CN107892572A - A kind of method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics - Google Patents

A kind of method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics Download PDF

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CN107892572A
CN107892572A CN201711406168.2A CN201711406168A CN107892572A CN 107892572 A CN107892572 A CN 107892572A CN 201711406168 A CN201711406168 A CN 201711406168A CN 107892572 A CN107892572 A CN 107892572A
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piezoelectric ceramics
scnn
leadless piezoelectric
tungsten bronze
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CN107892572B (en
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王天畅
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CETC 4 Research Institute
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Abstract

The invention discloses a kind of method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, belong to electron ceramic material technical field.The composition formula of the SCNN leadless piezoelectric ceramics is：Sr2‑ xCaxNaNb5O15, wherein：X is molar fraction；The leadless piezoelectric ceramics is prepared using solid-phase synthesis, it is 0.14 0.155 to control it to form the scope of x in formula in preparation process, as x=0.14 0.155, the rule for falling before, raising again, declining again is showed with the piezoelectricity of piezoelectric ceramics prepared by the rise of sintering temperature；Meanwhile the rule is also presented in density, unit cell dimension and the dielectric property of the piezoelectric ceramics.

Description

A kind of method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics
Technical field
The present invention relates to electron ceramic material technical field, and in particular to one kind prepares tungsten bronze structure SCNN leadless piezoelectrics The method of ceramics.
Background technology
With the progress in epoch, the application of piezoelectric ceramics is more and more extensive.It is different from the mode of traditional magnetic life electricity, pressure Electroceramics is a kind of new way of power life electricity, and it is especially being believed in fields such as machinery, electronics, communication, precision control, military affairs The areas of information technology such as detection, conversion, processing and the storage of breath play an important role.It is however, big absolutely in the market Partial piezoelectric is lead piezoelectric ceramics, and because lead has harmfulness to human body and environment, development has independent intellectual production The leadless piezoelectric material material of power substitutes traditional lead base piezoelectric ceramics (PZT), and to turn into China investigation of materials person one urgent and with great The problem of Practical significance.
Sr2-xCaxNaNb5O15(abbreviation SCNN) piezoelectric ceramics has higher piezoelectric coefficient d because of it33Higher Curie Temperature receives much concern, and is the class-1 piezoelectric ceramics for having very much application potential.But SCNN piezoelectric ceramics prepared by conventional solid-state method exists SCNN studies dynamics deficiency on parameters adjusting, and influence of the proportioning parameter for piezoelectric ceramics performance be not still apparent, pin of the present invention Parameters adjusting is studied and process modification, to propose new preparation method.
The content of the invention
It is an object of the invention to provide a kind of method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, pass through control SCNN piezoelectric ceramics stoichiometric factor is in x=0.14 to x=0.155 interval range, with increasing for sintering temperature, SCNN pressures Electroceramics shows the rule of " fall before, then rise, finally decline ", and this rule is not only embodied in its piezoelectric properties On, also embodied in terms of density, unit cell dimension and dielectric property.
To achieve the above object, the technical solution adopted in the present invention is as follows：
The composition formula of the SCNN leadless piezoelectric ceramics is：Sr2-xCaxNaNb5O15, wherein：X is molar fraction；The nothing Lead piezoelectric ceramics are prepared using solid-phase synthesis, and it is 0.14-0.155 to control it to form the scope of x in formula in preparation process.
In the SCNN leadless piezoelectric ceramics preparation process, work as x=0.14-0.155, with prepared by the rise of sintering temperature The piezoelectric property of piezoelectric ceramics shows the rule fall before, raise again, declining again；Meanwhile density, the structure cell of the piezoelectric ceramics The rule is also presented in size and dielectric property.As x=0.145, every combination property is optimal.
The present invention prepares tungsten bronze structure SCNN leadless piezoelectric ceramics using solid-phase synthesis, and this method specifically includes as follows Step：
(1) dispensing：With analytically pure SrCO3(99.5%), CaCO3(99%), Nb2O5And Na (99.5%)2CO3 (99.8%) it is raw material, dispensing is carried out according to the composition of the leadless piezoelectric ceramics；
(2) ball millings：It will be put into after each raw material uniformly mixing containing agate bead (ZrO2) ball grinder in, with anhydrous second Alcohol is that medium carries out ball milling, and drying and processing is carried out after ball milling；Wherein：Ball-milling Time is 12 hours, rotating speed 225r/min；Dry Dry-cure temperature is 90 DEG C, is dried to ethanol and volatilizees completely (about 6 hours)；
(3) pre-burning：Compound after drying is put into Al2O3In crucible, using high temperature sintering furnace in 1150 DEG C of pre-burning 12h；
(4) secondary ball milling：The raw material that pre-burning is finished is poured into containing agate bead (ZrO2) ball grinder in, repeat step (2) ball milling and drying course；
(5) it is granulated：The sample after drying is taken out, addition 3mL binders PVA is granulated；Filter out the purpose of 80 mesh of granularity -140 Sample is as raw materials for sintering；
(6) shaping and dumping：Apply 2MPa pressure to mould, the sample of 80~140 mesh is pressed into the thin of about 1mm Piece, and the PVA suppressed in thin slice is excluded into tabletting；
(7) sinter：By the way of multi-laminate burning, the load bearing board of suitable size is selected, is uniformly plated in load bearing board bottom As bedding and padding, the powder that interlayer is more than 80 mesh using granularity after being granulated uses with sintering composition zirconium oxide as separation layer, top layer The consistent powder of granularity prevents from volatilizing, and sintering temperature is 1200-1450 DEG C, sintering time 2-4h.
(8) prepare electrode and polarize：Polarized after preparing electrode using burning infiltration method, during polarization under the conditions of 150 DEG C, adopted The polarization of 25 minutes by a definite date is carried out with 4000V/mm direct currents highfield.
In above-mentioned steps (5), the granulation process is：After adding binder in the sample, grinding is uniform；Then powder is used Last tablet press machine is compressed into piece under 14MPa pressure, and thickness in blocks is 18mm；Place into mortar and crush, by crushing Sample pours into sieve, collects the mesh powder of 80 mesh -140 as the raw material that will be sintered；Collect and be more than 140 mesh powders as burning Protective layer during knot between tabletting.
In above-mentioned steps (6), during the PVA suppressed in thin slice is excluded into tabletting, by heating, make in thin slice PVA heat absorption vaporizations, overflow from tabletting.
In above-mentioned steps (8), use burning infiltration method prepare the process of electrode for：The powdery for removing ceramics sample surface first is protected Sheath, its surface is polished clean；Then silver paste is brushed in ceramic surface, is sintered after naturally dry.
The invention has the advantages that and beneficial effect：
When preparing the SCNN leadless piezoelectric ceramics using the inventive method, in SCNN piezoelectric ceramics composition formula Sr2- xCaxNaNb5O15In, in interval ranges of its stoichiometric factor x in 0.14-0.155, with increasing for sintering temperature, SCNN pressures Electroceramics shows the rule of " fall before, then rise, finally decline ", and this rule is not only embodied in its piezoelectric properties On, also embodied in terms of density, unit cell dimension and dielectric property.
Brief description of the drawings
Fig. 1 is SCNN ceramics preparation technology flow chart of the present invention.
Fig. 2 is the d of the SCNN piezoelectric ceramics under each sintering temperature in embodiment 133(pC/N)。
Embodiment
The present invention is described in detail below in conjunction with drawings and examples.
Embodiment 1：
The composition formula Sr of the SCNN leadless piezoelectric ceramics2-xCaxNaNb5O15, wherein：X is molar fraction；X= 0.14-0.155.The present embodiment prepares SCNN piezoelectric ceramics using solid phase method.Solid-phase process preparation comprises the following steps：(1) Dispensing, (2) ball millings, (3) drying, (4) pre-burning, (5) secondary ball milling, (6) drying, (7) granulation, (8) shaping, (9) dumping, (10) sintering, (11) are polarized by electrode, (12).
(1) dispensing：Raw material is calculated according to the stoichiometric factor in composition formula, weighed with being mixed.Choose high-purity Commercially available SrCO3(99.5%), CaCO3(99%), Nb2O5(99.5%), Na2CO3(99.8%) reagent, during to react needed for avoiding Between exceed planned time, should choose as far as possible exquisiteness particle.The raw material of high-purity, impurities part is less, more likely Ensure the purity of product, and its physical arrangement also can be closer to expected product；Live on fine and smooth its surface of particle reagents of quality Change can be higher, helps to increase the contact area of reactant, makes reaction more thorough, the closer expected product of product.According to change The amount that equation calculate each raw material is learned, in the FA2205B types electronic scale electricity of Shanghai Precision Scientific Apparatus Co., Ltd's production (accuracy 0.0001g) is weighed on sub- scale.
(2) ball millings：The raw material that weighing is finished is put into containing agate bead (ZrO after uniformly mixing2) ball grinder in, Add the process that absolute ethyl alcohol is ground as medium.The planetary ball of QM-3SP2 types manufactured using Nanjing Univ. Instrument Factory The rotation of grinding machine, the zirconia ball in ball grinder is driven, and then powder raw material is ground with zirconia ball.Due to by grinding The surface free energy of the powder raw material of mill is higher, the reaction between powdered granule can be made more abundant, therefore ball milling contributes to chemistry The progress of reaction.Because raw material water imbibition is stronger, so to ensure grinding more fully, it is necessary to add 80ml absolute ethyl alcohols.Then Ball milling is carried out with planetary ball mill, and Ball-milling Time is 12 hours, rotating speed 225r/min.
(3) dry：After ball milling, dispensing is taken out, dispensing is poured into the vessel of cleaning, vessel is placed on 90oC's In the 104-9 electric heating air blast thermostatic drying chambers of Hangzhou blue sky assay apparatus factory production, dry 6 hours, wait ethanol to volatilize completely.
(4) pre-burning：Original raw material is set to ultimately generate a kind of process of product.In this flow, the control of calcined temperature It is particularly important, if calcined temperature is too low, may cause to react not thorough, the material made may contain impurity；If pre-burning Temperature is too high, may produce uneven little crystal grain during pre-burning in sample interior, this can cause bad to follow-up every technique Influence, meanwhile, at high operating temperatures, the crystallization water and oxide of sample interior can produce decomposing phenomenon, can cause to a certain degree Gas overflowing, and these processes mostly occur at low-temperature space (before 600 " C), and this requires temperature-rise period too fast[7]。 This research uses powdery pre-burning method, the purpose is to increase the contact area between raw material, makes reaction more thorough.By matching somebody with somebody after drying Material is uniformly poured into Al2O3Crucible, burnt using the KSL-1700X molding box formulas high temperature of Hefei Ke Jing Materials Technology Ltd. production Freezing of a furnace pre-burning 12h at a temperature of 1150oC.
(5) secondary ball milling：The raw material that pre-burning is finished is poured into containing agate bead (ZrO2) ball grinder in, repeat more than Step (2).
(6) dry：Repeat step (3).
(7) it is granulated：In order to obtain the raw material being of close texture, it is necessary to be screened for the material of pre-burning, this process Exactly it is granulated.The dispensing after drying is taken out, is poured into mortar, adds 3ml binder PVA, grinding is uniform, thick in 18mm setting Under degree, using the 769YP-248 powder compressing machines of Tianjin Ke Qi new and high technologies Co., Ltd production, under 14Mpa pressure It is compressed into sheet.After being pressed into sheet, it is put into mortar and crushes, the dispensing of crushing is poured into sieve, upper strata selects 80 mesh, under Layer choosing selects 140 mesh, collects the powder of centre as the raw material that will be sintered；When collecting lower floor's powder as sintering between tabletting Protective layer.
(8) it is molded：In order that will be sintered material after sintering be easier is used (such as measure piezoelectricity, dielectric system Number, density etc.), it is necessary to which material to be made to certain shape.Because the material hardness after oversintering is very big, it is difficult to change shape Shape, therefore we are just made into ideal form before material is through oversintering, this process is exactly to be molded.Use laboratory Mould, under 3.3mm setting thickness, by applying 2Mpa pressure to mould, the sample of 80~140 mesh is pressed into about 1mm thin slice.
(9) dumping：PVA in tabletting is excluded to the process of tabletting.By heating, the PVA in raw material is absorbed heat and vaporize, Overflowed from tabletting.All of every a material and powder are placed on inside a crucible, closed the lid above, but can not be close Envelope, is placed in stove and heats up.Temperature setting is as shown in table 1：
The dumping process temperature of table 1 is set with the time
(10) sinter：By the way of multi-laminate burning, the load bearing board of suitable size is selected, is uniformly plated in load bearing board bottom Dystectic zirconium oxide is as bedding and padding, and using the particle after being granulated as separation layer, top layer uses consistent with sintering composition interlayer Powder prevent from volatilizing, select different temperature to be sintered respectively each sample, in the present embodiment sintering temperature selection 1220 DEG C, 1260 DEG C, sinter 3h at 1300 DEG C and 1340 DEG C.
(11) burning infiltration method prepares electrode：The powdery protective layer on ceramics sample surface is removed first, its surface is polished clean. After polishing, silver paste is uniformly applied to ceramic surface with the writing brush of jewelry, expensive clothing and other valuables.It is worth noting that, between silver paste and edge extremely There are 0.5mm intervals less, otherwise may be in the sintering process in later stage, the silver paste at edge drops onto lower surface, so as to occur The breakdown phenomenon of material in polarization process.After coating, when its naturally dry, capping plate, which is positioned in burner hearth, to be burnt.
(12) polarize：In ferroelectric, consistent zonule is arranged comprising several spontaneous polarization molecule electric moment directions, it is this Zonule we be commonly referred to as electricdomain.Its internal polarised direction of each electricdomain is consistent, therefore individually electricdomain possesses pressure Electrically, we term it single domain state for this property.But polarised direction between electricdomain and electricdomain and differ, in order that material Possess piezoelectricity, it is necessary to which the electricdomain of material internal is arranged in the same direction, i.e., become single domain state from polycrystalline isotropism.Cause This, it would be desirable under the high temperature conditions, apply high-voltage dc, so that material possesses piezoelectricity.This process, is referred to as Polarization.In this research, the HYJH-3-4 types piezoelectric polarization that we are produced using Xianyang Hui Yuan automation equipments Co., Ltd fills Put, under the condition of high temperature (150oC), the polarization of 25 minutes by a definite date is carried out using direct current highfield (4000V).It is noticeable It is that, in order to ensure the success of polarization process, in the temperature-fall period stage after polarization, polarizing voltage should not change.
(13) test：The YE2730A type static measurement instrument produced with Lianneng Science ＆ Technology Co., Ltd. Shanghai determines its piezoelectricity system Number, seen using the JSM-6460 types STUDY ON Scanning Electron Microscope (SEM) and X-ray diffractometer (XRD) of Jeol Ltd.'s production Examine.
The d for the SCNN leadless piezoelectric ceramics that the present embodiment is prepared in each sintering temperature33(pC/N) as shown in table 2 and Fig. 2.
The d of each temperature class SCNN piezoelectric ceramics at room temperature of table 233(pC/N)
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.

Claims (7)

  1. A kind of 1. method for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：The SCNN leadless piezoelectrics pottery The composition formula of porcelain is：Sr2-xCaxNaNb5O15, wherein：X is molar fraction；The leadless piezoelectric ceramics uses synthesis in solid state legal system Standby, it is 0.14-0.155 to control it to form the scope of x in formula in preparation process.
  2. 2. the method according to claim 1 for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：It is described In SCNN leadless piezoelectric ceramics preparation process, work as x=0.14-0.155, with the pressure of piezoelectric ceramics prepared by the rise of sintering temperature Electrically show the rule fall before, raise again, declining again；Meanwhile density, unit cell dimension and the dielectric property of the piezoelectric ceramics Also the rule is presented.
  3. 3. the method according to claim 2 for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：X= 0.145。
  4. 4. according to any described methods for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics of claim 1-3, its feature exists In：This method is solid-phase synthesis, is specifically comprised the following steps：
    (1) dispensing：With analytically pure SrCO3(99.5%), CaCO3(99%), Nb2O5And Na (99.5%)2CO3(99.8%) it is Raw material, dispensing is carried out according to the composition of the leadless piezoelectric ceramics；
    (2) ball millings：It will be put into after each raw material uniformly mixing containing agate bead (ZrO2) ball grinder in, using absolute ethyl alcohol as Medium carries out ball milling, and drying and processing is carried out after ball milling；Wherein：Ball-milling Time is 12 hours, rotating speed 225r/min；At drying It is 90 DEG C to manage temperature, is dried to ethanol and volatilizees completely (about 6 hours)；
    (3) pre-burning：Compound after drying is put into Al2O3In crucible, using high temperature sintering furnace in 1150 DEG C of pre-burning 12h；
    (4) secondary ball milling：The raw material that pre-burning is finished is poured into containing agate bead (ZrO2) ball grinder in, repeat step (2) ball milling And drying course；
    (5) it is granulated：The sample after drying is taken out, addition 3mL binders PVA is granulated；Filter out the sample of the mesh of 80 mesh of granularity -140 As raw materials for sintering；
    (6) shaping and dumping：Apply 2MPa pressure to mould, the sample of 80~140 mesh is pressed into about 1mm thin slice, and The PVA suppressed in thin slice is excluded into tabletting；
    (7) sinter：By the way of multi-laminate burning, the load bearing board of suitable size is selected, oxidation is uniformly plated in load bearing board bottom As bedding and padding, the powder that interlayer is more than 80 mesh using granularity after being granulated uses with sintering component particle size zirconium as separation layer, top layer Consistent powder prevents from volatilizing, and sintering temperature is 1200-1450 DEG C, sintering time 2-4h.
    (8) prepare electrode and polarize：Polarized after preparing electrode using burning infiltration method, during polarization under the conditions of 150 DEG C, used 4000V/mm direct currents highfield carries out the polarization of 25 minutes by a definite date.
  5. 5. the method according to claim 4 for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：Step (5) in, the granulation process is：After adding binder in the sample, grinding is uniform；Then using powder compressing machine in 14MPa Pressure under be compressed into piece, thickness in blocks is 18mm；Place into mortar and crush, the sample of crushing is poured into sieve, receive Collect the mesh powder of 80 mesh -140 as the raw material that will be sintered；Collect when being more than 140 mesh powders as sintering between tabletting Protective layer.
  6. 6. the method according to claim 4 for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：Step (6) in, during the PVA suppressed in thin slice is excluded into tabletting, by heating, the PVA in thin slice is absorbed heat and vaporize, from pressure Overflowed in piece.
  7. 7. the method according to claim 4 for preparing tungsten bronze structure SCNN leadless piezoelectric ceramics, it is characterised in that：Step (8) in, use burning infiltration method prepare the process of electrode for：The powdery protective layer on ceramics sample surface is removed first, and its surface is beaten Mill is clean；Then silver paste is brushed in ceramic surface, is sintered after naturally dry.
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