CN106007705B - A kind of perovskite-like layer structure system solid solution material and preparation method thereof - Google Patents

A kind of perovskite-like layer structure system solid solution material and preparation method thereof Download PDF

Info

Publication number
CN106007705B
CN106007705B CN201610313241.0A CN201610313241A CN106007705B CN 106007705 B CN106007705 B CN 106007705B CN 201610313241 A CN201610313241 A CN 201610313241A CN 106007705 B CN106007705 B CN 106007705B
Authority
CN
China
Prior art keywords
powder
perovskite
source compound
solid solution
manganese
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.)
Active
Application number
CN201610313241.0A
Other languages
Chinese (zh)
Other versions
CN106007705A (en
Inventor
陆亚林
王建林
陈泽志
彭冉冉
傅正平
黄浩亮
刘宇
邹维
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.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
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 University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN201610313241.0A priority Critical patent/CN106007705B/en
Publication of CN106007705A publication Critical patent/CN106007705A/en
Application granted granted Critical
Publication of CN106007705B publication Critical patent/CN106007705B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/475—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
    • 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
    • C04B2235/3213—Strontium 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide 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
    • C04B2235/30—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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate

Landscapes

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

Abstract

The present invention is inserted into bismuth Layered Perovskite Bi for LSMO layers by perovskite structure4Ti3O12In material, the Bi under specific components is realized4Ti3O12‑La1‑xSrxMnO3It is dissolved single_phase system new material.Such new material has four layers of perovskite-like layer structure, meet the structure feature of Aurivillius phase materials, simultaneously again with the adjustable characteristic of semiconductor of resistivity in a certain range, the high resistance insulation characterisitic for greatly reducing original bismuth titanates class material has expanded application potential of this kind of material in the field of functional materials such as semiconductor devices, the energy, information.

Description

A kind of perovskite-like layer structure system solid solution material and preparation method thereof
Technical field
The invention belongs to technical field of ceramic material, and in particular to a kind of perovskite-like layer structure system solid solution material and Preparation method.
Background technology
Bismuth laminated Aurivillius phase materials be it is a series of have Perovskite-type oxides functional material, General structure is (Bi2O2)(An-1BnO3n+1), wherein n is more than or equal to 1, A and indicates 12 larger coordination cations of ionic radius, B Indicate smaller 6 coordination cations [document Aurivillius B., Ark.Kemi., 463 (1949)] of ionic radius.This kind of material The structure of material is by bismuth oxygen layer (Bi2O2 2+) and perovskite-like layer (An-1BnO3n+1 2-) be alternately stacked and formed on c-axis direction, wherein Perovskite-like layer is the thickness of n-layer octahedral layer.Aurivillius phases bismuth Layered Perovskite structure is made pottery in multilayered structure at present Porcelain condenser [patent US5638252A, J.D.Drab, et al., 1995], non-volatile ferroelectric random access memory [document C.A-P.D.Araujo,et al.,Nature,374:627 (1995)], leadless piezoelectric device [patent CN104402433A, Pu Yongping etc., 2015] and magneto-electric coupled function multi-iron material [document Jianlin Wang, et al., Materials Horizons,2:232 (2015)] etc. fields be widely used.
Bismuth titanates (Bi4Ti3O12, BTO) and it is typical bismuth-containing laminated perovskite structure, by 2 (Bi2O2)2+3 are pressed from both sides between layer The octahedra calcium titanium ore bed constituted of layer titanyl (Ti-O) forms similar sandwich structure [document N.A.Lomanova, et al.Inorganic Materials.42,189(2006)].BTO materials with~675 DEG C of high-curie temperature point and it is big from Hair polarization.This excellent ferroelectric properties is thought to originate from Bi3+The 6s of ion2Lone electron pair.Bismuth titanates and its dopant material Generally there is high-insulativity, dielectric constant, while it generally has good ferroelectricity, piezoelectricity and higher Curie transition temperature Degree, and because being free of lead, there is environment friendly, in non-volatility ferroelectric random access memory and high temperature ferroelectricity, piezoelectric device Etc. have wide practical use.Currently, bismuth titanates class material generally has high resistivity, such as patent CN104402433A Its Bi is disclosed4Ti3O12The room temperature resistivity of material is up to 1 × 106Good insulating properties is presented in cm or more, however in some applications Occasion, it is intended that material has semiconductor property, to adapt to loss requirement of the device under specific occasion, and in energy The application in source, functional material (such as oxide semiconductor, thermoelectric material) etc..Therefore, chemistry is carried out to bismuth titanates class material The improvement and innovation of composition obtain the bismuth laminated oxide material with certain conductive capability, become and meet specified conditions The research direction that lower device material requires.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of perovskite-like layer structure system solid solution material Material and preparation method thereof, perovskite-like layer structure system solid solution material provided by the invention meets Aurivillius phase materials Structure feature, while again have a certain range in the adjustable characteristic of semiconductor of resistivity.
The present invention provides a kind of perovskite-like layer structure system solid solution materials, have molecular formula shown in formula (I)：
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
The present invention also provides a kind of perovskite-like layer structure system solid solution materials with molecular formula shown in formula (I) Preparation method, include the following steps：
A) bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound are mixed, obtained Mixed powder；
B it is ground after the mixed powder) is carried out pre-burning, obtains initial powder；
C it is sintered after) being molded the initial powder, obtains the perovskite-like layer with molecular formula shown in formula (I) Shape structure system solid solution material；
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
Preferably, the bismuth source compound is selected from bismuth oxide or five nitric hydrate bismuths；
The lanthanum source compound is selected from lanthana or lanthanum nitrate hydrate；
The barium source compound is selected from strontium carbonate or strontium nitrate；
The manganese source compound is selected from manganese dioxide, four hydration manganese acetates, four acetate hydrate manganese or manganese nitrate hydrate；
The titanium source compound is selected from titanium dioxide or tetrabutyl titanate.
The present invention also provides a kind of perovskite-like layer structure system solid solution materials with molecular formula shown in formula (I) Preparation method, include the following steps：
A) by Bi4Ti3O12Powder and La1-xSrxMnO3Powder mixes, and obtains mixed powder；
B) it is ground after the mixed powder being carried out pre-burning, obtains initial powder；
C) it is sintered after being molded the initial powder, obtains the perovskite-like layer with molecular formula shown in formula (I) Shape structure system solid solution material；
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
Preferably, the temperature of the pre-burning is 700~900 DEG C, and the time of the pre-burning is 2~5h.
Preferably, the heating rate of the pre-burning is 3~8 DEG C/min.
Preferably, the temperature of the sintering is 900~1000 DEG C, and the time of the sintering is 2~6h.
Preferably, the heating rate of the sintering is 1~5 DEG C/min.
Preferably, the Bi4Ti3O12Powder and La1-xSrxMnO3The molar ratio of powder is 1:1.
Compared with prior art, the present invention provides a kind of perovskite-like layer structure system solid solution materials, have formula (I) Shown in molecular formula：Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.The present invention is inserted for LSMO layers by perovskite structure Enter bismuth Layered Perovskite Bi4Ti3O12In material, the Bi under specific components is realized4Ti3O12-La1-xSrxMnO3It is dissolved single-phase System new material.Such new material has four layers of perovskite-like layer structure, and the structure for meeting Aurivillius phase materials is special Sign, while there is the adjustable characteristic of semiconductor of resistivity in a certain range again, greatly reduce the height of original bismuth titanates class material Resistance insulation characteristic has expanded application potential of this kind of material in the field of functional materials such as semiconductor devices, the energy, information.
The result shows that resistivity of the perovskite-like layer structure system solid solution material provided by the invention in room temperature is 0.68~8 × 104Ω·cm。
Description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of sample in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of sample in the embodiment of the present invention 1；
Fig. 3 is the resistivity of sample in the embodiment of the present invention 1 with temperature curve；
Fig. 4 is the X-ray diffractogram (XRD) of sample in the embodiment of the present invention 2；
Fig. 5 is the resistivity of sample in the embodiment of the present invention 2 with temperature curve；
Fig. 6 is the X-ray diffractogram (XRD) of sample in the embodiment of the present invention 3；
Fig. 7 is the resistivity of sample in the embodiment of the present invention 3 with temperature curve.
Specific implementation mode
The present invention provides a kind of perovskite-like layer structure system solid solution materials, have molecular formula shown in formula (I)：
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
The present invention is inserted into bismuth Layered Perovskite Bi for LSMO layers by perovskite structure4Ti3O12In material, realize specific Bi under component4Ti3O12-La1-xSrxMnO3It is dissolved single_phase system new material.Such material has four layers of perovskite-like stratiform knot Structure meets the structure feature of Aurivillius phase materials, while having the adjustable semiconductor of resistivity in a certain range special again Property, the high resistance insulation characterisitic of original bismuth titanates class material is greatly reduced, has expanded this kind of material in semiconductor devices, energy Application potential in the field of functional materials such as source, information.
The present invention also provides a kind of perovskite-like layer structure system solid solution materials with molecular formula shown in formula (I) Preparation method, include the following steps：
A) bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound are mixed, obtained Mixed powder；
B it is ground after the mixed powder) is carried out pre-burning, obtains initial powder；
C it is sintered after) being molded the initial powder, obtains the perovskite-like layer with molecular formula shown in formula (I) Shape structure system solid solution material；
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
The present invention first mixes bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound It closes, obtains mixed powder.
The present invention there is no specifically limited, can be solid phase mixing method, also may be used to the preparation method of the mixed powder It is obtained by wet chemical method.
Wherein, the solid phase mixing method is specially：
Bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound are mixed, grinding obtains To mixed powder.
In the present invention, to the mode of the grinding there is no specifically limited, well known to a person skilled in the art grinding sides Method.In the present invention, it is preferred to be ground in the agate mortar, the time of the grinding is preferably 1~3h.
The wet chemistry methods are specially：
Bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound are dissolved in solvent Afterwards, complexing agent is added, mixture is obtained；
Ammonium hydroxide is added into the mixture and adjusts pH, obtains clarifying reaction solution；
The clarifying reaction solution is dried, mixed powder is obtained.
In the present invention, the solvent is preferably nitric acid.The complexing agent is preferably ethylenediamine tetra-acetic acid (EDTA) and lemon Lemon acid.Wherein, the molar ratio of metal ion is preferably 0.7 in the EDTA, citric acid and the mixture：1：1.
After obtaining the mixture, ammonium hydroxide is added dropwise into the mixture, adjusts pH to 7.Wherein, in the mistake that ammonium hydroxide is added dropwise The mixture is heated in journey, and coordinates uniform stirring.The temperature of the heating is preferably 80 DEG C.
Obtained clarifying reaction solution is faint yellow, and then the reaction solution is dried, obtains mixed powder.
The present invention there is no specifically limited, preferably obtains powder as follows to the method for the drying：
The reaction solution is placed in heating concentration in ceramic evaporation ware and burns into powder up to solution is evaporated.
In the present invention, the bismuth source compound is selected from bismuth oxide or five nitric hydrate bismuths；
The lanthanum source compound is selected from lanthana or lanthanum nitrate hydrate；
The barium source compound is selected from strontium carbonate or strontium nitrate；
The manganese source compound is selected from manganese dioxide, four acetate hydrate manganese or manganese nitrate hydrate；
The titanium source compound is selected from titanium dioxide or tetrabutyl titanate.
Wherein, when the present invention mixes above compound raw material, preferably by above-mentioned raw materials according to Bi4Ti3O12With La1-xSrxMnO3Molar ratio 1：1 carries out mixed ingredients, wherein 0<x<1.It is furthermore preferred that bismuth source compound is mixed in order to prevent Volatilization during conjunction, the bismuth source compound powder is with molar ratio excessive 3%~15%.
After obtaining mixed powder, is ground after the mixed powder is carried out pre-burning, obtain initial powder；
In the present invention, it is preferred to which the mixed powder is put into corundum crucible, it is placed in Muffle furnace and carries out pre-burning.It is described The temperature of pre-burning is preferably 700~900 DEG C, more preferably 750~850 DEG C；The time of the pre-burning is preferably 2~5h, more excellent It is selected as 3~4h.The heating rate of the pre-burning is preferably 3~8 DEG C/min, more preferably 4~7 DEG C/min.
After pre-burning, the product is cooled down, grinding obtains initial powder.The time of the grinding is preferably 1 ~2h.
After obtaining initial powder, it is sintered, is obtained with molecular formula shown in formula (I) after the initial powder is molded Perovskite-like layer structure system solid solution material.
In the present invention, it is preferred to after the initial powder is molded with dry press, then be placed in Muffle furnace and be sintered.Institute The temperature for stating sintering is preferably 900~1000 DEG C, more preferably 920~980 DEG C；The time of the sintering is preferably 2~6h, more Preferably 3~5h.The heating rate of the sintering is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/min.
In the present invention, the perovskite-like stratiform with molecular formula shown in formula (I) can also be carried out as follows The preparation of structure system solid solution material：
A) by Bi4Ti3O12Powder and La1-xSrxMnO3Powder mixes, and obtains mixed powder；
B) it is ground after the mixed powder being carried out pre-burning, obtains initial powder；
C) it is sintered after being molded the initial powder, obtains the perovskite-like layer with molecular formula shown in formula (I) Shape structure system solid solution material.
The present invention can also be by Bi4Ti3O12And La1-xSrxMnO3After being first prepared into powder, carrying out with shown in formula (I) Molecular formula perovskite-like layer structure system solid solution material preparation.
Specifically, the present invention is first by Bi4Ti3O12Powder and La1-xSrxMnO3Powder mixes, and obtains mixed powder.
Wherein, the Bi4Ti3O12Powder is preferably prepared as follows：
Calcining, grinding, obtain Bi after bismuth source compound and lanthanum source compound are mixed4Ti3O12Powder.
The temperature of the calcining is preferably 800~900 DEG C, and the time of the calcining is preferably 2~6h.
The La1-xSrxMnO3Powder can be solid phase mixing method, can also be obtained by wet chemical method.
The solid phase mixing method is preferably prepared as follows：
Calcining, grinding, obtain La after the lanthanum source compound, barium source compound and manganese source compound are mixed1-xSrxMnO3 Powder.
The temperature of the calcining is preferably 850~1000 DEG C, and the time of the calcining is preferably 3~6h.
The wet chemical method is preferably prepared as follows：
The lanthanum source compound, barium source compound and manganese source compound are dissolved in nitric acid, reaction solution is obtained；
It heats, is evaporated after the reaction solution is mixed with glycine, burn, obtain the fluffy powder of black；
By the fluffy powder sintering of the black, grinding, La is obtained1-xSrxMnO3Powder.
Wherein, the concentration of the salpeter solution is preferably 6mol/L.Cation rubs with glycine in the reaction solution You are than preferably 1：2.3.The temperature of the heating is preferably 400~500 DEG C.The temperature of the sintering is preferably 850~1000 DEG C, the time of the sintering is preferably 3~6h.
To the method for above-mentioned grinding there is no specifically limited, well known to a person skilled in the art grinding method to be the present invention It can.
In the above preparation method, the bismuth source compound is selected from bismuth oxide or five nitric hydrate bismuths；
The lanthanum source compound is selected from lanthana or lanthanum nitrate hydrate；
The barium source compound is selected from strontium carbonate or strontium nitrate；
The manganese source compound is selected from manganese dioxide, four hydration manganese acetates, four acetate hydrate manganese or manganese nitrate hydrate；
The titanium source compound is selected from titanium dioxide or tetrabutyl titanate.
Obtain Bi4Ti3O12Powder and La1-xSrxMnO3After powder, by the Bi4Ti3O12Powder and La1-xSrxMnO3Powder Mixing, obtains mixed powder；
Then, it is ground after the mixed powder being carried out pre-burning, obtains initial powder.
In the present invention, it is preferred to which the mixed powder is put into corundum crucible, it is placed in Muffle furnace and carries out pre-burning.It is described The temperature of pre-burning is preferably 700~900 DEG C, more preferably 750~850 DEG C；The time of the pre-burning is preferably 2~5h, more excellent It is selected as 3~4h.The heating rate of the pre-burning is preferably 3~8 DEG C/min, more preferably 4~7 DEG C/min.
After pre-burning, the product is cooled down, grinding obtains initial powder.The time of the grinding is preferably 1 ~2h.
After obtaining initial powder, it is sintered, is obtained with molecular formula shown in formula (I) after the initial powder is molded Perovskite-like layer structure system solid solution material.
In the present invention, it is preferred to after the initial powder is molded with dry press, then be placed in Muffle furnace and be sintered.Institute The temperature for stating sintering is preferably 900~1000 DEG C, more preferably 920~980 DEG C；The time of the sintering is preferably 2~6h, more Preferably 3~5h.The heating rate of the sintering is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/min.
Perovskite-like layer structure system solid solution material provided by the invention, which can be used for matching, is based on layer structure material Device impedance and other function semiconductor devices etc..
The present invention is inserted into bismuth Layered Perovskite Bi for LSMO layers by perovskite structure4Ti3O12In material, realize specific Bi under component4Ti3O12-La1-xSrxMnO3It is dissolved single_phase system new material.Such new material has four layers of perovskite-like stratiform Structure meets the structure feature of Aurivillius phase materials, while having the adjustable semiconductor of resistivity in a certain range special again Property, the high resistance insulation characterisitic of original bismuth titanates class material is greatly reduced, has expanded this kind of material in semiconductor devices, energy Application potential in the field of functional materials such as source, information.
The result shows that resistivity of the perovskite-like layer structure system solid solution material provided by the invention in room temperature is 0.68~8 × 104Ω·cm。
For a further understanding of the present invention, perovskite-like layer structure provided by the invention is dissolved with reference to embodiment System material and preparation method thereof illustrates, and protection scope of the present invention is not limited by the following examples.
Embodiment 1：
A kind of bismuth lanthanum-strontium manganese titania ceramics material with semiconducting behavior, molecular formula Bi4La0.67Sr0.33MnTi3O15, Preparation method includes the following steps：
(1) Chinese medicines group analytical reagents tetrabutyl titanate (C is used16H36O4Ti), five nitric hydrate bismuth (Bi (NO3)3· 5H2O), strontium nitrate (Sr (NO3)2), nitric hydrate iron (La (NO3)3·nH2O), four acetate hydrate manganese (C4H6MnO4·4H2O) it is Raw material, according to molar ratio Bi：La：Sr：Mn：Ti=4 (1+0.1)：0.67：0.33：1：3 weigh corresponding raw material, are dissolved in nitric acid In.Ethylenediamine tetra-acetic acid (EDTA) and citric acid is added as complexing agent, EDTA, citric acid and metal ion molar ratio are 0.7: 1:1。
(2) in 80 DEG C of thermal station, and under the cooperation of uniform stirring, ammonium hydroxide is added dropwise, when pH reaches 7, obtains clear solution, In faint yellow.Prepared solution is placed in heating concentration in ceramic evaporation ware, and, until solution is evaporated and burns into powder, gained powder exists 800 DEG C of pre-burnings 3 hours in Muffle furnace.
(3) by Bi obtained in (2)4La0.67Sr0.33MnTi3O15Initial powder takes a part, with Hefei Ke Jing companies 40 tons of type Manual tablet pressing machines 100MPa forming under the pressure be Φ 20mm × 4mm wafer sample.Wafer sample is placed in paving Have on the corundum gasket of quartz sand, room is cooled in 5 hours of 950 DEG C of heat preservation sinterings using the temperature rate of 3 DEG C/min It is warm to obtain target ceramics sample product.
(4) it by the sub-fraction of the sample obtained in step (3), is placed in agate mortar and pulverizes, use Rigaku Motor Corporation's Rigaku Smartlab type X-ray diffractometers carry out material phase analysis, and as shown in Fig. 1, Fig. 1 is that the present invention is implemented The X-ray diffractogram (XRD) of sample in example 1.By being compared with PDF standard cards, four layers that it is single object phase can be confirmed Shape perovskite-like structure Aurivillius phases.Using the JEM-ARM200F type spherical aberration corrections of Jeol Ltd. (JEOL) Transmission electron microscope observation selective electron diffraction picture and scanning transmission atom high resolution picture, as shown in Fig. 2, Fig. 2 are this hair The scanning electron microscope (SEM) photograph of sample in bright embodiment 1.Its four layer structure is high-visible.Meanwhile ceramics sample being cut into one small Strip is covered with four electrodes with silver paste painting, passes through the multi-functional physical measurement system testing of Quantum Design companies of the U.S. Sample resistivity variation with temperature curve, the resistivity of sample are reduced with the raising of temperature, show certain semiconductor Characteristic, its resistivity is 1.8 × 10 when room temperature4Ω cm, as shown in Fig. 3, Fig. 3 are the electricity of sample in the embodiment of the present invention 1 Resistance rate is with temperature curve.
Embodiment 2：
A kind of bismuth lanthanum-strontium manganese titania ceramics material with semiconducting behavior, molecular formula Bi4La0.5Sr0.5MnTi3O15, The preparation of its two-step method includes the following steps：
(1) Chinese medicines group analytical reagents bismuth oxide (Bi is used2O3), titanium dioxide (TiO2) according to molar ratio Bi2O3：TiO2=2:3 weigh corresponding raw material so that Bi4Ti3O12Moles total number be 0.04mol.By above-mentioned load weighted powder Body is put into agate mortar, is ground 3 hours so that powder is mixed thoroughly.Then mixed powder is placed in corundum crucible, 800 DEG C of pre-burnings 2 hours in Muffle furnace.After grinding 1 hour in the agate mortar after cooling, Bi is obtained4Ti3O12Powder.
(2) Chinese medicines group analytical reagents lanthana La is used2O3, strontium nitrate Sr (NO3)2, four acetate hydrate manganese C4H14MnO8, according to molar ratio La2O3:Sr(NO3)2:C4H14MnO8=1:2:4 weigh corresponding raw material so that La0.5Sr0.5MnO3Moles total number be 0.04mol.Above-mentioned load weighted powder is put into the nitric acid of a concentration of 6mol/L of 50ml Middle dissolving, obtains clear solution.Then Chinese medicines group analytical reagents glycine (C is used2H5NO2), according to sun total in solution Ion number ratio glycine is 1:2.3 weigh C2H5NO2It is placed in above-mentioned solution, using magnetic agitation 5 hours.It will be molten after stirring Liquid is placed on 400 DEG C of -500 DEG C of electric furnaces and heats, and evaporates the aqueous solvent in solution, reaches in beaker and occur after organic polymer fusing point Burning has the fluffy powder of black to spray.The powder after burning is collected, 1100 DEG C of pre-burnings 3 hours in Muffle furnace.In agate after cooling After being ground 1 hour in Nao mortars, La is obtained0.5Sr0.5MnO3Initial powder.
(3) by Bi made in (1)4Ti3O12Made La in initial powder and (2)0.5Sr0.5MnO3, according to molar ratio Bi4Ti3O12：La0.5Sr0.5MnO3=1：1 weighs corresponding raw material so that Bi4La0.5Sr0.5MnTi3O15Moles total number be 0.01mol.Above-mentioned load weighted powder is put into agate mortar, is ground 3 hours so that powder is mixed thoroughly.Then Uniformly mixed powder is placed in corundum crucible, 860 DEG C of pre-burnings 3 hours in Muffle furnace.It is ground in the agate mortar after cooling Mill obtains Bi after 1 hour4La0.5Sr0.5MnTi3O15Initial powder.
(4) by Bi obtained in (3)4La0.5Sr0.5MnTi3O15Initial powder takes a part, with Hefei Ke Jing companies 40 tons of type Manual tablet pressing machines 100MPa forming under the pressure be Φ 20mm × 4mm wafer sample.Wafer sample is placed in paving Have on the corundum gasket of quartz sand, room temperature is cooled in 3 hours of 960 DEG C of heat preservation sinterings using the heating rate of 3 DEG C/min Obtain target ceramics sample product.
(5) sample that will be obtained in step (4), after surface is polished, with Rigaku Motor Corporation Rigaku Smartlab type X-ray diffractometers carry out material phase analysis, and as shown in Fig. 4, Fig. 4 is the X-ray of sample in the embodiment of the present invention 2 Diffraction pattern (XRD).By being compared with PDF standard cards, the Bi for preparation can be confirmed4La0.5Sr0.5MnTi3O15For single object Four Layered Perovskite structure Aurivillius phases of phase.Ceramics sample is cut into a small strip, four are covered with silver paste painting A electrode, by the multi-functional physical measurement system testing sample resistivities of Quantum Design companies of the U.S. with the change of temperature Change curve, the resistivity of sample reduces with the raising of temperature, shows certain characteristic of semiconductor, its resistivity is when room temperature 6.8×103Ω cm, as shown in Fig. 5, Fig. 5 are the resistivity of sample in the embodiment of the present invention 2 with temperature curve.
Embodiment 3：
A kind of bismuth lanthanum-strontium manganese titania ceramics material with semiconducting behavior, molecular formula Bi4La0.7Sr0.3MnTi3O15, Preparation method includes the following steps：
(1) Chinese medicines group analytical reagents bismuth oxide (Bi is used2O3), strontium carbonate (SrCO3), manganese dioxide (MnO2), two Titanium oxide (TiO2) and high purity lanthanum oxide (La2O3), according to molar ratio Bi2O3:La2O3:SrCO3:MnO2:TiO2=2.1:0.25: 0.5:1:3 weigh corresponding raw material so that Bi4La0.7Sr0.3MnTi3O15Moles total number be 0.05mol.Well by above-mentioned weighing Powder be put into agate mortar, grind 3 hours so that powder is mixed thoroughly.Then mixed powder is placed in corundum earthenware In crucible, 860 DEG C of pre-burnings 3 hours in Muffle furnace.After grinding 1 hour in the agate mortar after cooling, obtain Bi4La0.7Sr0.3MnTi3O15Initial powder.
(2) by Bi obtained in (1)4La0.3Sr0.7MnTi3O15Initial powder takes a part, with Hefei Ke Jing companies 40 tons of type Manual tablet pressing machines 100MPa forming under the pressure be Φ 20mm × 4mm wafer sample.Wafer sample is placed in paving Have on the corundum gasket of quartz sand, room is cooled in 3 hours of 960 DEG C of heat preservation sinterings using the temperature rate of 3 DEG C/min It is warm to obtain target ceramics sample product.
(3) it by the sub-fraction of the sample obtained in step (2), is placed in agate mortar and pulverizes, use Rigaku Motor Corporation's Rigaku Smartlab type X-ray diffractometers carry out material phase analysis, and as shown in Fig. 6, Fig. 6 is that the present invention is implemented The X-ray diffractogram (XRD) of sample in example 3.By being compared with PDF standard cards, four layers that it is single object phase can be confirmed Shape perovskite-like structure Aurivillius phases.Ceramics sample is cut into a small strip, four electrodes are covered with silver paste painting, By the multi-functional physical measurement system testing sample resistor rate variation with temperature curve of Quantum Design companies of the U.S., The resistivity of sample is reduced with the raising of temperature, shows certain characteristic of semiconductor, its resistivity is 8 × 10 when room temperature4 Ω cm, as shown in Fig. 7, Fig. 7 are the resistivity of sample in the embodiment of the present invention 3 with temperature curve.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (6)

1. a kind of perovskite-like layer structure system solid solution material, which is characterized in that have molecular formula shown in formula (I)：
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1；
The preparation method with the perovskite-like layer structure system solid solution material of molecular formula shown in formula (I) includes following Step：
A) bismuth source compound, lanthanum source compound, barium source compound, manganese source compound and titanium source compound are mixed, mixed Powder；
B it is ground after the mixed powder) is carried out pre-burning, obtains initial powder；
C it is sintered after) being molded the initial powder, obtains the perovskite-like stratiform knot with molecular formula shown in formula (I) Structure system solid solution material；
The temperature of the sintering is 900~1000 DEG C, and time of the sintering is 2~6h, the heating rate of the sintering is 1~ 5℃/min。
2. perovskite-like layer structure system solid solution material according to claim 1, which is characterized in that
The bismuth source compound is selected from bismuth oxide or five nitric hydrate bismuths；
The lanthanum source compound is selected from lanthana or lanthanum nitrate hydrate；
The barium source compound is selected from strontium carbonate or strontium nitrate；
The manganese source compound is selected from manganese dioxide, four hydration manganese acetates, four acetate hydrate manganese or manganese nitrate hydrate；
The titanium source compound is selected from titanium dioxide or tetrabutyl titanate.
3. one kind having the preparation method of the perovskite-like layer structure system solid solution material of molecular formula shown in formula (I), special Sign is, includes the following steps：
A) by Bi4Ti3O12Powder and La1-xSrxMnO3Powder mixes, and obtains mixed powder；
B) it is ground after the mixed powder being carried out pre-burning, obtains initial powder；
C) it is sintered after being molded the initial powder, obtains the perovskite-like stratiform knot with molecular formula shown in formula (I) Structure system solid solution material；
The temperature of the sintering is 900~1000 DEG C, and time of the sintering is 2~6h, the heating rate of the sintering is 1~ 5℃/min；
Bi4Ti3O12-La1-xSrxMnO3Formula (I)；Wherein, 0<x<1.
4. preparation method according to claim 3, which is characterized in that the temperature of the pre-burning is 700~900 DEG C, described The time of pre-burning is 2~5h.
5. preparation method according to claim 3, which is characterized in that the heating rate of the pre-burning is 3~8 DEG C/min.
6. preparation method according to claim 3, which is characterized in that the Bi4Ti3O12Powder and La1-xSrxMnO3Powder Molar ratio be 1:1.
CN201610313241.0A 2016-05-11 2016-05-11 A kind of perovskite-like layer structure system solid solution material and preparation method thereof Active CN106007705B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610313241.0A CN106007705B (en) 2016-05-11 2016-05-11 A kind of perovskite-like layer structure system solid solution material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610313241.0A CN106007705B (en) 2016-05-11 2016-05-11 A kind of perovskite-like layer structure system solid solution material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106007705A CN106007705A (en) 2016-10-12
CN106007705B true CN106007705B (en) 2018-08-03

Family

ID=57100108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610313241.0A Active CN106007705B (en) 2016-05-11 2016-05-11 A kind of perovskite-like layer structure system solid solution material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106007705B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200577B (en) * 2017-05-31 2019-10-25 中国科学技术大学 A kind of perovskite-like lamellar structure compound and preparation method thereof
CN108465469B (en) * 2018-03-14 2021-04-20 武汉理工大学 Co-doped modified spherical SrMnO3Perovskite type oxide catalyst and preparation method and application thereof
CN110527954B (en) * 2019-09-17 2021-07-30 常州大学 LaMnO3Control of Bi4Ti3O12Band gap transition metal oxide ferroelectric film and preparation method thereof
CN116474760B (en) * 2023-04-27 2023-12-19 南京工业大学 Layered perovskite type SrBi 4-x La x Ti 4 O 15 Photocatalyst, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1768403A (en) * 2003-02-27 2006-05-03 Tdk株式会社 Thin film capacity element composition, high-permittivity insulation film, thin film capacity element, thin film multilayer capacitor, electronic circuit and electronic apparatus

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1768403A (en) * 2003-02-27 2006-05-03 Tdk株式会社 Thin film capacity element composition, high-permittivity insulation film, thin film capacity element, thin film multilayer capacitor, electronic circuit and electronic apparatus

Also Published As

Publication number Publication date
CN106007705A (en) 2016-10-12

Similar Documents

Publication Publication Date Title
Yin et al. Enhanced energy storage properties of {Bi0. 5 [(Na0. 8K0. 2) 1-zLiz] 0.5} 0.96 Sr0. 04 (Ti1-x-yTaxNby) O3 lead-free ceramics
Zhang et al. Preparation and electrical properties of bismuth layer-structured ceramic Bi3NbTiO9 solid solution
KR101268487B1 (en) Bismuth-based Complex Perovskite Lead-free Piezoelectric Ceramics and Manufacturing Method therefor
Gao et al. Microstructure, piezoelectric and ferroelectric properties of Mn-added Na0. 5Bi4. 5Ti4O15 ceramics
CN106007705B (en) A kind of perovskite-like layer structure system solid solution material and preparation method thereof
Chakrabarti et al. Effect of La-substitution on the structure and dielectric properties of BaBi4Ti4O15 ceramics
Liu et al. Enhanced ferroelectricity of CaBi2Nb2O9-based high-temperature piezoceramics by pseudo-tetragonal distortion
Zhao et al. Piezoelectric and ferroelectric properties of (Ba, Ca)(Ti, Sn) O3 lead-free ceramics sintered with Li2O additives: Analysis of point defects and phase structures
Sawangwan et al. The effect of Zr content on electrical properties of Ba (Ti 1-x Zr x) O 3 ceramics
Lin et al. Structure, dielectric and piezoelectric properties of Ba0. 90Ca0. 10Ti1− xSnxO3 lead-free ceramics
Mächler et al. Synthesis, doping and electrical bulk response of (Bi1/2Na1/2) xBa1-xTiO3+ CaO–based ceramics with positive temperature coefficient of resistivity (PTCR)
Purohit et al. Structural and electrical properties of lead-free perovskite: Bi (Sr0. 25Ti0. 25Fe0. 5) O3
Chen et al. Origin of ultrahigh thermal stability on dielectric permittivity and dipole glass-like behavior of 0.4 Ba0. 8Ca0. 2TiO3-0.6 Bi (Mg0. 5Ti0. 5) O3 based ceramics
Said et al. Dielectric, pyroelectric, and ferroelectric properties of gadolinium doped Sr0. 53Ba0. 47Nb2O6 ceramic
Gaikwad et al. Co-precipitation method for the preparation of fine ferroelectric BaBi2Nb2O9
Gaikwad et al. Coprecipitation method for the preparation of nanocrystalline ferroelectric CaBi2Ta2O9
CN107417267B (en) Bismuth ferrite multiferroic ceramic and preparation method thereof
Wongsaenmai et al. Improving ferroelectric properties of Pb (Zr0. 44Ti0. 56) O3 ceramics by Pb (Mg1/3Nb2/3) O3 addition
Pang et al. Multiferroic ternary solid solution system of BiFeO3-NdFeO3-PbTiO3
Cheng et al. Microstructure and electrical properties of Bi1/2Na1/2TiO3–BaTiO3–Y2NiMnO6 lead-free piezoelectric ceramics
Yu et al. Reddish orange-emitting and improved electrical properties of Sm 2 O 3-doped SrBi 4 Ti 4 O 15 multifunctional ceramics
Kumari et al. Enhanced Curie temperature with a significant reduction in sintering temperature for Cu2+/Bi3+ co-doped BCZT lead-free ceramics
Fang et al. Giant dielectric response at low frequency of B-site modified Aurivillius oxide potassium bismuth titanate
Rai et al. Structural and dielectric properties of Bi modified PLZT ceramics
Mahapatra et al. Dielectric, resistive and conduction characteristics of lead-free complex perovskite electro-ceramic:(Bi1/2K1/2)(Zn1/2W1/2) O3

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant