CN107235725A - Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation - Google Patents

Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation Download PDF

Info

Publication number
CN107235725A
CN107235725A CN201710331452.1A CN201710331452A CN107235725A CN 107235725 A CN107235725 A CN 107235725A CN 201710331452 A CN201710331452 A CN 201710331452A CN 107235725 A CN107235725 A CN 107235725A
Authority
CN
China
Prior art keywords
tungsten bronze
solution
sections
powder
tacl
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
CN201710331452.1A
Other languages
Chinese (zh)
Inventor
王卓
肖雨佳
王春
王添
陈浩楠
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 CN201710331452.1A priority Critical patent/CN107235725A/en
Publication of CN107235725A publication Critical patent/CN107235725A/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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/62635—Mixing details
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium 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
    • C04B2235/02—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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The tungsten bronze sections barium tantalate powder and method prepared the present invention relates to a kind of coprecipitation, first prepares Ba (NO3)2The aqueous solution, and to Ba (NO3)2Fe (NO are added in the aqueous solution3)3·9H2O, instills 1~3 and drips hydrogen peroxide, obtain mixed solution A after stirring；Wherein, Ba (NO3)2With Fe (NO3)3·9H2O mol ratio is 1:6~1:8；Prepare TaCl5Ethanol solution and add in mixed solution A, it is well mixed to obtain mixed solution B；Wherein, TaCl5With the Ba (NO of step (1)3)2Mol ratio be 6:6~6:9；Mixed solution B is titrated with aqueous slkali, obtains being co-precipitated presoma；Co-precipitation presoma is washed and dried, is then calcined at 1150~1250 DEG C, tungsten bronze sections barium tantalate powder is obtained.Powder purity produced by the present invention is high, good dispersion, compact structure and crystal grain is tiny.

Description

Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation
Technical field
Powder technology field is prepared the invention belongs to wet chemistry method, and in particular to tungsten bronze type prepared by a kind of coprecipitation Iron barium tantalate powder and method.
Background technology
The problems such as due to environment and resource pollution, people started using the leaded material of leadless electronic material substitution in recent years, Typical ABO3Type perovskite structure is used as the leadless piezoelectric material material being employed earliest.But the phase transformation near certain temperature causes Its dielectric properties is such as：Temperature stability is poor, limits application of the perovskite structure ceramics in high temperature and low-temperature region.Because Tungsten bronze type structure ferroelectric is the second major class ferroelectric for being only second to perocskite type, with its own excellent ferroelectricity, piezoelectricity, heat The performances such as electricity and nonlinear optics are released, are widely used in the fields such as capacitor, memory, driver and detector so that tungsten One upsurge of research as scientific circles of bronze type dielectric substance.Thus, tungsten bronze system receives the extensive pass of people Note, in recent years, is found that a series of high-ks (ε=120~180), low dielectric are damaged in the tantalic acid salt system of tungsten bronze Consume (tan δ=10-4) dielectric ceramic.Therefore, people have carried out a large amount of fruitful researchs, synthesized it is many it is new it is orthogonal, The tungsten bronze of tetragonal crystal system, such as Ba6FeTa9O30New type tungsten bronze crystal is full of etc. large quantities of.
In Ba6FeTa9O30The Fe and Ta of middle B bits element can cause the inhomogeneities of micro-area composition in structure, improve relaxation Disperse degree, so that widthization dielectric peak, improves the dielectric properties of tungsten bronze structure ceramic, its temperature stability is improved, while powder The granularity and uniformity of body is also the key factor for determining its dielectric properties.For now, almost all of tungsten bronze knot The ceramics of structure are all prepared with solid phase method, but are due to that traditional solid phase method powder preparation technology requires rougher, resulting Powder grain size it is larger, not only limit the slimming of dielectric layer, and easily cause the fluctuating of electronic device performance.
The content of the invention
For problems of the prior art, the present invention provides tungsten bronze sections barium tantalate prepared by a kind of coprecipitation Powder and method, this method technique are simple, and the cycle is short and saves the energy, diameter of particle is made small and uniform.
In order to achieve the above object, the present invention is to be achieved through the following technical solutions：
Comprise the following steps,
(1) Ba (NO are prepared3)2The aqueous solution, and to Ba (NO3)2Fe (NO are added in the aqueous solution3)3·9H2O, after stirring Instill 1~3 and drip hydrogen peroxide, obtain mixed solution A；Wherein, Ba (NO3)2With Fe (NO3)3·9H2O mol ratio is 1:6~1:8；
(2) TaCl is prepared5Ethanol solution and add in mixed solution A, it is well mixed to obtain mixed solution B；Wherein, TaCl5With the Ba (NO of step (1)3)2Mol ratio be 6:6~6:9；
(3) mixed solution B is titrated with aqueous slkali, obtains Ba6FeTa9O30Co-precipitation presoma；
(4) to Ba6FeTa9O30Co-precipitation presoma washed and dried, then at 1150~1250 DEG C calcine, Obtain tungsten bronze sections barium tantalate powder.
Further, in step (1), Ba (NO3)2The concentration of the aqueous solution is 0.06~0.09mol/L；Ba(NO3)2It is water-soluble Liquid and Fe (NO3)3·9H2The O mixing time is 1~2h.
Further, in step (1), the hydrogen peroxide volumetric concentration of dropwise addition is 30%.
Further, TaCl is prepared in step (2)5Ethanol solution when, TaCl5Dissolved stirring time be 10~15h； TaCl5Ethanol solution add mixed solution A in, stirring 1~2h after obtain mixed solution B.
Further, in step (2), TaCl5Ethanol solution concentration be 0.08~0.10mol/L.
Further, in step (3), aqueous slkali use volumetric concentration for 25%~28% NH3·H2O solution；NH3· H2O solution drop rate is 0.5~2mL/min, and stirred when being added dropwise that mixing time is 20~30min.
Further, in step (3), aqueous slkali titration mixed solution B is until pH value reaches 10~12 generation sepias Precipitation, obtains Ba6FeTa9O30Co-precipitation presoma.
Further, in step (4), Ba6FeTa9O30Co-precipitation presoma adopt and be washed with deionized 8~12 times；Or By 4~6 deionized water centrifuge washings, wherein centrifugation rate is 3000~5000r/min, the single spin time is 5~ 10min；Drying temperature is 80~100 DEG C.
Further, in step (4), the time of calcining is 2~3h.
One kind utilizes as above tungsten bronze sections barium tantalate powder made from method, it is characterised in that the particle diameter of the powder exists 200~400nm.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention prepares tungsten bronze type Ba using the coprecipitation of high-efficient simple6FeTa9O30Powder, tradition different from the past Solid phase method, the inventive method have the advantages that it is simpler efficiently and save the energy.Compared to other method is utilized, by this Constitutionally stable tungsten bronze type Ba can be made by planting controllable wet chemistry method6FeTa9O30Powder, this method first prepares Nb5+Before Liquid solution is driven, the Fe that hydrogen peroxide solution prevents from adding later is instilled3+It is reduced to Fe2+, while hydrogen peroxide is as accelerator and surely Determine agent, make powder granule evenly；By the source of iron and barium source sequentially added, the accurate control to stoichiometric proportion is realized, most Afterwards with aqueous slkali and after generation precipitation, drying calcining obtains product, and preparation technology is simple, and powder is uniform；By controlling calcining System, and suitable temperature is set, so as to improve the dissolution rate of calcined product, it is ensured that the purity of product and the utilization of raw material Rate；The present invention is beneficial to large-scale production, and the reaction time also greatly shortens, and reaction temperature is greatly lowered, simple to operate, work Skill is reproducible.So as to improve conventional solid-state method prepare the grain size brought during the powder larger, skewness, reality Test cycle length, calcining heat height and the low shortcoming of sinterability.
Further, by controlling TaCl5In the mixing time of absolute ethyl alcohol so that TaCl5It can be completely dissolved, so as to carry The accuracy of high stoichiometric proportion.
Further, by controlling the mixing time of mixed solution, so as to improve the uniformity of predecessor, so as to ensure The purity of product.
Further, by setting NH3·H2The rate of titration of O solution, and the multiple washing to sediment, are improved The purity of sample, it is ensured that its diameter of particle it is uniform.
Tungsten bronze type Ba prepared by the inventive method6FeTa9O30Powder purity is high, and good dispersion uniformly divides in corynebacterium Cloth, particle diameter is in 200~400nm, compact structure and crystal grain is tiny, the tungsten bronze type Ba for using the present invention to prepare6FeTa9O30Powder Body, can not only reduce the crystallite dimension of later stage ceramics, and the dielectric properties and multi-ferrum property of ceramics can be caused to obtain pole The earth improves so that the material is suitable for wider environmental condition, drastically increases its application value.
Brief description of the drawings
Fig. 1 is Ba prepared by the embodiment of the present invention 46FeTa9O30Powder X ray diffracting spectrum.
Fig. 2 is Ba prepared by the embodiment of the present invention 46FeTa9O30The SEM that powder amplifies in 80.0k multiples Image.
Fig. 3 is Ba prepared by the embodiment of the present invention 46FeTa9O30The SEM that powder amplifies in 6.00k multiples Image.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
A kind of coprecipitation of the present invention prepares tungsten bronze type Ba6FeTa9O30The method of powder, technique is simple, reaction temperature Low, the time is short, and the diameter of particle for can greatly save the energy, preparing is small, and stoichiometric proportion is controllable, to tungsten bronze type Ba6FeTa9O30It is a kind of excellent preparation method for powder synthesis.Specific such as following examples.
Embodiment 1
(1) compound concentration is 0.06mol/L Ba (NO3)2The aqueous solution；
(2) Ba (NO are pressed3)2With Fe (NO3)3·9H2O mol ratios are 1:6, by Fe (NO3)3·9H2O adds institute while stirring Ba (the NO obtained3)2In the aqueous solution, and continue stirring until solution colour uniformly, and it is 30% to instill 1 drop volume fraction thereto Hydrogen peroxide, obtains mixed solution A, and when being well mixed, mixing time is 1h.
(3) by TaCl5Add in appropriate absolute ethyl alcohol, be placed in magnetic stirring apparatus persistently stirring 10h, until TaCl5 It is completely dissolved, obtains the TaCl that concentration is 0.08mol/L5Ethanol solution；Wherein TaCl5With the Ba (NO of step (1)3)2Mole Than for 1:1；
(4) by TaCl under stirring5Ethanol solution be slowly added in mixed solution A, be sufficiently mixed it is uniform after To mixed solution B, mixing time is 1h.
(5) with the NH that volumetric concentration is 25%3·H2O solution titrates mixed solution B, controls NH3·H2O solution titration speed Rate is 0.5mL/min, and is quickly stirred when being added dropwise, and mixing time is 20min, until mixed solution B pH value is produced when reaching 10 Raw brown precipitation, forms Ba6FeTa9O30Co-precipitation presoma.
(6) washed 8 times or centrifuged 4 times using deionized water respectively with deionized water, centrifugation rate is 3000r/min, it is single Secondary centrifugation time is 5min, the Ba after filter washing or centrifugation6FeNb9O30Precursor solution is then heavy by what is be filtrated to get Starch calcines 2h at 1150 deg.f in 80 DEG C of drying, obtains the tungsten bronze type Ba that particle diameter is about 200nm6FeTa9O30Powder.
Embodiment 2
(1) compound concentration is 0.07mol/L Ba (NO3)2The aqueous solution；
(2) Ba (NO are pressed3)2With Fe (NO3)3·9H2O mol ratios are 1:6, by Fe (NO3)3·9H2O adds institute while stirring Ba (the NO obtained3)2Solution colour is continued stirring until in the aqueous solution uniformly, and instills the dioxygen that 2 drop volume fractions are 30% thereto Water, obtains mixed solution A, and when being well mixed, mixing time is 1.2h.
(3) by TaCl5Add in appropriate absolute ethyl alcohol, be placed in magnetic stirring apparatus persistently stirring 12h, until TaCl5 It is completely dissolved, obtains the TaCl that concentration is 0.08mol/L5Ethanol solution；Wherein TaCl5With the Ba (NO of step (1)3)2Mole Than for 6：7.
(4) by TaCl under stirring5Ethanol solution be slowly added in mixed solution A, be sufficiently mixed it is uniform after To mixed solution B, mixing time is 1h.
(5) with the NH that volumetric concentration is 25%3·H2O solution titrates mixed solution B, controls NH3·H2O solution titration speed Rate is 1mL/min, stirs 25min, until mixed solution B pH value produces brown precipitation when reaching 10.50, is formed Ba6FeTa9O30Co-precipitation presoma.
(6) washed 9 times or centrifuged 4 times using deionized water respectively with deionized water, centrifugation rate is 3000r/min, it is single Secondary centrifugation time is 7min, the Ba after filter washing or centrifugation6FeNb9O30Precursor solution is then heavy by what is be filtrated to get Starch calcines 2h in 80 DEG C of drying at 1150 DEG C, obtains the tungsten bronze type Ba that particle diameter is about 250nm6FeTa9O30Powder.
Embodiment 3
(1) compound concentration is 0.07mol/L Ba (NO3)2The aqueous solution；
(2) Ba (NO are pressed3)2With Fe (NO3)3·9H2O mol ratios are 1:7, by Fe (NO3)3·9H2O adds institute while stirring Ba (the NO obtained3)2Solution colour is continued stirring until in the aqueous solution uniformly, and instills the dioxygen that 2 drop volume fractions are 30% thereto Water, obtains mixed solution A, and when being well mixed, mixing time is 1.8h.
(3) by TaCl5Add in appropriate absolute ethyl alcohol, be placed in magnetic stirring apparatus persistently stirring 13h, until TaCl5 It is completely dissolved, obtains the TaCl that concentration is 0.09mol/L5Ethanol solution；Wherein TaCl5With the Ba (NO of step (1)3)2Mole Than for 6:8.
(4) by TaCl under stirring5Ethanol solution be slowly added in mixed solution A, be sufficiently mixed it is uniform after To mixed solution B, mixing time is 1.5h.
(5) with the NH that volumetric concentration is 27%3·H2O solution titrates mixed solution B, controls NH3·H2O solution titration speed Rate is 1mL/min, stirs 25min, until mixed solution B pH value produces brown precipitation when reaching 11.00, is formed Ba6FeTa9O30Co-precipitation presoma.
(6) washed 10 times or centrifuged 5 times using deionized water respectively with deionized water, centrifugation rate is 4000r/min, it is single Secondary centrifugation time is 8min, the Ba after filter washing or centrifugation6FeNb9O30Precursor solution is then heavy by what is be filtrated to get Starch calcines 2.5h in 90 DEG C of drying at 1200 DEG C, obtains the tungsten bronze type Ba that particle diameter is about 350nm6FeTa9O30Powder.
Embodiment 4
(1) compound concentration is 0.08mol/L Ba (NO3)2The aqueous solution；
(2) Ba (NO are pressed3)2With Fe (NO3)3·9H2O mol ratios are 1:8, by Fe (NO3)3·9H2O adds institute while stirring Ba (the NO obtained3)2Solution colour is continued stirring until in the aqueous solution uniformly, and instills the dioxygen that 3 drop volume fractions are 30% thereto Water, obtains mixed solution A, and when being well mixed, mixing time is 2h.
(3) by TaCl5Add in appropriate absolute ethyl alcohol, be placed in magnetic stirring apparatus persistently stirring 14h, until TaCl5 It is completely dissolved, obtains the TaCl that concentration is 0.1mol/L5Ethanol solution；Wherein TaCl5With the Ba (NO of step (1)3)2Mole Than for 6:9.
(4) by TaCl under stirring5Ethanol solution be slowly added in mixed solution A, be sufficiently mixed it is uniform after To mixed solution B, mixing time is 2h.
(5) with the NH that volumetric concentration is 28%3·H2O solution titrates mixed solution B, controls NH3·H2O solution titration speed Rate is 2mL/min, stirs 30min, until mixed solution B pH value produces brown precipitation when reaching 11.50, is formed Ba6FeTa9O30Co-precipitation presoma.
(6) washed 11 times or centrifuged 6 times using deionized water respectively with deionized water, centrifugation rate is 5000r/min, it is single Secondary centrifugation time is 9min, the Ba after filter washing or centrifugation6FeNb9O30Precursor solution is then heavy by what is be filtrated to get Starch calcines 3h in 100 DEG C of drying at 1200 DEG C, obtains tungsten bronze type Ba6FeTa9O30Powder.
By test, as a result as shown in Figure 1 to Figure 3, as can be seen from Figure 1, produced by the present invention is the tungsten bronze of pure phase Structure；From figure 2, it is seen that individual particle particle diameter is in 200~300nm；As can be seen from Figure 3, even particle distribution.
Embodiment 5
(1) compound concentration is 0.09mol/L Ba (NO3)2The aqueous solution；
(2) Ba (NO are pressed3)2With Fe (NO3)3·9H2O mol ratios are 1:8, by Fe (NO3)3·9H2O adds institute while stirring Ba (the NO obtained3)2Solution colour is continued stirring until in the aqueous solution uniformly, and instills the dioxygen that 3 drop volume fractions are 30% thereto Water, obtains mixed solution A, and when being well mixed, mixing time is 2h.
(3) by TaCl5Add in appropriate ethanol solution, be placed in magnetic stirring apparatus persistently stirring 15h, until TaCl5It is completely dissolved, obtains the TaCl that concentration is 0.1mol/L5Ethanol solution；Wherein TaCl5With the Ba (NO of step (1)3)2's Mol ratio is 6:9.
(4) by TaCl under stirring5Ethanol solution be slowly added in mixed solution A, be sufficiently mixed it is uniform after To mixed solution B, mixing time is 2h.
(5) with the NH that volumetric concentration is 28%3·H2O solution titrates mixed solution B, controls NH3·H2O solution titration speed Rate is 2mL/min, stirs 30min, until mixed solution B pH value produces brown precipitation when reaching 12.00, is formed Ba6FeTa9O30Co-precipitation presoma.
(6) washed 12 times or centrifuged 6 times using deionized water respectively with deionized water, centrifugation rate is 5000r/min, it is single Secondary centrifugation time is 10min, the Ba after filter washing or centrifugation6FeNb9O30Precursor solution is then heavy by what is be filtrated to get Starch calcines 3h in 100 DEG C of drying at 1250 DEG C, obtains the tungsten bronze type Ba that particle diameter is about 400nm6FeTa9O30Powder.
Comparative example 1
By Ba (NO3)2With Fe (NO3)3·9H2O mol ratio is changed to 1 respectively:5,1:9, other condition be the same as Examples 1.
The tungsten bronze type Ba of pure phase can not be formed through XRD tests6FeTa9O30Powder, therefore, Ba (NO3)2And Fe (NO3)3·9H2The scope of O mol ratio is 1:6~1:8.
Comparative example 2
The powder calcination time after drying is changed to 1.5h and 4h, other condition be the same as Examples 1 respectively.
Tested through XRD, the powder that calcination time is changed to 1.5h can not form the tungsten bronze type Ba of pure phase6FeTa9O30Powder Body, there is a small amount of dephasign.The powder for being changed to 4h respectively through XRD test calcination times is pure phase, and tests its powder grain through SEM Footpath size is excessively big, reaches 800 μm, particle diameter crosses conference influence performance.Therefore, the powder calcination time after drying should be 2~3h.
Compared with traditional preparation methods, chemical precipitation method of the present invention uses liquid phase synthesis, significantly overcomes tradition side The shortcoming of method, can obtain that thing is mutually pure, yardstick is smaller, good dispersion powder at low temperature, so as in low sintering temperature Lower obtain has compact texture and the tiny ceramic material with superior dielectric performance of crystal grain.This not only reduces the wave of the energy Take, further improve the dielectric properties of tungsten bronze type ceramics.Therefore, had using chemical precipitation method preparation function electronic ceramics important Research and application value.

Claims (10)

1. a kind of method that coprecipitation prepares tungsten bronze sections barium tantalate powder, it is characterised in that comprise the following steps,
(1) Ba (NO are prepared3)2The aqueous solution, and to Ba (NO3)2Fe (NO are added in the aqueous solution3)3·9H2O, 1 is instilled after stirring ~3 drop hydrogen peroxide, obtain mixed solution A；Wherein, Ba (NO3)2With Fe (NO3)3·9H2O mol ratio is 1:6~1:8；
(2) TaCl is prepared5Ethanol solution and add in mixed solution A, it is well mixed to obtain mixed solution B；Wherein, TaCl5With Ba (the NO of step (1)3)2Mol ratio be 6:6~6:9；
(3) mixed solution B is titrated with aqueous slkali, obtains Ba6FeTa9O30Co-precipitation presoma；
(4) to Ba6FeTa9O30Co-precipitation presoma washed and dried, then at 1150~1250 DEG C calcine, obtain Tungsten bronze sections barium tantalate powder.
2. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In, in step (1), Ba (NO3)2The concentration of the aqueous solution is 0.06~0.09mol/L；Ba(NO3)2The aqueous solution and Fe (NO3)3· 9H2The O mixing time is 1~2h.
3. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In in step (1), the hydrogen peroxide volumetric concentration of dropwise addition is 30%.
4. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In preparation TaCl in step (2)5Ethanol solution when, TaCl5Dissolved stirring time be 10~15h；TaCl5Ethanol solution Add in mixed solution A, mixed solution B is obtained after 1~2h of stirring.
5. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In, in step (2), TaCl5Ethanol solution concentration be 0.08~0.10mol/L.
6. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In, in step (3), aqueous slkali use volumetric concentration for 25%~28% NH3·H2O solution；NH3·H2O solution drop rates For 0.5~2mL/min, and stirred when being added dropwise, mixing time is 20~30min.
7. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In in step (3), aqueous slkali titration mixed solution B reaches the precipitations of 10~12 generation sepias up to pH value, obtains Ba6FeTa9O30Co-precipitation presoma.
8. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In, in step (4), Ba6FeTa9O30Co-precipitation presoma adopt and be washed with deionized 8~12 times；Or by go for 4~6 times from Sub- water centrifuge washing, wherein centrifugation rate are 3000~5000r/min, and the single spin time is 5~10min；Drying temperature is 80~100 DEG C.
9. the method that a kind of coprecipitation according to claim 1 prepares tungsten bronze sections barium tantalate powder, its feature exists In in step (4), the time of calcining is 2~3h.
10. one kind utilizes tungsten bronze sections barium tantalate powder made from claim 1 methods described, it is characterised in that the powder Particle diameter in 200~400nm.
CN201710331452.1A 2017-05-11 2017-05-11 Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation Pending CN107235725A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710331452.1A CN107235725A (en) 2017-05-11 2017-05-11 Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710331452.1A CN107235725A (en) 2017-05-11 2017-05-11 Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation

Publications (1)

Publication Number Publication Date
CN107235725A true CN107235725A (en) 2017-10-10

Family

ID=59984371

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710331452.1A Pending CN107235725A (en) 2017-05-11 2017-05-11 Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation

Country Status (1)

Country Link
CN (1) CN107235725A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125987A1 (en) * 2009-04-27 2010-11-04 Canon Kabushiki Kaisha Tungsten bronze-type piezoelectric material and production method therefor
CN103833082A (en) * 2014-01-13 2014-06-04 陕西科技大学 Method for preparing nanometer Ba(Fe0.5Nb0.5)O3 powder by coprecipitation
CN106032320A (en) * 2016-05-23 2016-10-19 陕西科技大学 Method for preparing nanometer Ba(Fe0.5Ta0.5)O3 powder with low cost
CN106478098A (en) * 2016-09-29 2017-03-08 陕西科技大学 A kind of microwave-hydrothermal method prepares tungsten bronze type nanometer Ba6FeNb9O30The method of powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125987A1 (en) * 2009-04-27 2010-11-04 Canon Kabushiki Kaisha Tungsten bronze-type piezoelectric material and production method therefor
CN103833082A (en) * 2014-01-13 2014-06-04 陕西科技大学 Method for preparing nanometer Ba(Fe0.5Nb0.5)O3 powder by coprecipitation
CN106032320A (en) * 2016-05-23 2016-10-19 陕西科技大学 Method for preparing nanometer Ba(Fe0.5Ta0.5)O3 powder with low cost
CN106478098A (en) * 2016-09-29 2017-03-08 陕西科技大学 A kind of microwave-hydrothermal method prepares tungsten bronze type nanometer Ba6FeNb9O30The method of powder

Similar Documents

Publication Publication Date Title
CN103833082B (en) A kind of coprecipitation method prepares nanometer Ba (Fe 0.5nb 0.5) O 3the method of powder
CN103606669A (en) Preparation method of trivalent scandium or chromium-doped spinel-type lithium-rich lithium manganate cathode material
CN103594704B (en) The preparation method of the spinel lithium-rich lithium manganate cathode material of doping titanic ion
CN107235725A (en) Tungsten bronze sections barium tantalate powder and method prepared by a kind of coprecipitation
CN107903072B (en) Method for preparing strontium barium niobate nano powder by two-step coprecipitation method
CN103594706A (en) Preparation method for yttrium-doped spinel lithium-rich lithium manganate positive electrode material
CN103992102A (en) Sol-gel preparation method for copper yttrium titanate giant dielectric ceramic material
CN103594703A (en) Preparation method of divalent cation-doped spinel lithium-rich lithium manganate cathode material
CN103594700A (en) Preparation method of vanadium-doped spinel lithium-rich lithium manganate cathode material
CN104108931B (en) A kind of preparation method of submicron rank relaxation ferroelectric
CN108726877B (en) High-temperature spinning glass Ca3CoMnO6Preparation method of (1)
CN103594702A (en) Method for preparing tin-doped spinel lithium-rich lithium manganate cathode material by using two-stage sintering process
CN103594701A (en) Preparation method of nickel-doped spinel lithium-rich lithium manganate cathode material
CN106865612B (en) A kind of coprecipitation prepares the method that indium niobium is co-doped with titanium dioxide powder
CN103746105A (en) Method for preparing spinel type lithium-rich lithium manganate cathode material by doping molybdenum ions
CN109850938B (en) Preparation method of strontium titanate spherical nanocrystal
CN106892450A (en) One kind synthesizes PbTiO by La ion dopings3The method of disk
CN109712819B (en) KNb3O8Preparation method of nanosheet/carbon cloth composite material
CN104030684B (en) A kind of coprecipitation method prepares nanometer Sr (Fe 0.5nb 0.5) O 3the method of powder
CN104496462B (en) A kind of coprecipitation prepares nanometer Ba [(Fe0.5nb0.5)xti1-x] O3the method of powder body
CN105645476B (en) A kind of microwave-hydrothermal method prepares nanometer Sr (Fe0.5Nb0.5)O3The method of powder
CN107188558B (en) A kind of alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density and preparation method thereof
CN103992103A (en) Binary-system copper yttrium titanate-strontium titanate giant dielectric ceramic material and preparation method thereof
CN109399708A (en) A kind of spherical bismuth-sodium titanate powder and preparation method thereof of hydro-thermal method preparation
CN103594705A (en) Preparation method for tetravalent rare earth ion-doped spinel lithium-rich lithium manganate positive electrode material

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: 20171010