CN106673643A - Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics - Google Patents

Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics Download PDF

Info

Publication number
CN106673643A
CN106673643A CN201611092099.8A CN201611092099A CN106673643A CN 106673643 A CN106673643 A CN 106673643A CN 201611092099 A CN201611092099 A CN 201611092099A CN 106673643 A CN106673643 A CN 106673643A
Authority
CN
China
Prior art keywords
tio
preparation
srco
sample
mol ratio
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.)
Pending
Application number
CN201611092099.8A
Other languages
Chinese (zh)
Inventor
蒲永平
崔晨薇
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi 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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201611092099.8A priority Critical patent/CN106673643A/en
Publication of CN106673643A publication Critical patent/CN106673643A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics. The method comprises the steps of firstly weighing corresponding masses of Na2CO3, Bi2O3, SrCO3 and TiO2 according to the molar ratio to obtain a mixture; carrying out ball milling, drying and briquetting on the mixture to form a whole ingredient, sequentially carrying out pelleting and sieving on the whole ingredient to form a granulated material; pressing the granulated material to prepare a sample and sintering the prepared sample to obtain a sintered sample; and finally polishing and cleaning the sintered sample, evenly coating the front surface and the back surface of the polished and cleaned sintered sample with electrode slurry, and sintering the sample coated with a silver electrode to obtain the (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics. The (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics obtained by the method has a high dielectric constant and obvious relaxation characteristics, is suitable for a wider temperature range, adopts a simple preparation process, is low in material cost, environmentally friendly, and becomes an excellent important candidate material used as a high-end industrial application material instead of a lead-based ceramic material in technology and economy.

Description

One kind (Bi0.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system
Technical field
The present invention relates to ceramic dielectric material field, and in particular to one kind (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation of system The ferroelectric preparation method in Henan.
Background technology
Relaxation ferroelectric shows high dielectric constant, big piezoelectric response, strong nonlinear effect and has aobvious The temperature dependency and frequency dependence of work.These special Relaxivities are to account for leading domain structure by shortrange order to cause. And the most important feature of relaxation ferroelectric, show as dielectric constant have wide extreme value scope and correspondence one it is relatively wide Temperature position (Tm), and it is different from traditional ferroelectric Curie point (TC).With the ferroelectricity body phase of traditional perovskite structure Than, the maximum is not to change to long-range order ferroelectric phase from paraelectric phase, along with being polarized in the uniform state in macro-regions, but Regional area appearance is polarized in, causes the generation of nanometer polarization microcell (PNRs).These excellent performances so that relaxation ferroelectric Become first-selected high-end commercial Application material.
At present, many scholars conduct extensive research relaxation ferroelectric ceramic material, but most system Still it is leaded, will suffer exit.Bi0.5Na0.5TiO3(BNT) as a kind of relaxation ferroelectric of antiferroelectric type, not only have The broad peak of dielectric constant, and the property such as four directions is symmetrical of the frequency dependence exception with dielectric constant and local, into For study hotspot.However, BNT is due to complicated structure, experiencing from paraelectrics Emission in Cubic (Pm3m) to anti-ferrum at 547 DEG C The phase transition process of electric Tetragonal (P4bm), subsequently carries out the phase transition process of ferroelectricity iris phase (R3c) at 320 DEG C.It is additionally considered that Four directions and Emission in Cubic are coexisted within the temperature range of 510-540 DEG C, and tiltedly side is mutually and Tetragonal is in 257-417 DEG C of temperature model ([1] Y.Hiruma, H.Nagata, T.Takenaka, Phase transition temperatures and coexists in enclosing piezoelectric properties of (Bi1/2Na1/2)TiO3-(Bi1/2K1/2)TiO3-BaTiO3lead-free piezoelectric ceramics,Jpn.J.Appl.Phys.45(2006)7409-7412.[2]Y.Hiruma,Y.Imai, Y.Watanabe,H.Nagata,T.Takenaka,Large electrostrain near the phase transition temperature of Bi0.5Na0.5TiO3-SrTiO3ferroelectric ceramics,Appl.Phys.Lett.92 (2008)262904.
[3]G.O.Jones,P.A.Thomas,The tetragonal phase of Na0.5Bi0.5TiO3-a new variant of the perovskite structure,Acta Crystallogr.,Sect.B:Struct.Sci.56 (2000)426-300.[4]G.O.Jones,P.A.Thomas,Investigation of the structure and phase transitions in the novel A-site substituted distorted perovskite compound Na0.5Bi0.5TiO3,Acta Crystallogr.,Sect.B:Struct.Sci.58(2002)168-178.)。 These multiple temperature spots of phase transition process correspondence, its relaxation scope are not wide.Also, high Tm(~320 DEG C) make its dielectric constant Just there is maximum in higher temperature, and dielectric constant is much smaller than T at room temperaturemThe dielectric constant at place, so as to greatly limit Its performance.Therefore its T must be made by doping vario-propertymReduce, dielectric constant increase, suitable for broader temperature range.
The content of the invention
It is an object of the invention to provide one kind (Bi0.5Na0.5)1-xSrxTiO3The preparation side of the unleaded relaxation ferroelectric of system Method, with the ceramic material that the defect for overcoming above-mentioned prior art to exist, profit are obtained by the present invention, not only with obvious Relaxation phenomena, and with high dielectric constant, effectively relaxation corresponding temperature is moved to low temperature direction, preparation technology letter Single, the cost of material is low, environmental friendliness, it is adaptable to broader temperature range.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
One kind (Bi0.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, comprises the following steps：
Step one：The Na of respective quality is weighed respectively according to mol ratio2CO3、Bi2O3、SrCO3、TiO2Mixture is obtained, and Ball milling, drying are carried out after this mixture is mixed with zirconium oxide ballstone, deionized water, after briquetting, it is little in 840~860 DEG C of insulations 3 When form full dispensing, then full dispensing is carried out pelletize successively and is sieved, formed granulation material；
Step 2：The granulation material that step one is obtained is pressed into sample under the pressure of 100~120MPa, and will make Sample is sintered and obtains sintered specimen；
Step 3：The sintered specimen that polishing, cleaning step two are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is sintered and obtains (Bi0.5Na0.5)1-xSrxTiO3System ceramics.
Further, weighing is distinguished according to mol ratio in step one, its method is：(Bi0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain, wherein x=0.45,0.55,0.65,0.75 or 0.85；
A, as x=0.45, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 11:11:9:53；
B, as x=0.55, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 9:9:11:47；
C, as x=0.65, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 7:7:13:41；
D, as x=0.75, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 1:1:3:7；
E, as x=0.85, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 3:3:17:29.
Further, by Na in step one2CO3、Bi2O3、SrCO3And TiO2Mixture and zirconium oxide ballstone, deionization Water, according to mass ratio 1:2:Ball milling is carried out after 1 mixing.
Further, the Ball-milling Time in step one is 12h.
Further, drying material is carried out into pelletize successively in step one and is sieved, the process for forming granulation material is：Will bonding Agent is added to full dispensing carries out pelletize, wherein 80 mesh and 120 mesh sieves take middle material as granulation material excessively respectively when sieving.
Further, described binding agent is the matter of polyvinyl alcohol in polyvinyl alcohol water solution, and polyvinyl alcohol water solution Amount concentration is 4~7%.
Further, the sintering condition in step 2 is：60min is incubated after 500~510 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min is incubated 60min after being warming up to 1000~1100 DEG C, when being warming up to 1270~1290 DEG C with 5 DEG C/min 2~4h of insulation it Afterwards, it is cooled to after 500~510 DEG C with 5 DEG C/min, cools to room temperature with the furnace.
Further, the sintering condition in step 3 is：10~15min is sintered at a temperature of 600~610 DEG C.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention prepares powder body using solid phase method, and granule soilless sticking, fillibility are good, low cost, yield are big, preparation technology is simple It is single, easy control of reaction conditions, the unleaded (Bi that in addition prepared by the inventive method0.5Na0.5)1-xSrxTiO3System relaxation ferroelectric Ceramics, not only with high dielectric constant, it will be apparent that relaxation behavior, it is adaptable to broader temperature range, and preparation technology letter Single, the cost of material is low, environmental protection, becomes replacement lead base ceramic material and is used as high-end commercial Application material technically and economically And excellent important candidate material.
Further, the present invention passes through Sr2+Ion doping concentration change, introduces SrxTiO3With low Curie temperature (TC =-250 DEG C), to realize the controllable adjustment of curie point, by Sr2+Ion doping concentration change, large radius ionDoping minor radius ionExpand lattice, Ti4+Ion Generation relaxation exercise, so as to produce strong internal electric field in intracell, there is strong electron displacement polarization in oxonium ion, from this The raising of ceramic dielectric constant is realized in matter, by Sr2+Ion doping concentration change, can strengthen (Bi0.5Na0.5)1- xSrxTiO3The relaxation behavior of system ceramics, to realize carrying out controllable adjustment to the Relaxivity of the system ceramics so as to wider Within the temperature range of have good relaxation behavior.
Description of the drawings
Fig. 1 is (Bi0.5Na0.5)1-xSrxTiO3The XRD figure of system ceramics；
Fig. 2 is (Bi0.5Na0.5)1-xSrxTiO3System ceramic dielectric constant-temperature curve；
Fig. 3 is (Bi0.5Na0.5)1-xSrxTiO3System ceramic dielectric constant inverse varies with temperature curve；
Fig. 4 is (Bi0.5Na0.5)1-xSrxTiO3System ceramics Curie's weiss matched curve；
Fig. 5 is (Bi0.5Na0.5)1-xSrxTiO3System ceramic dielectric constant is with x change curves；
Fig. 6 is (Bi0.5Na0.5)1-xSrxTiO3System ceramics TmWith x change curves.
Specific embodiment
Below the present invention is described in further detail：
A kind of new (Bi0.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, comprises the following steps：
Step one：(Bi0.5Na0.5)1-xSrxTiO3System ceramics (x=0.45,0.55,0.65,0.75,0.85),
A, as x=0.45, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 11:11:9:53；
B, as x=0.55, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 9:9:11:47；
C, as x=0.65, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 7:7:13:41；
D, as x=0.75, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 1:1:3:7；
E, as x=0.85, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 3:3:17:29；
The Na of respective quality is weighed respectively according to above-mentioned mol ratio2CO3、Bi2O3、SrCO3、TiO2Mixture is obtained, and will This mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling, drying are carried out after 1 mixing, drying material is obtained；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 840~860 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous Mixture (polyvinyl alcohol water solution, in polyvinyl alcohol water solution the mass concentration of polyvinyl alcohol be 4~7%) add to full dispensing Row pelletize, wherein, per 3-5g full dispensings in plus 1ml binding agents, cross 80 mesh when sieving respectively and 120 mesh sieves take middle material as making Pellet；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 100~120MPa, and will make Sample is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then aluminium oxide saggar is placed in high temperature box furnace and is sintered Sintered specimen is obtained, wherein sintering condition is：60min is incubated after 500~510 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min liters Temperature is incubated 60min to after 1000~1100 DEG C, when being warming up to 1270~1290 DEG C with 5 DEG C/min after 2~4h of insulation, with 5 DEG C/ After min is cooled to 500~510 DEG C, room temperature is cooled to high temperature box furnace；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 10~15min and obtain (Bi at a temperature of 600~610 DEG C0.5Na0.5)1- xSrxTiO3System ceramics.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
The present invention (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation ferroelectric of system, its formula are (Bi0.5Na0.5)1- xSrxTiO3, wherein x=0.45, x are molar percentage.
Step one：According to mol ratio 11:11:9:53 Na for weighing respective quality respectively2CO3、Bi2O3、SrCO3、TiO2 To mixture, and by this mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling is carried out after 1 mixing, is dried It is dry, obtain drying material；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 840 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous (polyvinyl alcohol water solution, in polyvinyl alcohol water solution, the mass concentration of polyvinyl alcohol is carried out mixture 4%) to add to full dispensing Pelletize, wherein, add 1ml binding agents in the full dispensings of every 3g, 80 mesh are crossed respectively when sieving and 120 mesh sieves take middle material as pelletize Material；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 100MPa, and by the sample for making It is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then is placed in be sintered in high temperature box furnace by aluminium oxide saggar and obtains Sintered specimen, wherein sintering condition are：60min is incubated after 500 DEG C are warming up to 2 DEG C/min, 1000 DEG C is warming up to 3 DEG C/min After be incubated 60min, when being warming up to 1270 DEG C with 5 DEG C/min after insulation 2h, be cooled to after 500 DEG C, with high-temperature cabinet with 5 DEG C/min Formula stove is cooled to room temperature；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 10min and obtain (Bi at a temperature of 600 DEG C0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain.
Embodiment 2
The present invention (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation ferroelectric of system, its formula are (Bi0.5Na0.5)1- xSrxTiO3, wherein x=0.55, x are molar percentage.
Step one：According to mol ratio 9:9:11:47 Na for weighing respective quality respectively2CO3、Bi2O3、SrCO3、TiO2Obtain Mixture, and by this mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling, drying are carried out after 1 mixing, Obtain drying material；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 850 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous (polyvinyl alcohol water solution, in polyvinyl alcohol water solution, the mass concentration of polyvinyl alcohol is carried out mixture 5%) to add to full dispensing Pelletize, wherein, add 1ml binding agents in the full dispensings of every 4g, 80 mesh are crossed respectively when sieving and 120 mesh sieves take middle material as pelletize Material；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 110MPa, and by the sample for making It is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then is placed in be sintered in high temperature box furnace by aluminium oxide saggar and obtains Sintered specimen, wherein sintering condition are：60min is incubated after 505 DEG C are warming up to 2 DEG C/min, 1050 DEG C is warming up to 3 DEG C/min After be incubated 60min, when being warming up to 1280 DEG C with 5 DEG C/min after 2~4h of insulation, be cooled to after 505 DEG C, with height with 5 DEG C/min Warm batch-type furnace is cooled to room temperature；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 12min and obtain (Bi at a temperature of 605 DEG C0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain.
Embodiment 3
The present invention (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation ferroelectric of system, its formula are (Bi0.5Na0.5)1- xSrxTiO3, wherein x=0.65, x are molar percentage.
Step one：According to mol ratio 7:7:13:41 Na for weighing respective quality respectively2CO3、Bi2O3、SrCO3、TiO2Obtain Mixture, and by this mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling, drying are carried out after 1 mixing, Obtain drying material；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 860 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous (polyvinyl alcohol water solution, in polyvinyl alcohol water solution, the mass concentration of polyvinyl alcohol is carried out mixture 7%) to add to full dispensing Pelletize, wherein, add 1ml binding agents in the full dispensings of every 5g, 80 mesh are crossed respectively when sieving and 120 mesh sieves take middle material as pelletize Material；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 120MPa, and by the sample for making It is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then is placed in be sintered in high temperature box furnace by aluminium oxide saggar and obtains Sintered specimen, wherein sintering condition are：60min is incubated after 510 DEG C are warming up to 2 DEG C/min, 1100 DEG C is warming up to 3 DEG C/min After be incubated 60min, when being warming up to 1290 DEG C with 5 DEG C/min after insulation 4h, be cooled to after 510 DEG C, with high-temperature cabinet with 5 DEG C/min Formula stove is cooled to room temperature；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 15min and obtain (Bi at a temperature of 610 DEG C0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain.
Embodiment 4
The present invention (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation ferroelectric of system, its formula are (Bi0.5Na0.5)1- xSrxTiO3, wherein x=0.75, x are molar percentage.
Step one：According to mol ratio 1:1:3:7 Na for weighing respective quality respectively2CO3、Bi2O3、SrCO3、TiO2Mixed Compound, and by this mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling, drying are carried out after 1 mixing, is obtained To drying material；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 850 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous (polyvinyl alcohol water solution, in polyvinyl alcohol water solution, the mass concentration of polyvinyl alcohol is carried out mixture 6%) to add to full dispensing Pelletize, wherein, add 1ml binding agents in the full dispensings of every 4g, 80 mesh are crossed respectively when sieving and 120 mesh sieves take middle material as pelletize Material；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 120MPa, and by the sample for making It is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then is placed in be sintered in high temperature box furnace by aluminium oxide saggar and obtains Sintered specimen, wherein sintering condition are：60min is incubated after 510 DEG C are warming up to 2 DEG C/min, 1000 DEG C is warming up to 3 DEG C/min After be incubated 60min, when being warming up to 1280 DEG C with 5 DEG C/min after 2~4h of insulation, be cooled to after 510 DEG C, with height with 5 DEG C/min Warm batch-type furnace is cooled to room temperature；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 15min and obtain (Bi at a temperature of 600 DEG C0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain.
Embodiment 5
The present invention (Bi0.5Na0.5)1-xSrxTiO3The unleaded relaxation ferroelectric of system, its formula are (Bi0.5Na0.5)1- xSrxTiO3, wherein x=0.85, x are molar percentage.
Step one：According to mol ratio 3:3:17:29 Na for weighing respective quality respectively2CO3、Bi2O3、SrCO3、TiO2Obtain Mixture, and by this mixture and zirconium oxide ballstone, deionized water, according to mass ratio 1:2:Ball milling, drying are carried out after 1 mixing, Obtain drying material；
Step 2：After by drying material briquetting, be placed in Muffle furnace and full dispensing formed within 3 hours in 860 DEG C of insulations；
Step 3：The full dispensing that step 2 is obtained carries out pelletize successively and sieves, and the process for forming granulation material is：Will be viscous (polyvinyl alcohol water solution, in polyvinyl alcohol water solution, the mass concentration of polyvinyl alcohol is carried out mixture 7%) to add to full dispensing Pelletize, wherein, add 1ml binding agents in the full dispensings of every 5g, 80 mesh are crossed respectively when sieving and 120 mesh sieves take middle material as pelletize Material；
Step 4：The granulation material that step 3 is obtained is pressed into sample under the pressure of 110MPa, and by the sample for making It is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then is placed in be sintered in high temperature box furnace by aluminium oxide saggar and obtains Sintered specimen, wherein sintering condition are：60min is incubated after 505 DEG C are warming up to 2 DEG C/min, 1000 DEG C is warming up to 3 DEG C/min After be incubated 60min, when being warming up to 1270 DEG C with 5 DEG C/min after insulation 4h, be cooled to after 505 DEG C, with high-temperature cabinet with 5 DEG C/min Formula stove is cooled to room temperature；
Step 5：The sintered specimen that polishing, cleaning step four are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample of coating silver electrode is placed in the aluminium oxide saggar with zirconium oxide as backing plate, then will Aluminium oxide saggar is placed in batch-type furnace, sinters 10min and obtain (Bi at a temperature of 610 DEG C0.5Na0.5)1-xSrxTiO3System is made pottery Porcelain.
The ceramic medium material prepared by example 1 to example 5 is can be seen that from Fig. 1 to Fig. 6, by adding Sr2+Ion, The solid solution ceramic of Ca-Ti ore type is formed, pseudo- cubic structure is presented, and is not had second mutually to produce.With Sr2+Ion doping is dense The raising of degree, is effectively reduced TmSo as to low temperature direction move, as x=0.55, dielectric constant reached maximum (~ 5500), meanwhile, (Bi0.5Na0.5)1-xSrxTiO3System ceramics occur in that obvious relaxation behavior.Two of relaxation behavior are important Phenomenon is respectively Diffuse phase transition and frequency dispersion.Wherein, Diffuse phase transition refer to Phase transitions be it is gradually nonmutationed, Show as the widthization at dielectric constant and temperature curve dielectric peak；Frequency dispersion refers to low temperature side dielectric peak with test frequency Raising and slightly move to high temperature direction, and dielectric peak value is slightly reduced.The two phenomenons have in the system ceramics fills The embodiment for dividing.In order to further study and characterize relaxation behavior, we pass through Curie-weiss formula fitting curve as shown in figure 3, Wherein T0It is referred to as characteristic temperature, TCFor normal frroelectrics under theory by the opposite paraelectric phase of ferroelectricity transition temperature, can be with from figure Find out, when there is Diffuse phase transition behavior, dielectric constant with temperature change curve can deviate from Curie-weiss formula, deviation Scope shows that more greatly sample is more unsatisfactory for Curie-Weiss law, and the short distance order between this deviation behavior and nano-area has Close.Additionally, in order to determine quantifier elimination (Bi0.5Na0.5)1-xSrxTiO3The relaxation degree of system ceramics, we are by deviateing outside Curie This formula fitting curve as shown in figure 4, wherein γ be disperse index, γ spans be 1~2, γ=1 be normal frroelectrics, γ=2 are relaxation ferroelectric, the γ value between 1~2 the coexisting for normal frroelectrics and relaxation ferroelectric that show sample.From figure As can be seen that (Bi in 40.5Na0.5)0.35Sr,0.65TiO3Ceramics have superior Relaxivity (γ=1.9).Institute of the present invention (the Bi for preparing0.5Na0.5)0.35Sr,0.65TiO3Unleaded relaxation ferroelectric ceramic material, not only with high dielectric constant, hence it is evident that Relaxation behavior, it is adaptable to broader temperature range, and preparation process is simple, the cost of material is low, environmental protection, becomes replacement Lead base ceramic material is used as high-end commercial Application material technically and economically and excellent important candidate material.

Claims (8)

1. one kind (Bi0.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, it is characterised in that including following Step：
Step one：According to Na2CO3、Bi2O3、SrCO3And TiO2Mol ratio weigh the Na of respective quality respectively2CO3、Bi2O3、 SrCO3、TiO2Mixture is obtained, and after this mixture is mixed with zirconium oxide ballstone, deionized water, carries out ball milling, drying, briquetting Afterwards, full dispensing is formed within 3 hours in 840~860 DEG C of insulations, then full dispensing is carried out pelletize successively and is sieved, form granulation material, Wherein x=0.45~0.85；
Step 2：The granulation material that step one is obtained is pressed into sample under the pressure of 100~120MPa, and by the sample for making It is sintered and obtains sintered specimen；
Step 3：The sintered specimen that polishing, cleaning step two are obtained, the sintered specimen tow sides after polishing and cleaning are uniform Coating silver electrode paste, the sample of coating silver electrode is sintered and obtains (Bi0.5Na0.5)1-xSrxTiO3System ceramics.
2. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, distinguishing weighing according to mol ratio in step one, its method is：(Bi0.5Na0.5)1-xSrxTiO3System ceramics, its Middle x=0.45,0.55,0.65,0.75 or 0.85；
A, as x=0.45, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 11:11:9:53；
B, as x=0.55, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 9:9:11:47；
C, as x=0.65, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 7:7:13:41；
D, as x=0.75, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 1:1:3:7；
E, as x=0.85, Na2CO3、Bi2O3、SrCO3、TiO2Mol ratio be 3:3:17:29.
3. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, by Na in step one2CO3、Bi2O3、SrCO3And TiO2Mixture and zirconium oxide ballstone, deionized water, according to Mass ratio 1:2:Ball milling is carried out after 1 mixing.
4. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, the Ball-milling Time in step one is 12h.
5. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, drying material being carried out pelletize successively in step one and being sieved, the process for forming granulation material is：Binding agent is added Pelletize is carried out to full dispensing, wherein 80 mesh and 120 mesh sieves take middle material as granulation material excessively respectively when sieving.
6. one kind (Bi according to claim 50.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, described binding agent is the mass concentration of polyvinyl alcohol in polyvinyl alcohol water solution, and polyvinyl alcohol water solution For 4~7%.
7. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, the sintering condition in step 2 is：60min is incubated after 500~510 DEG C are warming up to 2 DEG C/min, with 3 DEG C/ Min is incubated 60min after being warming up to 1000~1100 DEG C, when being warming up to 1270~1290 DEG C with 5 DEG C/min after 2~4h of insulation, It is cooled to after 500~510 DEG C with 5 DEG C/min, cools to room temperature with the furnace.
8. one kind (Bi according to claim 10.5Na0.5)1-xSrxTiO3The preparation method of the unleaded relaxation ferroelectric of system, Characterized in that, the sintering condition in step 3 is：10~15min is sintered at a temperature of 600~610 DEG C.
CN201611092099.8A 2016-12-01 2016-12-01 Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics Pending CN106673643A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611092099.8A CN106673643A (en) 2016-12-01 2016-12-01 Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611092099.8A CN106673643A (en) 2016-12-01 2016-12-01 Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics

Publications (1)

Publication Number Publication Date
CN106673643A true CN106673643A (en) 2017-05-17

Family

ID=58866232

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611092099.8A Pending CN106673643A (en) 2016-12-01 2016-12-01 Preparation method of (Bi<0.5>Na<0.5>)<1-x>SrxTiO3 system-based lead-free relaxor ferroelectrics

Country Status (1)

Country Link
CN (1) CN106673643A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107935589A (en) * 2017-12-14 2018-04-20 陕西科技大学 A kind of micro zirconium dioxide addition ST NBT energy storage ceramics and preparation method thereof
CN109516800A (en) * 2018-12-14 2019-03-26 陕西科技大学 A kind of high energy-storage property media ceramic, preparation method and applications
CN109734442A (en) * 2019-03-21 2019-05-10 河南城建学院 A kind of high performance piezoelectric ceramic material and preparation method
CN112552040A (en) * 2020-12-24 2021-03-26 电子科技大学 Pulse energy storage ceramic material and preparation method thereof
CN112620347A (en) * 2020-12-14 2021-04-09 瑞安市五星铜业有限公司 Processing technology of high-shaping brass strip for producing H90 bullet cartridge case

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446450A (en) * 2014-11-28 2015-03-25 宁波大学 Lead-free ferroelectric refrigeration material as well as preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446450A (en) * 2014-11-28 2015-03-25 宁波大学 Lead-free ferroelectric refrigeration material as well as preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
B.PARIJA ET AL.: "Structure microstructure and dielectric properties of 100-x(Bi0.5Na0.5)TiO3-xSrTiO3 composites ceramics", 《APPLIED PHYSICS A》 *
WERNER KRAUSS ET AL.: "Piezoelectric properties and phase transition temperatures of the solid solution of (1-x)(Bi0.5Na0.5)TiO3-xSrTiO3", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107935589A (en) * 2017-12-14 2018-04-20 陕西科技大学 A kind of micro zirconium dioxide addition ST NBT energy storage ceramics and preparation method thereof
CN107935589B (en) * 2017-12-14 2021-06-25 陕西科技大学 Micro zirconium dioxide added ST-NBT energy storage ceramic and preparation method thereof
CN109516800A (en) * 2018-12-14 2019-03-26 陕西科技大学 A kind of high energy-storage property media ceramic, preparation method and applications
CN109516800B (en) * 2018-12-14 2021-04-27 陕西科技大学 High-energy-storage-performance dielectric ceramic, and preparation method and application thereof
CN109734442A (en) * 2019-03-21 2019-05-10 河南城建学院 A kind of high performance piezoelectric ceramic material and preparation method
CN112620347A (en) * 2020-12-14 2021-04-09 瑞安市五星铜业有限公司 Processing technology of high-shaping brass strip for producing H90 bullet cartridge case
CN112552040A (en) * 2020-12-24 2021-03-26 电子科技大学 Pulse energy storage ceramic material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106673643A (en) Preparation method of (Bi&lt;0.5&gt;Na&lt;0.5&gt;)&lt;1-x&gt;SrxTiO3 system-based lead-free relaxor ferroelectrics
CN109574656A (en) A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof
Xu et al. Synthesis and piezoelectric and ferroelectric properties of (Na0. 5Bi0. 5) 1− xBaxTiO3 ceramics
CN109180178A (en) A kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and preparation method thereof
CN101648807A (en) Calcium barium zirconate titanate base piezoceramics and preparation method thereof
CN109704762B (en) Strontium niobate-based antiferroelectric ceramic and preparation method and application thereof
CN102674832B (en) Barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and preparation method thereof
CN101885607A (en) Barium zirconate titanate-potassium sodium niobate piezoelectric ceramics and preparation method thereof
CN101891474A (en) Potassium-sodium niobate-sodium potassium bismuth titanate piezoelectric ceramics and preparation method thereof
CN102976748B (en) High-density barium strontium titanate ceramic and preparation method thereof
CN111004030B (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN109320244B (en) Low-temperature sintered piezoelectric ceramic material and preparation method thereof
CN105669195B (en) Low dielectric constant and high Q value microwave dielectric ceramic materials and preparation method thereof
CN114085079A (en) High-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and preparation method thereof
CN111747740B (en) Samarium ion doped lead zirconate titanate based high-performance piezoelectric ceramic and preparation method thereof
CN104098330B (en) Post growth annealing is adopted to prepare the method for high-performance barium strontium titanate pyroelectric ceramics
CN106699176A (en) Barium titanate-based leadless piezoelectric ceramic and preparation method and application thereof
CN111170736B (en) Lead-based perovskite structure high-temperature piezoelectric ceramic and preparation method thereof
CN105254295B (en) A kind of preparation method of neodymium-doped titanium acid barium nano-ceramic powder
CN109293353B (en) Lead-free BiFeO with high energy storage density and high energy storage efficiency3Ferroelectric ceramic material and its preparation method
CN111217604A (en) Sodium bismuth titanate-based electronic ceramic with high energy storage density and high efficiency and preparation method thereof
CN108002836B (en) Medium dielectric constant microwave dielectric ceramic material and preparation method thereof
CN106957174A (en) BNT-BA-KNN non-plumbum ferroelectric Phase transformation ceramics and preparation method thereof
CN107021754B (en) Dispersant modified relaxation type niobium nickel zirconium lead titanate piezoelectric ceramic and preparation method thereof
CN109678501A (en) A kind of dedicated piezoelectric vibrator ceramic formula of smoke alarm and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170517