CN101307490A - 6H-BaRuO3 crystal and method for making same - Google Patents
6H-BaRuO3 crystal and method for making same Download PDFInfo
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- CN101307490A CN101307490A CNA2008100575145A CN200810057514A CN101307490A CN 101307490 A CN101307490 A CN 101307490A CN A2008100575145 A CNA2008100575145 A CN A2008100575145A CN 200810057514 A CN200810057514 A CN 200810057514A CN 101307490 A CN101307490 A CN 101307490A
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Abstract
The invention relates to a 6H-BaRuO3 crystal and a method for preparing the same. The method is as follows: firstly, a solid-state chemical method is adopted to prepare single-phase 9R-BaRuO3; secondly, high temperature and high pressure conditions are utilized to treat the single-phase 9R-BaRuO3; and finally the single-phase 6H-BaRuO3 crystal is synthesized by quenching the single-phase 9R-BaRuO3, wherein, the high temperature and high pressure conditions are as follows: the temperature is between 900 and 1100 DEG C, the pressure is between 3 and 5GPa, and the heat preservation time is more than 30 minutes. The magnetism of the 6H-BaRuO3 crystal comprises two parts, namely Curie paramagnetism and Pauli paramagnetism with strengthened exchange, and the 6H-BaRuO3 crystal can be used as paramagnetic metal.
Description
Technical field
The present invention relates to a kind of 6H-BaRuO
3Crystal and preparation method thereof particularly relates to a kind of single-phase 6H-BaRuO of high temperature and high pressure method synthetic that utilizes
3Crystal and prepare this crystalline high temperature and high pressure method.
Background technology
In recent years, because ru oxide has the character of a lot of novelties, people have launched extensive studies work to it.ARuO
3(A=Ca, Sr, Ba) is an important system in the ru oxide, SrRuO
3And CaRuO
3Belong to perovskite structure, spacer is Pbnm.The former is a ferromagnetic metal, and the latter is a paramagnetic metal.Because Ba
2+Ion and Ru
4+It is bigger that ionic radius differs, BaRuO
3Be difficult for forming perovskite structure, and form six sides (or tripartite) laminate structure easily.Its normal pressure phase (9R-BaRuO
3) be a kind of material with counterfeit energy gap.At BaRuO
3In, the Ba ion becomes BaO with O ion solid matter
3Plane, Ru ion are filled among the O ionic space, constitute RuO
6Octahedra.Different according to octahedra mode of connection (altogether summit and coplane), BaRuO
3Have three kinds of laminate structure: 9R, 4H and 6H, wherein, BaO in the numeral structure cell
3The planar number, the letter representation structure type.9R-BaRuO
3Can obtain by the solid state reaction under the normal pressure mutually, be trigonal crystal structure, its spacer is R-3m; 4H-BaRuO
3And 6H-BaRuO
3Be hexagonal structure mutually, its spacer is P6
3/ mmc.
But a difficult problem of failing to overcome at present is to synthesize monophasic 6H-BaRuO
3Crystal, thus can not characterize its structure and rerum natura.Because pressure is suitable for the uhligite material of Metacentre Height densification very much, is bringing into play in the research of material and important effect, be the important means of development ru oxide, so, based on this, for overcoming this difficult problem, we have adopted the High Temperature High Pressure synthetic method, by to 9R-BaRuO
3Carry out high temperature high pressure process mutually, thereby obtained monophasic 6H-BaRuO
3Crystal, and make its crystalline structure of research and physical properties become possibility.
Summary of the invention
One of purpose of the present invention provides a kind of monophasic 6H-BaRuO
3Crystal, this crystal are by handling monophasic 9R-BaRuO under High Temperature High Pressure
3Synthetic.
Another object of the present invention provides a kind of single-phase 6H-BaRuO
3The crystalline preparation method.
To achieve these goals, the present invention has adopted following technical scheme:
The invention provides a kind of monophasic 6H-BaRuO
3Crystal, its spacer are P6
3/ mmc, unit cell parameters is:
The invention provides a kind of single-phase 6H-BaRuO
3Crystalline preparation method, this method adopt the solid state chemistry method to prepare monophasic 9R-BaRuO earlier
3Utilize high-temperature and high-pressure conditions to handle monophasic 9R-BaRuO then
3, then through the synthetic single-phase 6H-BaRuO that quenches
3Crystal, above-mentioned high-temperature and high-pressure conditions is: 900 ℃-1100 ℃ of temperature, preferred 950 ℃-1050 ℃, more preferably 1000 ℃; Pressure 3-5GPa, preferred 4.5-5GPa, more preferably 5GPa; Soaking time is more than 30 minutes.
Above-mentioned single-phase 6H-BaRuO
3Among the crystalline preparation method, described solid state chemistry method is prepared single-phase 9R-BaRuO
3Concrete steps comprise:
Utilize solid state reaction under the normal pressure, with chemical pure BaCO
3(purity is not less than 99.9%) and Ru powder were with 1: 1 mixed in molar ratio, grinding, under 900 ℃-1000 ℃ condition, carry out first sintering, insulation is more than 12 hours, under 1100 ℃-1200 ℃ condition, carry out the sintering second time then, insulation is more than 24 hours, perhaps repeat sintering repeatedly the second time in the agglomerating temperature range again, preferred 2 times, finally obtain monophasic 9R-BaRuO
3
Wherein, preferred 1100 ℃ of sintering temperature for the second time.
Above-mentioned single-phase 6H-BaRuO
3Among the crystalline preparation method, high temperature and high pressure method is handled single-phase 9R-BaRuO
3Concrete steps comprise:
With the single-phase 9R-BaRuO that obtains under the normal pressure
3The sequin that is pressed into, preferred diameter is that 5mm, thickness are 1.5mm, and with goldleaf or platinum foil or parcel, this sample is put into graphite furnace, carries out height in the high pressure assembly of packing into and is pressed into, the medium of using in the graphite furnace is hexagonal boron nitride (h-BN).Sample synthesizes on slide block type cubic apparatus high-pressure unit and carries out, and at room temperature slowly boosts to 4.5-5GPa earlier, restarts heating schedule and is heated to 950 ℃-1050 ℃, is incubated then more than 30 minutes, is quenched to room temperature, release then (1GP,a=1 ten thousand normal atmosphere).
Wherein, before High-Voltage Experimentation, preferably carry out the demarcation of temperature and pressure, and control Heating temperature with the method for control heating power.
Utilize high-temperature and high-pressure conditions of the present invention, can be to the single-phase 9R-BaRuO of synthetic under the normal pressure
3Handle, thereby prepare monophasic 6H-BaRuO
3Crystal, this crystal structure quality is good, turns out to be single-phasely through X-ray diffraction, and its physical structure and performance is tested.6H-BaRuO of the present invention
3Crystalline magnetic comprises Curie paramagnetism and exchange enhanced Pauli paramagnetism two portions, and it can be used as paramagnetic metal and is used.
Description of drawings
Below in conjunction with drawings and Examples the present invention is done description further:
Fig. 1 is the assembly drawing of High Temperature High Pressure synthetic sample of the present invention.
Fig. 2 is the prepared 6H-BaRuO of high temperature and high pressure method of the present invention
3Crystalline XRD figure spectrum has been carried out indexing to main diffraction peak among the figure.
Fig. 3 is the prepared 6H-BaRuO of high temperature and high pressure method of the present invention
3Crystalline resistivity and susceptibility are with the variation of temperature graph of a relation.
Embodiment
Embodiment 1
1) under the normal pressure, utilize the solid state chemistry method to prepare monophasic 9R-BaRuO
3
Utilize solid state reaction, with the BaCO of 99.9% purity
3With mixed in molar ratio, the grinding with 1: 1 of the Ru powder of 99.9% purity, sintering under 900 ℃ condition is incubated 12 hours.Sintering 3 times under 1100 ℃ condition is incubated 24 hours then, just can obtain monophasic 9R-BaRuO
3Crystal.
2) utilize high temperature and high pressure method to synthesize monophasic 6H-BaRuO
3Crystal.
With the single-phase 9R-BaRuO that obtains under the normal pressure
3Be pressed into the sequin of diameter 5mm, thickness 1.5mm, wrap up with goldleaf.Sample is put into graphite furnace, carry out height in as shown in Figure 1 the high pressure assembly of packing into and be pressed into, wherein the medium of using in the graphite furnace is hexagonal boron nitride (h-BN).Sample synthesizes on slide block type cubic apparatus high-pressure unit and carries out, and at first carries out the demarcation of temperature and pressure before the High-Voltage Experimentation, with the method control Heating temperature of control heating power.Earlier at room temperature slowly boost to 5GPa, restart heating schedule and be heated to 1000 ℃, insulation is 30 minutes under high-temperature and high-pressure conditions, is quenched to room temperature, release then (1GP,a=1 ten thousand normal atmosphere).
The sample that the back of quenching is obtained carries out X-ray diffraction studies (the results are shown among Fig. 2), is found to be monophasic 6H-BaRuO
3Crystal, crystalline quality is better, and its spacer is P6
3/ mmc, unit cell parameters is:
Its resistivity and susceptibility are shown among Fig. 3 with the variation of temperature relation.
Embodiment 2
1) under the normal pressure, utilize the solid state chemistry method to prepare monophasic 9R-BaRuO
3
Utilize solid state reaction, with the BaCO of 99.9% purity
3With mixed in molar ratio, the grinding with 1: 1 of the Ru powder of 99.9% purity, sintering under 1000 ℃ condition is incubated 12 hours.Sintering 3 times under 1100 ℃ condition is incubated 24 hours at every turn then, just can obtain monophasic 9R-BaRuO
3
2) utilize high temperature and high pressure method to synthesize monophasic 6H-BaRuO
3Crystal.
With the single-phase 9R-BaRuO that obtains under the normal pressure
3Be pressed into the sequin of diameter 5mm, thickness 1.5mm, wrap up with platinum foil.Sample is put into graphite furnace, carry out height in the high pressure assembly of packing into and be pressed into, the medium of using in the graphite furnace is hexagonal boron nitride (h-BN).Sample synthesizes on slide block type cubic apparatus high-pressure unit and carries out, and at first carries out the demarcation of temperature and pressure before the High-Voltage Experimentation, with the method control Heating temperature of control heating power.Earlier at room temperature slowly boost to 4GPa, restart heating schedule and be heated to 1050 ℃, insulation is 60 minutes under high-temperature and high-pressure conditions, is quenched to room temperature, release then (1GP,a=1 ten thousand normal atmosphere).
With embodiment 1, the sample that the back of quenching is obtained carries out X-ray diffraction studies, is found to be monophasic 6H-BaRuO
3Crystal, crystalline quality is better.
Embodiment 3
1) under the normal pressure, utilize the solid state chemistry method to prepare monophasic 9R-BaRuO
3
Utilize solid state reaction, with the BaCO of 99.9% purity
3With mixed in molar ratio, the grinding with 1: 1 of the Ru powder of 99.9% purity, sintering under 900 ℃ condition is incubated 12 hours.Sintering 3 times under 1200 ℃ condition is incubated 24 hours at every turn then, just can obtain monophasic 9R-BaRuO
3
2) utilize high temperature and high pressure method to synthesize monophasic 6H-BaRuO
3Crystal.
With the single-phase 9R-BaRuO that obtains under the normal pressure
3Be pressed into the sequin of diameter 5mm, thickness 1.5mm, wrap up with goldleaf.Sample is put into graphite furnace, carry out height in the high pressure assembly of packing into and be pressed into, the medium of using in the graphite furnace is hexagonal boron nitride (h-BN).Sample synthesizes on slide block type cubic apparatus high-pressure unit and carries out, and at first carries out the demarcation of temperature and pressure before the High-Voltage Experimentation, with the method control Heating temperature of control heating power.Earlier at room temperature slowly boost to 3GPa, restart heating schedule and be heated to 1100 ℃, insulation is 30 minutes under high-temperature and high-pressure conditions, is quenched to room temperature, release then (1GP,a=1 ten thousand normal atmosphere).
With embodiment 1, the sample that the back of quenching is obtained carries out X-ray diffraction studies, is found to be monophasic 6H-BaRuO
3Crystal, crystalline quality is better.
Embodiment 4
Except high pressure adopts 5GPa, temperature adopts 900 ℃, be incubated 120 minutes beyond, all the other are with embodiment 2.
Embodiment 5
Except high pressure adopts 4.5GPa, temperature adopts 950 ℃, be incubated 100 minutes beyond, all the other are with embodiment 1.
It should be noted that; above in conjunction with the embodiments technical scheme of the present invention is had been described in detail; but those skilled in the art will find apparent that; on the technical solution of the present invention basis; can carry out variations and modifications to technical scheme of the present invention, but not break away from the generalized scope of the present invention's claims required for protection.
Claims (10)
1, a kind of monophasic 6H-BaRuO
3Crystal, its spacer are P6
3/ mmc, unit cell parameters is:
2, a kind of single-phase 6H-BaRuO
3Crystalline preparation method, this method adopt the solid state chemistry method to prepare monophasic 9R-BaRuO earlier
3, utilize high-temperature and high-pressure conditions to handle monophasic 9R-BaRuO again
3, then through the synthetic single-phase 6H-BaRuO that quenches
3Crystal is characterized in that, described high-temperature and high-pressure conditions is: 900 ℃-1100 ℃ of temperature; Pressure 3-5GPa; Soaking time is more than 30 minutes.
3, preparation method as claimed in claim 2 is characterized in that, described high-temperature and high-pressure conditions is: 950 ℃-1050 ℃ of temperature; Pressure 4.5-5GPa.
4, preparation method as claimed in claim 2 is characterized in that, described high-temperature and high-pressure conditions adopts graphite furnace to carry out height and is pressed into, and the medium in the graphite furnace is hexagonal boron nitride (h-BN).
As each described preparation method of claim 2-4, it is characterized in that 5, described solid state chemistry method is prepared single-phase 9R-BaRuO
3Concrete steps comprise:
Utilize solid state reaction under the normal pressure, with chemical pure BaCO
3With of mixed in molar ratio, the grinding of Ru powder with 1: 1, under 900 ℃-1000 ℃ condition, carry out first sintering, insulation is more than 12 hours; Carry out the sintering second time then under 1100 ℃-1200 ℃ temperature condition, insulation perhaps repeats sintering repeatedly the second time in the agglomerating temperature range more than 24 hours again, finally obtains monophasic 9R-BaRuO
3
6, preparation method as claimed in claim 5 is characterized in that, described chemical pure purity is not less than 99.9%; Described agglomerating repetition sintering second time number of times repeatedly is 2 times.
7, as each described preparation method of claim 2-4, it is characterized in that described high temperature and high pressure method is handled single-phase 9R-BaRuO
3Concrete steps comprise:
With the single-phase 9R-BaRuO that obtains under the normal pressure
3Be pressed into sequin, and with goldleaf or platinum foil parcel, this sample is put into graphite furnace, carry out height in the high pressure assembly of packing into and be pressed into, the medium of using in the graphite furnace is hexagonal boron nitride (h-BN), sample synthesizes on slide block type cubic apparatus high-pressure unit and carries out, earlier at room temperature slowly boost to 4.5-5GPa, restart heating schedule and be heated to 950 ℃-1050 ℃, be incubated then more than 30 minutes, be quenched to room temperature, then release.
8, preparation method as claimed in claim 7 is characterized in that, before described height is pressed into, carries out the demarcation of temperature and pressure, and controls Heating temperature with the method for control heating power.
9, preparation method as claimed in claim 7 is characterized in that, the diameter of described sequin is that 5mm, thickness are 1.5mm.
10, a kind of monophasic 6H-BaRuO
3The crystalline purposes, this 6H-BaRuO
3Crystal can be used as paramagnetic metal to be used.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100575145A CN101307490A (en) | 2008-02-02 | 2008-02-02 | 6H-BaRuO3 crystal and method for making same |
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|---|---|---|---|
| CNA2008100575145A CN101307490A (en) | 2008-02-02 | 2008-02-02 | 6H-BaRuO3 crystal and method for making same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935878A (en) * | 2010-09-13 | 2011-01-05 | 中国科学院物理研究所 | 6H-phase perovskite BaCrO3 crystal and preparation method thereof |
| CN105887199A (en) * | 2016-04-20 | 2016-08-24 | 中国科学院物理研究所 | Novel compound Ca2CrO4 crystal and preparation method thereof |
| CN113755880A (en) * | 2021-09-15 | 2021-12-07 | 中山大学 | Application of ruthenate material in electrocatalytic hydrogen evolution reaction |
| CN114890782A (en) * | 2022-04-27 | 2022-08-12 | 湖北华磁电子科技有限公司 | Soft magnetic ferrite material for inverters in photovoltaic industry and preparation process thereof |
-
2008
- 2008-02-02 CN CNA2008100575145A patent/CN101307490A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935878A (en) * | 2010-09-13 | 2011-01-05 | 中国科学院物理研究所 | 6H-phase perovskite BaCrO3 crystal and preparation method thereof |
| CN101935878B (en) * | 2010-09-13 | 2013-04-17 | 中国科学院物理研究所 | 6H-phase perovskite BaCrO3 crystal and preparation method thereof |
| CN105887199A (en) * | 2016-04-20 | 2016-08-24 | 中国科学院物理研究所 | Novel compound Ca2CrO4 crystal and preparation method thereof |
| CN113755880A (en) * | 2021-09-15 | 2021-12-07 | 中山大学 | Application of ruthenate material in electrocatalytic hydrogen evolution reaction |
| CN113755880B (en) * | 2021-09-15 | 2022-08-02 | 中山大学 | Application of ruthenate material in electrocatalytic hydrogen evolution reaction |
| CN114890782A (en) * | 2022-04-27 | 2022-08-12 | 湖北华磁电子科技有限公司 | Soft magnetic ferrite material for inverters in photovoltaic industry and preparation process thereof |
| CN114890782B (en) * | 2022-04-27 | 2022-12-02 | 湖北华磁电子科技有限公司 | Soft magnetic ferrite material for inverters in photovoltaic industry and preparation process thereof |
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Open date: 20081119 |