CN102491427B - PrMnO3 doped with Na at position A and sol-gel preparation method thereof - Google Patents
PrMnO3 doped with Na at position A and sol-gel preparation method thereof Download PDFInfo
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- CN102491427B CN102491427B CN 201110418059 CN201110418059A CN102491427B CN 102491427 B CN102491427 B CN 102491427B CN 201110418059 CN201110418059 CN 201110418059 CN 201110418059 A CN201110418059 A CN 201110418059A CN 102491427 B CN102491427 B CN 102491427B
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Abstract
The invention discloses PrMnO3 doped with Na at a position A and a sol-gel preparation method thereof, which relate to PrMnO3 doped with Na at the position A and a preparation method thereof. The invention aims to solve the problems of long period, large energy consumption, small doped amount of Na and high monophasic property of NaxMnO3 synthesis by the conventional high-temperature solid-phase reaction method. The molecular formula of the PrMnO3 doped with Na at the position A is Pr1-xNaxMnO3, wherein x may be 0.25 or 0.35; and the PrMnO3 doped with Na at the position A is prepared by the sol-gel method. The preparation method has the advantages of preventing Na volatilization, increasing doped amount of Na, enhancing monophasic property of the PrMnO3 doped with Na at the position A, along with simple operation, short synthesis period and low energy consumption.
Description
Technical field
The present invention relates to the A position and mix the PrMnO of Na
3And preparation method thereof.
Background technology
Ln
1-xA
xMnO
3The magnetic property of (A=Ca, Sr, Ba, K, Na) has become the focus of magnetics research in recent years.Wherein that most study is Mn
3+: Mn
4+=2: 1 and two kinds of situations of 1: 1, the B position is transition metal element doped in (they distinguish corresponding ferromegnetism and the strongest situation of antiferromagnetism) and these two kinds of situations.Difference corresponding x=0.1667 and 0.25 when A=Na is at Pr
1-xNa
xMnO
3Preparation in international counterparts all adopted high-temperature solid phase reaction method.Because the volatility of Na salt even if add excessive Na salt, still can cause the deficiency of Na content, and the deficiency of Na content can cause separating out of Mn oxide compound, thereby can't make the single phase property product in the raw material.The incorporation of the highest Na is x=0.19 in the world at present.This has seriously restricted Pr
1-xNa
xMnO
3And Pr
0.75Na
0.25Mn
1-yM
yO
3The research of (M is the transition metal such as Cr, Fe, Co, Ni) magnetic property.In addition, long with the high temperature solid-state method synthesis cycle, power consumption is large.
Summary of the invention
The present invention will solve the existing synthetic Pr of high-temperature solid phase reaction method that solves
1-xNa
xMnO
3Exist the cycle long, power consumption is large, the problem of the low and single phase property that improves of the incorporation of Na; And provide the A position to mix the PrMnO of Na
3And sol-gel method prepares the PrMnO that Na is mixed in the A position
3Method.
A mixes the position PrMnO of Na
3Molecular formula be Pr
1-XNa
XMnO
3, X is 0.25 or 0.35.
Sol-gel method prepares the PrMnO that Na is mixed in the A position
3Method carry out in the steps below: step 1, press Pr
1-XNa
XMnO
3Stoichiometric ratio take by weighing nitrate, the NaNO of Pr
3And Mn (NO
3)
2, X is 0.25 or 0.35, with nitrate, the NaNO of Pr
3And Mn (NO
3)
2Reach citric acid and be dissolved in the deionized water, the mol ratio of the total amount of substance of praseodymium ion, sodium ion and mn ion and citric acid is 1.1: 1, the nitrate of Pr, NaNO
3, Mn (NO
3)
2With the mass percent concentration of citric acid be 5%～10%; Step 2, then in 70～100 ℃ water-bath, stir with 200～240 rev/mins rotating speed and make it form gel; Step 3, gel is placed in the loft drier at 60～90 ℃ of lower dry 46～50h; Step 4, xerogel is lighted, under 400 ℃ of conditions in retort furnace sintering, and insulation 4h; Gel after burning is ground at mortar, use the tabletting machine compressing tablet, under 500 ℃ of conditions in retort furnace sintering, be incubated 4h; Under 700 ℃ of conditions, burn 6h; Then grind compressing tablet and burn 1000 ℃ of insulation 6h, namely obtain the PrMnO that Na is mixed in the A position
3
Because separating out of the volatilization of alkalimetal ion and the Mn oxide that causes thus, so that the Pr of Satoh (Joumal of Alloys and Compounds 333 (2002) 21-27) and the preparation of J.hejtm á nek (J.Solid State Chem.132 (1997), 98) solid reaction process
0.75Na
0.25MnO
3The maximum incorporation of middle Na is only for being 0.19.And the incorporation of Na is 0.25 o'clock, Mn
3+/ Mn
4+～1: 1, this moment, electric charge was the strongest in order, and in fields such as magnetic control quantum switches potential application was arranged.The incorporation of Na was convenient to study the various character of highly doped sample greater than 0.25 o'clock.Therefore, seeking incorporation that suitable sample preparation methods improves Na has important fundamental research and is worth and potential application prospect.
The present invention has simple to operate, and synthesis cycle is short, consumes energy low, can prevent the Na volatilization, improves the incorporation of Na, improves the advantage of product single phase property.
Description of drawings
Fig. 1 is Pr
0.75Na
0.25MnO
3Powder X-ray RD spectrogram; Fig. 2 is Pr
0.65Na
0.35MnO
3Powder X-ray RD spectrogram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: A mixes the position PrMnO of Na in the present embodiment
3Molecular formula be Pr
1-XNa
XMnO
3, X is 0.25 or 0.35.
Embodiment two: sol-gel method prepares the PrMnO that Na is mixed in the A position in the present embodiment
3Method carry out in the steps below:
Step 1, press Pr
1-XNa
XMnO
3Stoichiometric ratio take by weighing nitrate, the NaNO of Pr
3And Mn (NO
3)
2, X is 0.25 or 0.35, with nitrate, the NaNO of Pr
3And Mn (NO
3)
2Reach citric acid and be dissolved in the deionized water, the mol ratio of the total amount of substance of praseodymium ion, sodium ion and mn ion and citric acid is 1.1: 1, the nitrate of Pr, NaNO
3, Mn (NO
3)
2With the mass percent concentration of citric acid be 5%～10%;
Step 2, then in 70～100 ℃ water-bath, stir with 200～240 rev/mins rotating speed and make it form gel;
Step 3, gel is placed in the loft drier at 60～90 ℃ of lower dry 46～50h;
Step 4, xerogel is lighted, under 400 ℃ of conditions in retort furnace sintering, and insulation 4h; Gel after burning is ground at mortar, use the tabletting machine compressing tablet, under 500 ℃ of conditions in retort furnace sintering, be incubated 4h; Under 700 ℃ of conditions, burn 6h; Then grind compressing tablet and burn 1000 ℃ of insulation 6h, namely obtain the PrMnO that Na is mixed in the A position
3
Embodiment three: what present embodiment and embodiment one were different is: the temperature of the heating in water bath described in the step 2 is 80～90 ℃.Other step is identical with embodiment one with parameter.
Embodiment four: what present embodiment was different from embodiment two or three is: step 2 stirs with 210～230 rev/mins rotating speed.Other step is identical with embodiment two or three with parameter.
Embodiment five: what present embodiment was different from one of embodiment two to four is: the described drying temperature of step 3 is 70～80 ℃.Other step is identical with one of embodiment two to four with parameter.
Embodiment six: what present embodiment was different from one of embodiment two to five is: the preparation method of the nitrate of the described Pr of step 1: the oxide compound of praseodymium is added in excessive 10% the concentrated nitric acid, dissolving is (until the oxide compound of black praseodymium all dissolves in 80～95 ℃ water-bath, about 1 hour), continue heating in water bath to excessive concentrated nitric acid evaporation; Obtain the nitrate of Pr.Other step is identical with one of embodiment two to five with parameter.
Embodiment seven: what present embodiment and embodiment six were different is: dissolve in 90～95 ℃ water-bath.Other step is identical with embodiment six with parameter.
Adopt following verification experimental verification effect of the present invention:
Sol-gel method prepares the PrMnO that Na is mixed in the A position
3Method carry out in the steps below:
Step 1, press Pr
1-XNa
XMnO
3Stoichiometric ratio take by weighing nitrate, the NaNO of Pr
3And Mn (NO
3)
2, X is 0.25 or 0.35, with nitrate, the NaNO of Pr
3And Mn (NO
3)
2Reach citric acid and be dissolved in the deionized water, the mol ratio of the total amount of substance of praseodymium ion, sodium ion and mn ion and citric acid is 1.1: 1, the nitrate of Pr, NaNO
3, Mn (NO
3)
2With the mass percent concentration of citric acid be 8%;
Step 2, then stir with 220 rev/mins rotating speed in 80 ℃ the water-bath and make it form gel;
Step 3, gel is placed in the loft drier at 70 ℃ of lower dry 48h;
Step 4, xerogel is lighted, under 400 ℃ of conditions in retort furnace sintering, and insulation 4h; Gel after burning is ground at mortar, use the tabletting machine compressing tablet, under 500 ℃ of conditions in retort furnace sintering, be incubated 4h; Under 700 ℃ of conditions, burn 6h; Then grind compressing tablet and burn 1000 ℃ of insulation 6h, namely obtain the PrMnO that Na is mixed in the A position
3
The preparation method of the nitrate of the described Pr of step 1: the oxide compound of praseodymium added in excessive 10% the concentrated nitric acid, dissolving is (until the oxide compound of black praseodymium all dissolves in 90 ℃ water-bath, about 1 hour), continue heating in water bath to excessive concentrated nitric acid evaporation; Obtain the nitrate of Pr.
At Pr
1-xNa
xMnO
3Preparation in international counterparts all adopted high-temperature solid phase reaction method.Because the volatility of Na salt even if add excessive Na salt, still can cause the deficiency of Na content, and the deficiency of Na content can cause separating out of Mn oxide compound, thereby can't make the single phase property product in the raw material.The present invention has adopted sol-gel method to prepare the Pr that Na is mixed in the A position
1-xNa
xMnO
3, bring up to x=0.35 with the incorporation of bibliographical information (S.Zouari etc., Joumal of Alloys and Compounds333 (2002) 21-27) Na that compares from x=0.19.The method has not only significantly improved the incorporation content of Na, and has improved the single phase property (referring to Fig. 1, Fig. 2) of product.For to Pr
1-xNa
xMnO
3And Pr
0.75Na
0.25Mn
1-yM
yO
3New prospect has been opened up in the research of (M is the transition metal such as Cr, Fe, Co, Ni) magnetic property.
Claims (1)
1. sol-gel method prepares the PrMnO that Na is mixed in the A position
3Method, it is characterized in that sol-gel method prepares the PrMnO that Na is mixed in the A position
3Method carry out in the steps below:
Step 1, press Pr
1-XNa
XMnO
3Stoichiometric ratio take by weighing nitrate, the NaNO of Pr
3And Mn (NO
3)
2, X is 0.35, with nitrate, the NaNO of Pr
3And Mn (NO
3)
2Reach citric acid and be dissolved in the deionized water, the mol ratio of the total amount of substance of praseodymium ion, sodium ion and mn ion and citric acid is 1.1: 1, the nitrate of Pr, NaNO
3, Mn (NO
3)
2With the mass percent concentration of citric acid be 8%;
Step 2, then in 80 ℃ water-bath, stir with 220 rev/mins rotating speed and make it form gel;
Step 3, gel is placed in the loft drier at 70 ℃ of lower dry 48h;
Step 4, xerogel is lighted, under 400 ℃ of conditions in retort furnace sintering, and insulation 4h; Gel after burning is ground at mortar, use the tabletting machine compressing tablet, under 500 ℃ of conditions in retort furnace sintering, be incubated 4h; Under 700 ℃ of conditions, burn 6h; Then grind compressing tablet and burn 1000 ℃ of insulation 6h, namely obtain the PrMnO that Na is mixed in the A position
3
The preparation method of the nitrate of the described Pr of step 1: the oxide compound of praseodymium added in excessive 10% the concentrated nitric acid, in 90 ℃ water-bath, dissolve, continue heating in water bath to excessive concentrated nitric acid evaporation; Obtain the nitrate of Pr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110418059 CN102491427B (en) | 2011-12-14 | 2011-12-14 | PrMnO3 doped with Na at position A and sol-gel preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110418059 CN102491427B (en) | 2011-12-14 | 2011-12-14 | PrMnO3 doped with Na at position A and sol-gel preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102491427A CN102491427A (en) | 2012-06-13 |
| CN102491427B true CN102491427B (en) | 2013-10-23 |
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| CN111484080B (en) * | 2020-04-21 | 2022-12-27 | 桂林电子科技大学 | Neodymium-doped praseodymium manganese oxide wave-absorbing powder material and preparation method thereof |
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2011
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Non-Patent Citations (4)
| Title |
|---|
| M.Dlouha.NEUTRON POWDER DIFFRACTION STUDY OF THE MIXED-VALENCE MANGANITES.《Acta Cryst.》.2002, |
| NEUTRON POWDER DIFFRACTION STUDY OF THE MIXED-VALENCE MANGANITES;M.Dlouha;《Acta Cryst.》;20021231 * |
| Pr0.75Na0.25Mn1-xFexO3的制备及磁学和输运性质研究;李玉;《低温物理学报》;20100228;第32卷(第1期);第28、29页 * |
| 李玉.Pr0.75Na0.25Mn1-xFexO3的制备及磁学和输运性质研究.《低温物理学报》.2010,第32卷(第1期), |
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