CN1388088A - Ferroelectric-ferromagnetic functional complex in three-layer perovskite-like structure and its prepn - Google Patents

Ferroelectric-ferromagnetic functional complex in three-layer perovskite-like structure and its prepn Download PDF

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CN1388088A
CN1388088A CN 02115947 CN02115947A CN1388088A CN 1388088 A CN1388088 A CN 1388088A CN 02115947 CN02115947 CN 02115947 CN 02115947 A CN02115947 A CN 02115947A CN 1388088 A CN1388088 A CN 1388088A
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perovskite
complex
ferromagnetic
ion
ferroelectric
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方亮
张辉
袁润章
杨卫明
鄢俊兵
安继明
刘韩星
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Wuhan University of Science and Engineering WUSE
Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The functional complex structure has alternately arranged nano level perovskite-like ferroelectric layer and ferromagnetic layer. It is prepared through chemical reaction to synthesize three-layer perovskite-like niobate or tantalite AB2M3O10, where A=K, Na Li, Rb, Cs and their composite iron, B=Sr, Ba, Ca, Pb and their composite iron, and M=Nb, Ta and their composite ion, acid treatment, inserting organic amine layer; ion exchange in water solution of [Fe3(OCOCH3)7OH.2H2O]No3; heat treatment in reduction atmosphere; and forming interlayer ferromagnetic oxide or ferromagnetic metal so as to obtain the invented composite body.

Description

Three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex and preparation method thereof
One, technical field:
The invention belongs to the ferroelectric-ferromagnetic functional complex, a kind of three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex and preparation method thereof are provided.
Two, background technology:
Because magnetoelectric material has good magnetoelectric effect, wide application prospect is arranged in fields such as the current measurement of microwave regime, ultra-high-tension power transmission line, the magnetic detection of wideband section, magnetic sensors.
Since the sixties in last century, the research to magnetoelectric material has bigger progress in the world, has found Cr 2O 3Etc. multiple monophasic magnetoelectric material, still the Neel temperature of this type of material or Curie temperature are far below room temperature mostly, and magnetic-electric coefficient is little, makes it be difficult to satisfy practical requirement.
Study own design at present and prepared the ferroelectric-ferromagnetic functional complex, it has the magnetoelectric effect unique than single-phase magnetoelectric material (referring to document 1-6).1972, the Philips laboratory used the spinel structure magnetoelectricity ferrite of original position compounding technology exploitation (as CoFe 2O 4) with the perovskite structure piezoelectrics (as BaTiO 3) two-phase blended novel ferroelectric-ferromagnetic functional complex, its magnetoelectricity series numerical value reaches 130mv/cmOe.At present, the preparation method of this type of complex body has following several:
(1) in-situ compositing, its demanding temperature of fusion, and the third phase that is difficult to control complex body generates.
(2) sintering process, its advantage makes technology simple, and the low and phase composite of cost, particle diameter controllability are strong.But above two kinds of methods all need synthetic respectively ferroelectrics and ferro-magnetic, after mixing then, make.The possibility that this will cause two-phase to react, and all can only realize compound on micro-meter scale of ferroelectrics and ferro-magnetic, can not realize ferroelectric phase and ferromagnetic mutually intercrystalline complete product coupling, unavoidably there is defective in complex body, thereby causes some mis-behave of complex body.The magnetic-electric coefficient of complex body is still on the low side, does not reach application request.
(3) there is bibliographical information that one deck Pb-based lanthanumdoped zirconate titanates (PZT) piezoelectric interlayer is obtained a kind of novel lamellar ferroelectric-ferromagnetic functional complex recently between two-layer TbDyFe2 (Terfenol-D) giant magnetostrictive material, has magnetic-electric coefficient up to 4.68v/cmOe.
Through our years of researches, finding and having determined to exist a class chemical general formula is AB 2M 3O 10(A=K, Na, Li, Rb, Cs and compound ion thereof; B=Ba, Sr, Ca, Pb and compound ion thereof; M=Nb, Ta and compound ion thereof) the three layers of ferroelectric new niobium of perovskite-like structure (tantalum) hydrochlorate, its constitutional features is three layers of ferroelectric perovskite-like unit layer [B that links to each other with drift angle 2M 3O 10] -With interlayer macrocation A +Layer is alternately arranged (referring to document 7-9) along the C-axle in accurate four directions.
Reference: 1.J.Van den Boomgaard and R.A.J.Born, " A sintered Magnetoelectric Composite Material BaTiO 3-Ni (Co, Mn) Fe 3O 4"; J.Mater.Sci.; 13; 1538-48 (1978) 2.J.Van den Boomgaard; A.M.J.G.Van Run; and J.Van Suchtelen, " Magnetoelectricity in Piezoelectric-Magnetostrictive Composites " Ferroelectrics, 10,295-98 (1976) 3.J.Van den Boomgaard, D.R.Terrell, R.A.J.Bom, and H.F.J.I.Giller, " An Insitu Grown Eutectic Magnetoelectric Composite Material:Part I; composition and Unidirectional Solidification ", J.Mater.Sci., 9,1705-709 (1974) 4.Jungho Ryu, Shashank Priya, Alfredo Vazquez Carazo, and Kenji Uchino, " Effect of the Magnetostrictive Layer on Magnetoelectric Properties in Lead Zirconate Titanate/Terfenol-D Laminate Composites " J.Am.Cream.Soc., 84 [12] 2905-908 (2001) 5.JUNGHO Ryu, Alfredo Vazquez Carazo, Kenji Uchino﹠amp; Hyoun-E E Kim, " Piezoelectric and Magnetoelectric Properties of Lead Zirconate Titanate/Ni-Ferrite Particulate Composites ", Journal of Electroceramics, 7,17-24 (2001) 6.Jungho Ryu, Alfredo Vazquez Carazo, Kenji Uchino ﹠amp; Hyoun-Ee KIM, " Magnetoelectric Properties in Piezoelectric and Magnetostrictive Laminate Composites ", Jpn.J Appl.Phys., 40,4948-4951 (2001) 7. side is bright, Zhang Hui, Wu Bailin, Yuan Runzhang. the new tantalate KSr of perovskite-like structure 2Ta 3O 10Synthetic, structure and interlayer characteristic. SCI .2000 (11): 16398. sides are bright, the doctorate paper, Wuhan Polytechnical Univ, 1998,9. sides are bright in Wuhan, Zhang Hui, Wu Bailin, Yuan Runzhang etc. the new niobate Sr of Layered Perovskite type 2KNb 3O 10. Chinese Journal of Inorganic Chemistry, 1999,15[4]: p505
Three, summary of the invention:
A kind of three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex are provided, and this complex structure makes perovskite-like ferroelectric layer and alternately arrangement of ferromagnetic substance on the nanoscale, to solve the shortcoming of above-mentioned complex body.Its mechanism: because AB 2M 3O 10The ferroelectric new niobium of Layered Perovskite (tantalum) hydrochlorate, interlayer charge density is lower, guest molecule can carry out ion-exchange and the intercalation interlayer position to the perovskite-like layer, guest molecule is in be subject to the two-dimensional nano spatial new stable state of interlayer, obtains a series of have high-performance, multi-functional complex bodys.
The technical scheme for preparing complex body of the present invention is as follows:
(1) utilize chemical reaction in 300-1500 ℃ of scope, synthetic three layers of perovskite-like structure niobium, tantalate AB 2M 3O 10(A=K, Na, Li, Rb, Cs and compound ion thereof; B=Sr, Ba, Ca, Pb and compound ion thereof; M=Nb, Ta and compound ion thereof).
(2) with above-mentioned product after acid (as concentrated hydrochloric acid, the vitriol oil, concentrated nitric acid) is handled 48 hours, with distilled water flush away acid ion and the alkalimetal ion A that exchanges out +, carried out intercalation with organic amine (as normal hexyl Amine, n-amylamine, n-Butyl Amine 99, Tri N-Propyl Amine) in 1～7 day 60 ℃ of vigorous stirring again, introduce organic amine at the perovskite-like interlayer, the interlayer position is strutted, obtain amine-pillared perovskite-like structure niobium (tantalum) hydrochlorate.
(3) with Fe (NO 3) 39H 2O and 50% diacetyl oxide ethanolic soln react the organic complex [Fe that makes iron under condition of ice bath 3(OCOCH 3) 7OH2H 2O] NO 3
(4) [Fe 3(OCOCH 3) 7OH2H 2O] NO 3Be made into 0.04moldm -1The aqueous solution, add concentration again and be 1% amine-pillared perovskite-like structure niobium (tantalum) hydrochlorate suspension liquid, before its molar weight is less than 1/5 of thing, under 60 ℃, carries out ion exchange reaction and make [Fe 3(OCOCH 3) 7OH2H 2O] +Enter the interlayer position of perovskite-like structure, form the organic complex positively charged ion of iron and the complex body that calcium titanium ore bed is alternately arranged.
(5) above-mentioned complex body is mixed a certain amount of graphite,, make the organic complex positively charged ion of iron in the complex body slough water and organic composition and form the stable ferromagnetic Fe that has through 300～800 ℃ of thermal treatments 3O 4Thereby, obtain three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex; Also can feed H 2The complex body that the organic complex positively charged ion and the calcium titanium ore bed of iron are alternately arranged is heat-treated at 300～800 ℃, organic complex positively charged ion in the interlayer position with iron is reduced to ferromagnetic metal Fe, thereby obtains three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex.
Technical process as shown in Figure 1
Four, description of drawings:
Introduced the method for three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex of a kind of preparation among the last figure, the method that organic complex ion and three layers of perovskite-like structure niobium of amine-pillared (tantalum) hydrochlorate by Fe carries out ion-exchange is synthesized the ferroelectric-ferromagnetic functional complex;
Five, embodiment:
Example:
1.AB 2M 3O 10(A=K, Na, Li, Rb, Cs and compound ion thereof; B=Ba, Sr, Ca, Pb and compound ion thereof; M=Nb, Ta and compound ion thereof) synthetic:
With raw material BCO 3, A 2CO 3, M 2O 5BCO in molar ratio 3: A 2CO 3: M 2O 5=4: 1: 3 batching, consider A 2CO 3Volatility at high temperature should have more than needed 5% during batching.Three kinds of raw materials burn till under 800-1650 ℃ after uniform mixing, the abundant grinding, are incubated 2～48 hours, obtain AB 2M 3O 10
As KSr 2Nb 3O 10Synthetic, with SrCO 3, K 2CO 3With Nb 2O 5Prepared burden in 4: 1: 3 in molar ratio, and added excessive 5% K again 2CO 3, mix, insert in the Pt crucible, be heated between 1300～1500 ℃, be incubated 5 hours postcooling and take out to room temperature, obtain KSr 2Nb 3O 10
2. acid treatment
As the KSr that will make 2Nb 3O 10Acid treatment with the salt acid soak of excessive 5mol/L 48 hours, fully clean with distilled water, make and do not contain K in the sample +And Cl +, under infrared lamp, dry.
3. organic amine (as normal hexyl Amine, n-amylamine, n-Butyl Amine 99, Tri N-Propyl Amine) intercalation
As get KSr after the 10g acid treatment 2Nb 3O 10Put into three-necked bottle, add 50% normal hexyl Amine ethanolic soln 100mL again, stirred 1～7 day down at 60 ℃.Reacted back centrifugation collecting precipitation thing, washed 3 times with 50% ethanolic soln bubble, cleaned 3 times with distilled water, infrared lamp oven dry down obtains white n-HexNH 3Sr 2Nb 3O 10Sample.
4.[Fe 3(OCOCH 3) 7OH2H 2O] NO 3Preparation
Get 48.80g Fe (NO 3) 39H 2O joins in the 30mL dehydrated alcohol, dropwise adds the diacetyl oxide of 86mL then.When reaction has tangible heat to emit, cool off with ice bath.After reaction finishes, filter the collecting precipitation thing, natural air drying obtains red-brown [Fe in air 3(OCOCH 3) 7OH2H 2O] NO 3Sample.
5. the alternately preparation of the complex body of arrangement of the organic complex positively charged ion of iron and perovskite-like layer
As take by weighing 13.57g[Fe 3(OCOCH 3) 7OH2H 2O] NO 3, be made into the aqueous solution of 0.04mol/L, get 2g n-HexNH again 3Sr 2Nb 3O 10Be made into 1% suspension liquid, the two mixing,, stirred 7 days down at 35 ℃.Centrifugation collecting precipitation thing after reaction is finished, washing, oven dry obtain the organic complex positively charged ion of iron and the complex body that the perovskite-like layer is alternately arranged.
6. thermal treatment
Complex body is mixed a certain amount of graphite place 500～800 ℃ of thermal treatments in High Temperature Furnaces Heating Apparatus inherence 1～3 hour, make it slough water and organic composition, the weak reducing atmosphere that utilizes graphite to produce makes [the Fe of interlayer 3(OCOCH 3) 7OH2H 2O] +Be transformed into and have ferromagnetic Fe 3O 4Thereby, obtain three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex.
Also can feed H 2, complex body to be heat-treated at 300～800 ℃, the organic complex positively charged ion in the interlayer position with iron is reduced to ferromagnetic metal Fe, thereby obtains three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex.

Claims (2)

1. three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex is characterized in that complex structure makes perovskite-like ferroelectric layer and alternately arrangement of ferromagnetic substance on the nanoscale.
2. the preparation method of three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex is characterized in that:
A. utilize chemical reaction, in 300-1500 ℃ of scope, synthetic three layers of perovskite-like structure niobium (tantalum) hydrochlorate AB 2M 3O 10(A=K, Na, Li, Rb, Cs and compound ion thereof; B=Sr, Ba, Ca, Pb and compound ion thereof; M=Nb, Ta and compound ion thereof).
B. with above-mentioned product after acid (as concentrated hydrochloric acid, the vitriol oil, concentrated nitric acid) is handled 48 hours, with distilled water flush away acid ion and the alkalimetal ion A that exchanges out +, carried out intercalation in 1～7 day with organic amine (as normal hexyl Amine, n-amylamine, n-Butyl Amine 99, Tri N-Propyl Amine) 60 ℃ of vigorous stirring again, between calcium titanium ore bed, introduce organic amine, its interlayer position is strutted, obtain amine-pillared perovskite-like structure niobium (tantalum) hydrochlorate.
C. use Fe (NO 3) 39H 2O and 50% diacetyl oxide ethanolic soln react the organic complex [Fe that makes iron under condition of ice bath 3(OCOCH 3) 7OH2H 2O] NO 3
D. [Fe 3(OCOCH 3) 7OH2H 2O] NO 3Be made into 0.04moldm -1The aqueous solution, add concentration again and be 1% amine-pillared perovskite-like structure niobium (tantalum) hydrochlorate suspension liquid, before its molar weight is less than 1/5 of thing, under 60 ℃, carries out ion exchange reaction and make [Fe 3(OCOCH 3) 7OH2H 2O] +Enter the interlayer position of perovskite-like structure, form the organic complex positively charged ion of iron and the complex body that calcium titanium ore bed is alternately arranged.
E. above-mentioned complex body is mixed a certain amount of graphite,, make the organic complex positively charged ion of iron in the complex body slough water and organic composition and form the stable ferromagnetic Fe that has through 300～800 ℃ of thermal treatments 3O 4Thereby, obtain three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex; Also can feed H 2The complex body that the organic complex positively charged ion and the calcium titanium ore bed of iron are alternately arranged is heat-treated at 300～800 ℃, organic complex positively charged ion in the interlayer position with iron is reduced to ferromagnetic metal Fe, thereby obtains three layers of perovskite-like structure ferroelectric-ferromagnetic functional complex.
CN 02115947 2002-06-10 2002-06-10 Ferroelectric-ferromagnetic functional complex in three-layer perovskite-like structure and its prepn Pending CN1388088A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347127C (en) * 2005-10-28 2007-11-07 清华大学 Composite material with capacitance and inductance performance and its preparing method
CN100398485C (en) * 2006-09-20 2008-07-02 浙江大学 Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347127C (en) * 2005-10-28 2007-11-07 清华大学 Composite material with capacitance and inductance performance and its preparing method
CN100398485C (en) * 2006-09-20 2008-07-02 浙江大学 Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic

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