CN103467096A - Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof - Google Patents

Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof Download PDF

Info

Publication number
CN103467096A
CN103467096A CN2013104238527A CN201310423852A CN103467096A CN 103467096 A CN103467096 A CN 103467096A CN 2013104238527 A CN2013104238527 A CN 2013104238527A CN 201310423852 A CN201310423852 A CN 201310423852A CN 103467096 A CN103467096 A CN 103467096A
Authority
CN
China
Prior art keywords
piezoelectric ceramics
leadless piezoelectric
zno
temperature
potassium niobate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013104238527A
Other languages
Chinese (zh)
Other versions
CN103467096B (en
Inventor
李海涛
闫焉服
王维
许荣辉
刘伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Science and Technology
Original Assignee
Henan University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN201310423852.7A priority Critical patent/CN103467096B/en
Publication of CN103467096A publication Critical patent/CN103467096A/en
Application granted granted Critical
Publication of CN103467096B publication Critical patent/CN103467096B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a novel potassium sodium niobate-based leadless piezoelectric ceramics and a preparation method thereof. The potassium sodium niobate-based leadless piezoelectric ceramics which is higher in density, excellent in piezoelectric property and environment-friendly is prepared by adjusting the components of the potassium sodium niobate-based leadless piezoelectric ceramics and adopting the technologies such as microwave sintering, silver roasting, polarization, etc. The novel potassium sodium niobate-based leadless piezoelectric ceramics is prepared from the raw materials of chemical pure Na2CO3, K2CO3, Li2CO3, Nb2O5, Ta2O5 and Sb2O3, and the additives of chemical pure ZnO, ZnCO3 or 5ZnO.4CO2.6H2O; the composition of the leadless piezoelectric ceramics is expressed as the chemical formula: (Na 0.52 K0.46 Li 0.06) (Nb 0.86 Tb 0.08 Sb 0.06) O(3+x) ZnO, wherein x is equal to 0.00-0.05.

Description

A kind of novel potassium niobate sodium base leadless piezoelectric ceramics and preparation method thereof
Technical field
The present invention relates to a kind of novel piezo-electric ceramic material, relate in particular to a kind of potassium niobate sodium-based leadless piezoelectric ceramic and preparation method thereof.
Background technology
Piezoelectric ceramics is that a class is at the widely used new and high technology material of electron trade.But that extensive use is Pb-based lanthanumdoped zirconate titanates Pb (Zr, Ti) O at present 3base piezoelectric ceramic (being called the PZT base piezoelectric ceramic), in the PZT base piezoelectric ceramic, Pb content, up to more than 60wt. %, all can work the mischief to human body health and living environment thereof in its preparation, use, discarded process.Therefore research and develop the piezoelectric property excellence, eco-friendly leadless piezoelectric ceramics is urgent, as to have an important social effect problem.
In the leadless piezoelectric ceramics system, potassium-sodium niobate (K, Na) NbO 3based leadless piezoelectric ceramics (being called the KNN base piezoelectric ceramic), because it has higher Curie temperature and electromechanical coupling performance preferably, be considered to one of candidate material of the most potential replacement lead base piezoelectric ceramics.But the KNN ceramic dense degree prepared by conventional sintering technique is not high, and piezoelectric property is also poor.Its reason mainly contain following some: KNbO 3-NaNbO 3the phase equilibrium temperature of sosoloid is below 1140 ℃; Basic metal in the KNN pottery easily volatilizees during sintering under comparatively high temps, causes ceramic actual constituent nonstoichiometry formula, easily forms second-phase and reduces its piezoelectric property; Higher sintering temperature and longer soaking time, easily make ceramic part crystal grain the abnormal growth phenomenon occur, makes the distribution of crystal grain the two poles of the earth distribution situation occur.
Be expected to overcome above-mentioned shortcoming by adjusting the measures such as preparation technology or doping vario-property.The sintering method of preparation KNN pottery mainly contains hot pressed sintering, discharge plasma sintering etc. at present.Although these sintering technologies can improve the density of stupalith, its apparatus expensive, the shape of sample and quantity all are subject to strict restriction, are not suitable for suitability for industrialized production.Current research data shows, the factor that affects KNN base pottery alkali metal volatilization in sintering process mainly contains sintering temperature and sintering time.The sintering temperature of conventional sintering technique is higher, and sintering time is long, is unfavorable for the sintering of KNN base pottery, so the piezoelectric constant of the KNN pottery for preparing of conventional sintering technique d 33only have 80 pC/N.
Summary of the invention
The present invention seeks in order to solve the problems of the technologies described above the deficiency of existence, potassium niobate sodium-based leadless piezoelectric ceramic of high, the comprehensive piezoelectric property excellence of a kind of density and environmental protection and preparation method thereof is provided.
The technical solution adopted in the present invention is: by adjusting the composition of potassium niobate sodium-based leadless piezoelectric ceramic, adopt the preparation technologies such as microwave sintering, roasting silver, polarization, prepare in lower sintering temperature and shorter sintering time that density is higher, piezoelectric property is excellent and the potassium niobate sodium-based leadless piezoelectric ceramic of environmental protection.The present invention is raw materials used is chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, additive is chemical pure ZnO, ZnCO 3or 5ZnO4CO 26H 2o; The one-tenth of this pottery is grouped into available chemical formulation: (Na 0.52k 0.46li 0.06) (Nb 0.86tb 0.08sb 0.06) O 3+ xznO, wherein, x=0.00 ~ 0.05.
The technological process that microwave sintering of the present invention prepares potassium niobate sodium-based leadless piezoelectric ceramic is:
Step 1, the present invention is raw materials used is chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, additive is chemical pure ZnO, ZnCO 3or 5ZnO4CO 26H 2o; Raw material is pressed to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86tb 0.08sb 0.06) O 3+ xznO( x=0.00 ~ 0.05) proportioning is carried out weighing, batching, with dehydrated alcohol, as ball-milling medium, with planetary ball mill ball milling 4～8 h, then slurry is placed in loft drier and obtains dry powder after 100 ℃ of oven dry 8 h;
Step 2, step 1 gained dry powder is put into to the temperature programmed control box-type furnace, with the speed continuous warming to 800 of 5 ℃/min～900 ℃, be incubated 4～6 h, synthetic potassium-sodium niobate-based ceramic powder;
Step 3, using the polyvinyl alcohol that adds 5wt.% in step 2 gained ceramic powder as binding agent, stir, put into mould, with Manual tablet pressing machine compression moulding under 200MPa;
Step 4, the biscuit that step 3 is suppressed are put into the temperature programmed control box-type furnace, with the temperature rise rate of 10 ℃/min, rise to 650 ℃, and insulation 60min carries out binder removal, then is cooled to room temperature;
Step 5, the ceramics sample after the step 4 binder removal is placed in microwave agglomerating furnace, at 1000～1100 ℃ of temperature, is incubated the densification sintering that 20～60 min carry out ceramics sample;
Step 6, with 600 order sand paper, ceramic plate is polished, after polishing, at two surface uniforms, coated the silver slurry, be heated to 520 ℃ in the temperature programmed control box-type furnace, be incubated 20 min and roast silver-colored; Put into silicone oil after ceramic plate after roasting silver and polarized, the polarization temperature is: 80～100 ℃; Polarizing voltage is 3～5 kV/mm; Polarization time is 20 min; Obtain this potassium niobate sodium-based leadless piezoelectric ceramic.
Raw material in described step 1 will be dried 10 h at 120 ℃ before weighing, in order thoroughly to get rid of the moisture in raw material.
In described step 1, ball-milling medium is dehydrated alcohol and zirconia ball, and the mass ratio of raw material, dehydrated alcohol and zirconia ball is: 1:1:2, drum's speed of rotation is 250-300 r/min.
In described step 5, the microwave sintering warming machine is made as: the temperature rise rate before 1000 ℃ is 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.
The invention has the advantages that, by 8 drift angles at perovskite structure, add excess base metal K and Na, with the volatilization of K, Na in the compensation sintering process, keep the perovskite structure of ceramic crystal; By adding ZnO, ZnCO 3or 5ZnO4CO 26H 2o, to reduce ceramic sintering temperature, thereby improved ceramic density and mechanical quality factor.
The present invention has adopted Microwave Sintering Techniques, and microwave sintering is a kind of energy-efficient sintering method, and compared following advantage with traditional solid state sintering: heating rate is fast, and soaking time is short, has suppressed alkali-metal volatilization in sintering process; Micro-wave energy directly penetrates the sample of certain depth, at different depths, heats simultaneously, does not need heat transfer process, has avoided the abnormal growth of ceramic crystalline grain in the sintering process, can prepare at a lower temperature the stupalith that uniform crystal particles distributes; By regulating the output rating of microwave, can make the heating state of sample that the inertialess change occurs immediately, be convenient to automatically control and operate continuously; The thermal inertia of microwave sintering is little, energy fast cooling after sintering finishes, and heat utilization rate is high; Can shorten sintering time, thereby suppress the uniformity coefficient of alkali-metal volatilization and regulation and control ceramic crystalline grain simultaneously.Use this method that preparation cycle is shortened, thereby be more conducive to suitability for industrialized production.
The present invention adopts and to put into the temperature programmed control box-type furnace at the biscuit suppressed, and with the temperature rise rate of 10 ℃/min, rises to 650 ℃, and insulation 60min carries out binder removal, makes the binder decomposed volatilization; Adopt the roasting silver process, at the ceramic plate two ends, prepare silver electrode; Adopt polarization process, make piezoelectric ceramics there is better piezoelectric property.
The present invention has been carried out to electrical performance testing, and performance index are as follows: piezoelectric constant d 33be 221 ~ 305 pC/N; Planar electromechanical coupling factor k pbe 24 ~ 48%; Mechanical quality factor q mbe 110 ~ 214; Specific inductivity ε rbe 694 ~ 872; Dielectric loss tan δbe 0.024 ~ 0.04; Relative density ρ rbe 86.8 ~ 96.5%; Remnant polarization p rbe 15.6 ~ 28.6 μ C/cm 2; Curie temperature t cit is 442 ~ 464 ℃.
The present invention is different from traditional piezoelectric ceramics, and not leaded and any objectionable impurities, not only be beneficial to the healthy of the producer, and to environment without any pollution.
Embodiment
Following examples understand the present invention in detail.
Embodiment 1:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.005, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 306:356:46:1267:196:97:5.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 30min by the microwave sintering method at 1100 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 612347DEST_PATH_IMAGE001
。
embodiment 2:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.010, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 305:355:46:1265:196:97:9.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 30min by the microwave sintering method at 1050 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 732750DEST_PATH_IMAGE002
。
embodiment 3:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.015, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 305:354:46:1262:196:97:13.5.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 30min by the microwave sintering method at 1020 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 512487DEST_PATH_IMAGE003
。
embodiment 4:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.020, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 304:354:46:1259:196:96:18.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 30min by the microwave sintering method at 1000 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 579800DEST_PATH_IMAGE004
。
embodiment 5:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.025, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 303:353:46:1256:194:96:22.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 30min by the microwave sintering method at 1000 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 331855DEST_PATH_IMAGE005
。
embodiment 6:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.010, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 305:355:46:1265:196:97:9.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 50min by the microwave sintering method at 1050 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 357580DEST_PATH_IMAGE006
。
embodiment 7:
With chemical pure Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3with ZnO be raw material, according to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86ta 0.08sb 0.06) O 3+ xznO, get x=0.010, prepared burden; Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, each raw material of ZnO mass ratio be: 305:355:46:1265:196:97:9.By the mass ratio of above raw material 50 g that prepare burden, using dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, slip is dried 8 h at 100 ℃.Dry powder is incubated 4 h under 800 ℃, synthetic potassium-sodium niobate-based ceramic powder.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use the conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then being incubated 60min by the microwave sintering method at 1050 ℃, 1000 ℃ of temperature rise rates in the past are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, under 520 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil and be heated to 80～100 ℃, under 3～5kV/mm voltage, keep 20min to be polarized, after static 24 h, carry out electrical performance testing.Result is as follows:
Figure 296717DEST_PATH_IMAGE007
。

Claims (7)

1. a novel potassium niobate sodium base leadless piezoelectric ceramics, is characterized in that: the raw materials used chemical pure Na of being 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, additive is chemical pure ZnO, ZnCO 3or 5ZnO4CO 26H 2o; The one-tenth of this pottery is grouped into available chemical formulation: (Na 0.52k 0.46li 0.06) (Nb 0.86tb 0.08sb 0.06) O 3+ xznO, wherein, x=0.00 ~ 0.05.
2. novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 1, is characterized in that: Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, the ZnO mass ratio is: 306:356:46:1267:196:97:5.
3. novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 1, is characterized in that: Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, the ZnO mass ratio is: 304:354:46:1259:196:96:18.
4. novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 1, is characterized in that: Na 2cO 3, K 2cO 3, Li 2cO 3, Nb 2o 5, Ta 2o 5, Sb 2o 3, the ZnO mass ratio is: 305:355:46:1265:196:97:9.
5. the preparation method of novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 1 is characterized in that:
Step 1, raw material is pressed to chemical formula (Na 0.52k 0.46li 0.06) (Nb 0.86tb 0.08sb 0.06) O 3+ xznO, wherein, x=0.00 ~ 0.05, proportioning carry out weighing, batching,,, with planetary ball mill ball milling 4～8 h then slurry be placed in loft drier to 100 ℃ obtain dry powder after drying 8 h as ball-milling medium with dehydrated alcohol;
Step 2, step 1 gained dry powder is put into to the temperature programmed control box-type furnace, with the speed continuous warming to 800 of 5 ℃/min～900 ℃, be incubated 4～6 h, synthetic potassium-sodium niobate-based ceramic powder;
Step 3, using the polyvinyl alcohol that adds 5wt.% in step 2 gained ceramic powder as binding agent, stir, put into mould, with Manual tablet pressing machine compression moulding under 200MPa;
Step 4, the biscuit that step 3 is suppressed are put into the temperature programmed control box-type furnace, with the temperature rise rate of 10 ℃/min, rise to 650 ℃, and insulation 60min carries out binder removal, then is cooled to room temperature;
Step 5, the ceramics sample after the step 4 binder removal is placed in microwave agglomerating furnace, at 1000～1100 ℃ of temperature, is incubated the densification sintering that 20～60 min carry out ceramics sample;
Step 6, with 600 order sand paperings, ceramic plate is polished, after polishing, at two surface uniforms, coated the silver slurry, be heated to 520 ℃ in the temperature programmed control box-type furnace, be incubated 20 min and roast silver-colored; Put into silicone oil after ceramic plate after roasting silver and polarized, the polarization temperature is: 80～100 ℃; Polarizing voltage is: at 3～5 kV/mm; Polarization time is: 20 min; Obtain this potassium niobate sodium-based leadless piezoelectric ceramic.
6. the preparation method of novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 5, it is characterized in that: the raw material in step 1 will be dried 10 h at 120 ℃ before weighing.
7. the preparation method of novel potassium niobate sodium base leadless piezoelectric ceramics according to claim 5, it is characterized in that: in step 5, the microwave sintering warming machine is made as: the temperature rise rates before 1000 ℃ are 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.
CN201310423852.7A 2013-09-17 2013-09-17 Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof Expired - Fee Related CN103467096B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310423852.7A CN103467096B (en) 2013-09-17 2013-09-17 Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310423852.7A CN103467096B (en) 2013-09-17 2013-09-17 Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103467096A true CN103467096A (en) 2013-12-25
CN103467096B CN103467096B (en) 2014-12-24

Family

ID=49792179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310423852.7A Expired - Fee Related CN103467096B (en) 2013-09-17 2013-09-17 Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103467096B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016674A (en) * 2014-06-17 2014-09-03 河南科技大学 Barium titanate-based leadless piezoelectric ceramic and preparation method thereof
CN106242568A (en) * 2016-07-22 2016-12-21 郑州大学 A kind of microwave synthesis method of potassium-sodium niobate leadless piezoelectric ceramic
CN106291142A (en) * 2016-09-19 2017-01-04 郑州大学 Piezoelectric ceramics and piezoelectric semiconductor's test specimen multiformity polarization experiment system
CN107176837A (en) * 2017-05-31 2017-09-19 哈尔滨理工大学 A kind of preparation method of ultra-high dielectric coefficient potassium tantalate-niobate ceramics
CN109206137A (en) * 2018-11-19 2019-01-15 福州大学 A kind of preparation method of potassium-sodium niobate-zinc titanate strontium crystalline ceramics
CN109721352A (en) * 2019-03-16 2019-05-07 信阳师范学院 A kind of bismuth-sodium titanate base lead-free piezoelectric ceramic and preparation method thereof using the preparation of microwave material research-on-research station
CN113461422A (en) * 2021-08-03 2021-10-01 四川大学 High-voltage anti-fatigue potassium-sodium niobate-based lead-free piezoelectric ceramic and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1511802A (en) * 2002-12-27 2004-07-14 四川大学 Multi constituent niobate lead-free piezoelectric ceramics
CN101318819A (en) * 2008-07-15 2008-12-10 北京科技大学 Zinc doped sodium-based leadless piezoelectric ceramic synthesized at low-temperature and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1511802A (en) * 2002-12-27 2004-07-14 四川大学 Multi constituent niobate lead-free piezoelectric ceramics
CN101318819A (en) * 2008-07-15 2008-12-10 北京科技大学 Zinc doped sodium-based leadless piezoelectric ceramic synthesized at low-temperature and manufacturing method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016674A (en) * 2014-06-17 2014-09-03 河南科技大学 Barium titanate-based leadless piezoelectric ceramic and preparation method thereof
CN104016674B (en) * 2014-06-17 2015-09-16 河南科技大学 A kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof
CN106242568A (en) * 2016-07-22 2016-12-21 郑州大学 A kind of microwave synthesis method of potassium-sodium niobate leadless piezoelectric ceramic
CN106291142A (en) * 2016-09-19 2017-01-04 郑州大学 Piezoelectric ceramics and piezoelectric semiconductor's test specimen multiformity polarization experiment system
CN106291142B (en) * 2016-09-19 2022-04-29 河南感联智能科技有限公司 Piezoelectric ceramic and piezoelectric semiconductor test piece diversity polarization experimental system
CN107176837A (en) * 2017-05-31 2017-09-19 哈尔滨理工大学 A kind of preparation method of ultra-high dielectric coefficient potassium tantalate-niobate ceramics
CN107176837B (en) * 2017-05-31 2019-12-06 哈尔滨理工大学 Preparation method of potassium tantalate niobate ceramic with ultrahigh dielectric constant
CN109206137A (en) * 2018-11-19 2019-01-15 福州大学 A kind of preparation method of potassium-sodium niobate-zinc titanate strontium crystalline ceramics
CN109721352A (en) * 2019-03-16 2019-05-07 信阳师范学院 A kind of bismuth-sodium titanate base lead-free piezoelectric ceramic and preparation method thereof using the preparation of microwave material research-on-research station
CN109721352B (en) * 2019-03-16 2021-08-20 信阳师范学院 Sodium bismuth titanate-based lead-free piezoelectric ceramic prepared by adopting microwave material scientific workstation and preparation method thereof
CN113461422A (en) * 2021-08-03 2021-10-01 四川大学 High-voltage anti-fatigue potassium-sodium niobate-based lead-free piezoelectric ceramic and preparation method thereof

Also Published As

Publication number Publication date
CN103467096B (en) 2014-12-24

Similar Documents

Publication Publication Date Title
CN103467096B (en) Novel potassium sodium niobate-based leadless piezoelectric ceramics and preparation method thereof
CN104016674B (en) A kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof
CN101188156B (en) Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method
CN101648807A (en) Calcium barium zirconate titanate base piezoceramics and preparation method thereof
CN102167585B (en) Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof
CN101423391B (en) Novel potassium niobate sodium base leadless piezoelectric ceramics and preparation method thereof
CN102910902B (en) BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof
CN101186502A (en) Method for preparing potassium sodium niobate base leadless piezoelectric ceramic
CN101885607A (en) Barium zirconate titanate-potassium sodium niobate piezoelectric ceramics and preparation method thereof
CN104876567A (en) High-piezoelectric coefficient potassium-sodium niobate based leadless piezoelectric ceramics and preparation method thereof
CN114621004B (en) High-entropy ceramic material with high energy storage density and preparation method thereof
CN111233465A (en) Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof
CN105198417A (en) Preparation method of zirconic acid sodium bismuthide lithium cerium doped potassium-sodium niobate based ceramic material
CN108275999A (en) A kind of preparation method of potassium niobate sodium-based leadless piezoelectric ceramic
CN103866386A (en) Preparation method of novel ternary piezoelectric crystal monophase material
Xu et al. Improved ferroelectricity of (1− x) Na0. 5Bi0. 5TiO3–xBaTiO3 ceramics rapidly sintered at low temperature
CN110357624B (en) High-dielectric-constant glass frit modified strontium zirconate doped potassium-sodium niobate lead-free transparent ceramic material and preparation method thereof
CN102515757B (en) Low-resistivity pyroelectric ceramic material with temperature ageing resistance and preparation method thereof
Huan et al. Low Temperature Sintering and Enhanced Piezoelectricity of Lead‐Free (Na 0.52 K 0.4425 Li 0.0375)(Nb 0.86 Ta 0.06 Sb 0.08) O 3 Ceramics Prepared from Nano‐Powders
CN102153345B (en) NBT-KBT (NaBiTiO-KBiTiO) piezoelectric ceramic and manufacturing method thereof
CN110550953A (en) Sodium bismuth titanate-based lead-free piezoelectric ceramic and preparation method thereof
CN111732430B (en) Sm and Eu co-doped CaBi 8 Ti 7 O 27 Preparation method of ceramic, product and application thereof
CN101289318A (en) Sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics and method for preparing same
CN103922722B (en) A kind of lithium, cerium, tantalum mix bismuth niobate calcium based piezoelectric ceramic materials and preparation method thereof altogether
CN101894641A (en) Method for improving thermosensitive resistor production efficiency

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141224

Termination date: 20150917

EXPY Termination of patent right or utility model