CN102176509B - Composite phase perovskite manganese oxide magnetoresistance material using metal adhesive - Google Patents
Composite phase perovskite manganese oxide magnetoresistance material using metal adhesive Download PDFInfo
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- CN102176509B CN102176509B CN 201110007969 CN201110007969A CN102176509B CN 102176509 B CN102176509 B CN 102176509B CN 201110007969 CN201110007969 CN 201110007969 CN 201110007969 A CN201110007969 A CN 201110007969A CN 102176509 B CN102176509 B CN 102176509B
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Abstract
The invention discloses a composite phase perovskite manganese oxide magnetoresistance material using metal adhesive. The composite material is compressed by directly introducing metal adhesive in manganese oxide (matrix), and no high-temperature sintering is carried out during the compositing process of materials. The composite material has obvious low-field magnetoresistance characteristic, and the low-field magnetoresistance value can be controlled by changing adhesive types and adhesive addition, thus widening the range of application. The method for preparing the composite material has simple preparation process, low energy consumption, low cost, short period, stable product performance, can be used for processing and manufacturing various complicated components and is convenient to use.
Description
Technical field:
The present invention relates to a kind of manganese oxide magneto-resistor material.
Background technology:
Rear-earth-doped perovskite manganese oxide material with huge magneto-resistance effect is class purposes functional material very widely, at aspects such as hard disc of computer magnetic reading head, Magnetic Sensor, highly-sensitive detector, magnetic random memory, magnetic refrigeration, optical switch, Spin Valve and spin transistors application promise in clinical practice is arranged.
Huge magneto-resistance effect is divided into High-Field magneto-resistance effect and a low magneto-resistance effect.The High-Field magneto-resistance effect is the intrinsic magneto-resistance effect that comes from the double crossing over effect, be the sensitivity function of temperature, reach peak value near Curie temperature Tc, temperature is during away from Curie temperature Tc, magneto-resistor reduces rapidly, and this makes that utilizing the magneto-resistance effect of intrinsic is not desirable selection.A low magneto-resistance effect is extrinsic magneto-resistor, generally occurs in the tangible polycrystalline sample of grain boundary effect.A low magneto-resistance effect only needs very little driving magnetic field, and to temperature-insensitive, has good application prospects.
In recent years, people are by introducing the second phase material in system, as the hybrid system of insulating properties oxide, electroconductive oxide, macromolecule organic composite material, magnetic material, two kinds of huge magnetic resistance materials etc., thereby strengthen a low magneto-resistance effect.Yet existing compound phase perovskite manganese oxide material mostly makes by the high temperature sintering method; The preparation process energy consumption is big, cost is high.Other has patent 200810045859.9 to announce a kind of adhesive joint type perovskite manganese oxide material, this proprietary material adopts high molecular epoxy resin to form as bonding agent is repressed, make the double second phase material of doing of epoxy resin in the thing, but this adhesive joint type perovskite manganese oxide poor-performing, low magneto-resistance effect (magnetoelectricity resistance) is little.
Summary of the invention:
The purpose of this invention is to provide the bonding manganese oxide magneto-resistor material of a kind of metal, the magneto-resistor performance of this kind composite material is good, and the magnetoelectricity resistance is bigger; And the size of magnetoelectricity resistance is introduced the control of bonding agent, can enlarge its scope of application by the kind of change bonding agent or the addition of bonding agent.
The present invention realizes that the technical scheme that its goal of the invention adopts is, the compound phase calcium titanium ore manganose oxide magnetic resistance material that a kind of metal is bonding, and it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3Or CaCO
3, MnO
2Raw material is by molecular formula La
1-xA
xMnO
3The atomic ratio of (0.1≤x≤0.9) is equipped with raw material, and A is Sr or Ca in the formula; After the raw material that is equipped with mixed, grinds, carry out 2～3 times calcining and the grinding after the calcining, it is 5-20 hour that each calcining heat is 1000 ℃～1300 ℃ times, makes La
1-xA
xMnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 5～40% Sn, Zn, Ag or In metal powder for forerunner's powder mixed, after grinding is even, compression moulding under 100～800Mpa pressure, namely.
Compared with prior art, the invention has the beneficial effects as follows:
One, the present invention selects for use Sn, Zn, Ag or In metal powder good as the perovskite manganese oxide material performance that the second phase material and forerunner's powder are mixed with, have low bigger magneto-resistor, in the temperature range of 210～350K, the magnetoelectricity resistance is more than 4%, and it is little to vary with temperature scope.
Two, the magnetoelectricity resistance size of material of the present invention can be controlled by the kind of change bonding agent (metal) or the addition of bonding agent (metal), thereby makes its use more extensive.
Three, because the fusing point of Sn, In is low, the ductility of Ag, Zn is good, makes it can play good bonding effect in pressing process, and need not the manganese oxide magneto-resistor material that high temperature sintering namely can be made into compound phase; Its preparation technology is simple, and is easy to operate, and cost is low, and energy consumption is little, and the cycle is short, easily is processed into the assembly of various complicated shapes, is convenient to utilize.
The present invention is described in further detail below in conjunction with accompanying drawing and concrete execution mode
Description of drawings
Fig. 1 is the X-ray diffractogram of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment one.
Fig. 2 is the stereoscan photograph of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment one.
Fig. 3 is the magneto-resistor-temperature curve of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment two.
Fig. 4 is the magneto-resistor-temperature curve of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment three.
Fig. 5 is the X-ray diffractogram of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment seven.
Fig. 6 is the stereoscan photograph of the compound phase calcium titanium ore manganose oxide magnetic resistance material of embodiment seven.
Embodiment
Embodiment one
A kind of embodiment of the present invention is, the compound phase calcium titanium ore manganose oxide magnetic resistance material that a kind of metal is bonding, and it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.3, A, Mn, wherein A is Sr, and the raw material that is equipped with is carried out 3 times calcining and the grinding after the calcining, it is 10 hours that each calcining heat is 1200 ℃ of times, namely gets La
0.7Sr
0.3MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 10% metallic tin (Sn) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 800Mpa pressure, namely.
Fig. 1,2 is respectively X-ray diffractogram and the stereoscan photograph of the material that the example method makes.As seen making thing by Fig. 1,2 is La
0.7Sr
0.3MnO
3With the mixture of metallic tin, and its crystal phase structure is good.
Embodiment two
This example is basic identical with embodiment one, and difference only is: the metallic tin that b added in the step is 5% of forerunner's grain weight amount.
Fig. 3 is the magneto-resistor-temperature curve that records under the 3kOe at externally-applied magnetic field for the example method makes thing, as seen from Figure 3, the material of this method preparation not only has the characteristic of a low magneto-resistor, and in the temperature range of 210～350K, the magnetoelectricity resistance is all more than 4%, and size varies with temperature scope and little.
Embodiment three
This example is basic identical with embodiment one, and difference only is: the metallic tin that b added in the step is 8% of forerunner's grain weight amount.
Fig. 4 is the magneto-resistor-temperature curve that records under the 3kOe for the example method makes thing at externally-applied magnetic field, and as seen from Figure 4, the material of this method preparation has the significantly feature of a low magneto-resistor, and has bigger magnetoelectricity resistance.
Embodiment four
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.3, A, Mn, wherein A is Sr, and the raw material that is equipped with is carried out 2 times calcining and the grinding after the calcining, it is 20 hours that each calcining heat is 1000 ℃ of times, namely gets La
0.7Sr
0.3MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 15% metallic tin (Sn) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 100Mpa pressure, namely.
Embodiment five
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.3, A, Mn, wherein A is Sr, and the raw material that is equipped with is carried out 2 times calcining and the grinding after the calcining, it is 5 hours that each calcining heat is 1300 ℃ of times, namely gets La
0.7Sr
0.3MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 10% metallic tin (Sn) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 400Mpa pressure, namely.
Embodiment six
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.9, A, Mn, wherein A is Ca, and the raw material that is equipped with is carried out 2 times calcining and the grinding after the calcining, it is 20 hours that each calcining heat is 1000 ℃ of times, namely gets La
0.1Ca
0.9MnO
3Forerunner's powder.
B, mix bonding
Forerunner's powder in a step and weight 8% indium metal (In) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 300Mpa pressure, namely.
Embodiment seven
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.2, A, Mn, wherein A is Sr, and the raw material that is equipped with is carried out 3 times calcining and the grinding after the calcining, it is 10 hours that each calcining heat is 1200 ℃ of times, namely gets La
0.8Sr
0.2MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 20% metallic zinc (Zn) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 800Mpa pressure, namely.
Fig. 5,6 is respectively X-ray diffractogram and the stereoscan photograph of the material that the example method makes.As seen making thing by Fig. 5,6 is La
0.8Sr
0.2MnO
3With the mixture of metallic zinc, and its crystal phase structure is good.
Embodiment eight
This example is basic identical with embodiment seven, and difference is: each calcining heat was 1000 ℃ during a went on foot, and the time is 20 hours; The metal zinc that b added in the step is 40% of forerunner's grain weight amount; The pressure of compression moulding is 100Mpa.
Embodiment nine
This example is basic identical with embodiment seven, and difference is: each calcining heat was 1300 ℃ during a went on foot, and the time is 5 hours; The metal zinc that b added in the step is 5% of forerunner's grain weight amount; The pressure of compression moulding is 400Mpa.
Embodiment ten
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.9, A, Mn, wherein A is Ca, and the raw material that is equipped with is carried out 3 times calcining and the grinding after the calcining, it is 10 hours that each calcining heat is 1200 ℃ of times, namely gets La
0.1Ca
0.9MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 10% silver powder for forerunner's powder is mixed, after grinding is even, compression moulding under 800Mpa pressure, namely.
Embodiment 11
This example is basic identical with embodiment ten, and difference is: the temperature that a calcined in the step at every turn is 1000 ℃, and the time is 20 hours; The silver powder that b added in the step is 30% of forerunner's grain weight amount, and the pressure of compression moulding is 600Mpa.
Embodiment 12
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.1, A, Mn, wherein A is Ca, and the raw material that is equipped with is carried out 2 times calcining and the grinding after the calcining, it is 15 hours that each calcining heat is 1000 ℃ of times, namely gets La
0.9Ca
0.1MnO
3Forerunner's powder.
B, bonding
Forerunner's powder in a step and weight 10% indium metal (In) powder for forerunner's powder is mixed, after grinding is even, compression moulding under 800Mpa pressure, namely.
Embodiment 13
The compound phase calcium titanium ore manganose oxide magnetic resistance material that this routine metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3And MnO
2By molecular formula La
1-xA
xMnO
3The atom proportion ingredient of the La of x=0.5, A, Mn, wherein A is Ca, and the raw material that is equipped with is carried out 3 times calcining and the grinding after the calcining, it is 10 hours that each calcining heat is 1100 ℃ of times, namely gets La
0.5Ca
0.5MnO
3Forerunner's powder.
B, mix bonding
Forerunner's powder in a step and weight are mixed for 15% Metallic Indium Powder of forerunner's powder, after grinding is even, compression moulding under 800Mpa pressure, namely.
Claims (1)
1. compound phase calcium titanium ore manganose oxide magnetic resistance material that metal is bonding, it is made by following method:
A, preparation forerunner powder
With La
2O
3, SrCO
3Or CaCO
3, MnO
2Raw material is by molecular formula La
1-xA
xMnO
3The atomic ratio of (0.1≤x≤0.9) is equipped with raw material, and A is Sr or Ca in the formula; After the raw material that is equipped with mixed, grinds, carry out 2～3 times calcining and the grinding after the calcining, it is 5-20 hour that each calcining heat is 1000 ℃～1300 ℃ times, makes La
1-xA
xMnO
3Forerunner's powder;
B, bonding
Forerunner's powder in a step and weight 5～40% Sn, Zn, Ag or In metal powder for forerunner's powder mixed, after grinding is even, compression moulding under 100～800Mpa pressure, namely.
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| CN102176509B true CN102176509B (en) | 2013-08-14 |
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| CN102610743B (en) * | 2012-02-28 | 2014-03-12 | 东南大学 | Composite material manufacturing method capable of controllably increasing low-field magnetoresistance |
| CN104600192B (en) * | 2013-11-01 | 2017-11-07 | 中国科学院物理研究所 | Change with orbital and charge ordering and anisotropy field sends a telegraph heterogeneous structure material of inhibition effect and its production and use |
| CN108559949A (en) * | 2018-04-27 | 2018-09-21 | 昆明理工大学 | A kind of preparation method of perovskite thin film |
| CN108689703B (en) * | 2018-06-26 | 2021-01-05 | 桂林电子科技大学 | Lead-free ferroelectric ceramic material with giant dielectric constant and electric tuning characteristics and preparation method thereof |
| CN113113202B (en) * | 2021-03-31 | 2021-12-21 | 深圳大学 | Magnetocaloric material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545151A (en) * | 2003-11-18 | 2004-11-10 | 河北师范大学 | Copper and zinc doped lanthanum, strontium, and manganese perovskite structure oxide magneto resistor material and preparation method thereof |
| CN1968912A (en) * | 2004-06-24 | 2007-05-23 | 阿鲁策株式会社 | Method for producing perovskite complex oxide |
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| US8974855B2 (en) * | 2005-08-05 | 2015-03-10 | The United States Department Of Energy | Manganite perovskite ceramics, their precursors and methods for forming |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545151A (en) * | 2003-11-18 | 2004-11-10 | 河北师范大学 | Copper and zinc doped lanthanum, strontium, and manganese perovskite structure oxide magneto resistor material and preparation method thereof |
| CN1968912A (en) * | 2004-06-24 | 2007-05-23 | 阿鲁策株式会社 | Method for producing perovskite complex oxide |
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