adopts traditional normal pressure-sintered technique, has synthesized NKN-BT based leadless piezoelectric ceramics, lower than currently reported sintering temperature in sintering range 900～1000 DEG C relatively low. The one-tenth of this pottery is grouped into useful chemical formula and is expressed as: (1-x) (NaaKbLic)NbO3-xBaTiO3-yMQ, in formula, M is metallic element, and Q is O or CO3 2-Namely, MQ is metal-oxide or metal carbonate, described M is at least one in copper, manganese, zinc, magnesium, ferrum, calcium, zirconium, lanthanum, strontium, barium, antimony, tantalum and tungsten, and a, b, c, x and y all represent molar fraction, and the scope of numerical value is respectively as follows: 0.30≤a≤0.80,0.30≤b≤0.80,0.00≤c≤0.30,0.01≤x≤0.25,0.00≤y≤0.35.
Low-temperature sintering of the present invention prepares the method for above-mentioned potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics, comprises the following steps:
(1) by raw material by (1-x) (NaaKbLic)NbO3-xBaTiO3The proportioning of-yMQ is calculated, weighs dispensing, ball milling 2～48 hours, obtains dry powder after drying;
(2) dry powder step (1) obtained carries out roasting at 750～900 DEG C, is incubated 2～12 hours, carries out chemosynthesis;
(3) powder body after step (2) roasting is carried out secondary ball milling;
(4) by the powder body after step (3) secondary ball milling, bonding agent, pelletize of sieving are added;
(5) powder after step (4) pelletize is put into mould inner pressure and make type;
(6) biscuit of ceramics after step (5) molding is carried out binder removal at 500～650 DEG C;
(7) ceramic green sheet after step (6) binder removal is sintered 2～6 hours at 900～1000 DEG C, obtains leadless piezoelectric ceramics sheet.
Preparation in accordance with the present invention, uses dehydrated alcohol as ball-milling medium in step (1) or (3), wherein, the consumption of dehydrated alcohol is the 60%～100% of raw material or powder body (i.e. ball milling raw material) gross mass.
Preparation in accordance with the present invention, the polyvinyl alcohol water solution that bonding agent is 5wt%～10wt% added in step (4); Materials are the 5%～15% of raw material gross mass; 60～80 mesh sieves crossed by the powder adding bonding agent.
Preparation in accordance with the present invention, in the temperature-rise period before step (7) described sintering, below 800 DEG C, heating rate is 100～200 DEG C/h; More than 800 DEG C heating rates are 40～80 DEG C/h.
The heating process of the present invention can use arbitrary firing equipment that can realize the present invention well known in the art, such as but not limited to resistance furnace, batch-type furnace and roaster etc., in order to make heating in the leadless piezoelectric ceramics preparation method of the present invention or roasting reach more excellent effect, present invention preferably uses program control batch-type furnace and be heated or roasting.
Preparation in accordance with the present invention, can also be fired Electrode treatment further to the leadless piezoelectric ceramics sheet of preparation, specifically include following steps:
(8) undertaken two-sided being polished to 1mm thickness by the leadless piezoelectric ceramics sheet that step (7) in leadless piezoelectric ceramics piece preparation method of the present invention prepares, Double-side brush fires silver electrode at 700～750 DEG C after silver slurry;
(9) potsherd after upper electrode is put in the silicone oil of 100～200 DEG C and polarize, after placing 24 hours, carry out electrical performance testing.
In above-mentioned steps (9), it is preferable that described polarizing voltage is 3～5kV/mm; Polarization time is 20～60min.
Specifically, as a preference, the low-temperature sintering of the present invention is prepared the technical process of potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics and prepares silver electrode and electrode polarization process is as follows:
(1) by raw material by (1-x) (NaaKbLic)NbO3-xBaTiO3The proportioning of-yMQ carries out weighing dispensing; Described raw material can be such as Na2CO3、K2CO3、BaCO3、TiO2、Nb2O5、CuO、MnO2、MnCO3、CaCO3、ZnO、Li2CO3And ZrO2Composition;
(2) powder after preparing is put in ball grinder, and with dehydrated alcohol as ball-milling medium, with planetary ball mill ball mill mixing 2～48 hours, rotating speed was 200～400 turns/min;
(3) batch mixing after ball milling is put in air dry oven, after drying under 80 DEG C of conditions, obtains dry powder;
(4) dry powder obtained is put into continuous warming to 750～900 DEG C in program control batch-type furnace and carries out roasting, be incubated 2～12 hours;
(5) ball grinder is put in the material grinding after roasting, add dehydrated alcohol, carry out secondary ball milling;
(6), after the powder drying after secondary ball milling, the polyvinyl alcohol water solution adding 5～10wt% carries out pelletize as bonding agent, crosses 60～80 mesh sieves;
(7) mould put into by the powder after pelletize, uses hydraulic press compressing under 100～300Mpa, obtains leadless piezoelectric ceramics biscuit;
(8) biscuit of ceramics after molding is put in program control batch-type furnace, at 500～650 DEG C of binder removal 30～90min;
(9) ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2～6h at 900～1000 DEG C, obtains the potsherd of densification;
(10) carry out the potsherd that obtains of sintering two-sided being polished to 1mm thickness on 800 order sand paper, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode; Potsherd after upper electrode being put in the silicone oil of 100～200 DEG C and polarize, polarizing voltage is 3～5kV/mm; Polarization time is 20～60min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Raw material of the present invention can be according to (1-x) (NaaKbLic)NbO3-xBaTiO3The proportioning of-yMQ prepares any salt or the oxide of leadless piezoelectric ceramics of the present invention, especially the oxide of Na, K, Li and metal M or carbonate. Raw material of the present invention all can be commercial, and as most preferred, raw material of the present invention can be adopt commercial Na2CO3、K2CO3、BaCO3、TiO2、Li2CO3、Nb2O5For raw material, with commercial CuO, MnO2、MnCO3、CaCO3, ZnO and ZrO2Deng for adding ingredient.
It is an advantage of the current invention that by the sintering temperature effectively reducing a kind of novel potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics of adulterating, in the low temperature range of 900～1000 DEG C, synthesized the ceramics sample of function admirable, piezoelectric constant d33Being not less than 140pC/N, electromechanical coupling factor Kp reaches 10%-50%.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that sample is stacked in sintering furnace.
Accompanying drawing labelling
1, powder 2, ceramic green sheet 3, alumina wafer 4, alumina crucible
Detailed description of the invention
Being listed below the preferred embodiment of the present invention, it is used only as explanation of the invention rather than restriction.
Na used herein2CO3、K2CO3、BaCO3、TiO2、Nb2O5、CuO、ZnO、Li2CO3、ZrO2It is commercially available Deng raw material.
Embodiment 1
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), ZnO (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) are raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.97 (Na0.353K0.767)NbO3-0.03BaTiO3-0.106ZnO carries out dispensing, puts in ball grinder by the raw material prepared, and addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 350 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash.Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; As it is shown in figure 1, the ceramic green sheet 2 after binder removal is placed on sprinkled with, on the alumina wafer 3 of powder after roasting 1, building with alumina crucible 4, around mouth of pot, sprinkle the powder 1 after roasting, be sintered 2h furnace cooling to room temperature at 960 DEG C, obtain potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 2
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%) is raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.97 (Na0.387K0.721Li0.049)NbO3-0.03BaTiO3Carrying out dispensing, put in ball grinder by the raw material prepared, addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 250 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash. Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30mim at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 3
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), MgO (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) are raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.95 (Na0.367K0.741Li0.056)NbO3-0.05BaTiO3Carrying out dispensing, put in ball grinder by the raw material prepared, addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 300 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash.Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 4
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), ZnO (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) are raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.97 (Na0.353K0.767Li0.041)NbO3-0.03BaTiO3-0.106ZnO carries out dispensing, puts in ball grinder by the raw material prepared, and addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 350 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash. Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; As it is shown in figure 1, the ceramic green sheet 2 after binder removal is placed on sprinkled with, on the alumina wafer 3 of powder after roasting 1, building with alumina crucible 4, around mouth of pot, sprinkle the powder 1 after roasting, be sintered 2h furnace cooling to room temperature at 960 DEG C, obtain potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 5
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), CuO (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) are raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.97 (Na0.387K0.721Li0.049)NbO3-0.03BaTiO3-0.121CuO carries out dispensing, puts in ball grinder by the raw material prepared, and addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 250 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash.Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30mim at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 6
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), MgO (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) are raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.95 (Na0.367K0.741Li0.056)NbO3-0.05BaTiO3-0.118MgO carries out dispensing, puts in ball grinder by the raw material prepared, and addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 300 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash. Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 7
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), MgCO3(Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) is raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.96 (Na0.316K0.692Li0.052)NbO3-0.04BaTiO3-0.115MgCO3Carrying out dispensing, put in ball grinder by the raw material prepared, addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 200 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash.Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 8
With commercially available K2CO3(Beijing chemical reagent factory, purity > 99.0%), Na2CO3(Beijing chemical reagent factory, purity > 99.8%), BaCO3(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), TiO2(Shanghai Inst of Chemical Reagent, spectroscopic pure), Li2CO3(Beijing chemical reagent factory, purity > 99.0%), Nb2O5(Yifeng, Jiangxi Gui Zutan niobium company limited, purity > 99.9%), MnO2(Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure) is raw material, raw material is placed in program control drying baker and dries 12 hours, according to chemical formula 0.96 (Na0.426K0.575Li0.061)NbO3-0.04BaTiO3-0.216MnO2Carrying out dispensing, put in ball grinder by the raw material prepared, addition dehydrated alcohol is ball-milling medium, and with planetary ball mill batch mixing 6 hours, rotating speed was 400 turns/min, and mixed slurry is put in air dry oven and dried at 80 DEG C, obtains dry mash. Dry powder is put in program control batch-type furnace, be incubated 4 hours at 750 DEG C, carry out chemosynthesis. Powder body after synthesis grinds puts into ball grinder, adds dehydrated alcohol, carries out secondary ball milling 4 hours, and rotational speed of ball-mill is 300 turns/min. Powder body after secondary ball milling adds the polyvinyl alcohol water solution of 5wt% as bonding agent after drying, and after mix homogeneously, crosses 80 mesh sieves, then powder is put into mould, uses hydraulic press compressing under 100Mpa, obtains biscuit of ceramics. Biscuit of ceramics after molding is put in program control batch-type furnace, at 500 DEG C of binder removal 30min; Ceramic green sheet after binder removal is placed on sprinkled with on the alumina wafer of powder after roasting, builds with alumina crucible, sprinkles the powder after roasting around mouth of pot, is sintered 2h furnace cooling to room temperature at 960 DEG C, obtains potsherd. Thick to 1mm with 800 order sand paper carry out two-sided polishing potsherd, Double-side brush is incubated 30min at 750 DEG C after silver slurry and fires silver electrode. Potsherd after upper electrode being put in the silicone oil of 100 DEG C and polarize, polarizing voltage is 3kV/mm, and the polarization time is 20min. Potsherd after polarization carries out electrical performance testing after placing 24 hours.
Embodiment 9
Potsherd electrode after polarization obtained by embodiment 1-8 is carried out piezoelectric property test. Dielectric properties are tested with 4294A type precise impedance analyser, and with the electromechanical coupling factor Kp of resonance-antiresonance method calculating sample, with ZJ-3AN type quasistatic d33The piezoelectric property of measuring instrument test sample.
The electric property of various embodiments above preparation pottery is as shown in table 1.
The electrical performance testing result of table 1 potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics
| d33(pC/N) | Kp (%) | ε33/ε0 | tanδ | Tc(℃) | |
| Embodiment 1 | 156 | 19 | 871 | 0.057 | 305 |
| Embodiment 2 | 151 | 17 | 855 | 0.051 | 302 |
| Embodiment 3 | 142 | 15 | 812 | 0.053 | 307 |
| Embodiment 4 | 223 | 32 | 1058 | 0.039 | 318 |
| Embodiment 5 | 216 | 29 | 1150 | 0.047 | 326 |
| Embodiment 6 | 205 | 27 | 1003 | 0.046 | 351 |
| Embodiment 7 | 231 | 36 | 1207 | 0.038 | 309 |
| Embodiment 8 | 191 | 26 | 989 | 0.046 | 306 |
The present invention sinters the potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics of preparation under not higher than 1000 DEG C of conditions and has excellent electric property, piezoelectric constant d33Being not less than 140pC/N, Curie temperature Tc reaches more than 300 DEG C.
Certainly; the present invention can also have various embodiments; when without departing substantially from present invention spirit and essence thereof; those of ordinary skill in the art can make various corresponding change and modification according to disclosure of the invention, but these change accordingly and deformation all should belong to the scope of the claims appended by the present invention.
Claims (10)
1. a potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics, it is characterised in that the constituent of described potassium-sodium niobate lithium barium titanate-based lead-free piezoelectric ceramics is (1-x) (NaaKbLic)NbO3-xBaTiO3-yMQ, in formula, M is metallic element, and Q is O or CO3 2-; A, b, c, x and y all represent molar fraction, and the scope of numerical value is respectively as follows: 0.30≤a≤0.80,0.30≤b≤0.80,0.00≤c≤0.30,0.01≤x≤0.25,0.00≤y≤0.35.
2. leadless piezoelectric ceramics according to claim 1, it is characterised in that described M is one or more in copper, manganese, zinc, magnesium, ferrum, calcium, zirconium, lanthanum, strontium, barium, antimony, tantalum and tungsten.
3. a preparation method for leadless piezoelectric ceramics described in claim 1 or 2, comprises the following steps:
(1) by raw material by (1-x) (NaaKbLic)NbO3-xBaTiO3The proportioning of-yMQ is calculated, weighs dispensing, ball milling 2～48 hours, obtains dry powder after drying;
(2) dry powder step (1) obtained carries out roasting at 750～900 DEG C, is incubated 2～12 hours, carries out chemosynthesis;
(3) powder body after step (2) roasting is carried out secondary ball milling;
(4) by the powder body after step (3) secondary ball milling, bonding agent, pelletize of sieving are added;
(5) powder after step (4) pelletize is put into mould inner pressure and make type;
(6) biscuit of ceramics after step (5) molding is carried out binder removal at 500～650 DEG C;
(7) ceramic green sheet after step (6) binder removal is sintered 2～6 hours at 900～1000 DEG C, obtains leadless piezoelectric ceramics sheet.
4. preparation method according to claim 3, it is characterised in that use dehydrated alcohol as ball-milling medium in step (1) or (3).
5. preparation method according to claim 4, it is characterised in that in step (1) or (3), the consumption of dehydrated alcohol is the 60%～100% of ball milling raw material gross mass.
6. preparation method according to claim 4, it is characterised in that the polyvinyl alcohol water solution that bonding agent is 5wt%～10wt% added in step (4); Materials are the 5%～15% of raw material gross mass.
7. preparation method according to claim 4, it is characterised in that 60～80 mesh sieves crossed by the powder adding bonding agent in step (4).
8. preparation method according to claim 3, it is characterised in that in the temperature-rise period of step (7) described sintering, below 800 DEG C, heating rate is 100～200 DEG C/h; More than 800 DEG C heating rates are 40～80 DEG C/h.
9. preparation method according to claim 3, it is characterised in that further comprising the steps of:
(8) undertaken two-sided being polished to 1mm thickness by the leadless piezoelectric ceramics sheet that step (7) prepares, Double-side brush fires silver electrode at 700～750 DEG C after silver slurry;
(9) potsherd after upper electrode is put in the silicone oil of 100～200 DEG C and polarize, after placing 24 hours, carry out electrical performance testing.
10. preparation method according to claim 9, it is characterised in that step (9) described polarizing voltage is 3～5kV/mm; Polarization time is 20～60min.
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| CN114621007A (en) * | 2020-12-14 | 2022-06-14 | 四川大学 | Low-temperature prepared high-performance PZT-based multielement modified piezoelectric ceramic |
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