CN102010012B - Method for preparing bismuth ferrite material by two-step solid-phase reaction - Google Patents
Method for preparing bismuth ferrite material by two-step solid-phase reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing a bismuth ferrite material by a two-step solid-phase reaction, in particular to a method for preparing uniform bismuth ferrite particles at a relatively low temperature. The method comprises the following steps of: performing a solid-phase reaction on raw materials at room temperature so as to obtain a reactant with a large specific surface area, high reaction activity and small particle size; and heating the reactant at a relatively low temperature so as to obtain a bismuth ferrite product. Compared with the prior art, the method has the advantages that: the method has relatively low synthesis temperature, simple process and high efficiency, is low in cost, is easy to control and expand, and the like. The bismuth ferrite product obtained by the method has high purity, small particle size and uniform particles.
Description
Technical field
The present invention relates to a kind of method of utilizing two single-step solid phase reactions to prepare the ferrous acid bismuth, belong to field of inorganic materials.
Background technology
Ferrous acid bismuth BiFeO
3Be a kind of typical multi-ferroic material, have antiferromagnetic Ne&1&el temperature (T far above room temperature
N=380 ℃) and ferroelectrie Curie temperature (T
c=830 ℃), be one of minority single phase multi-iron material of having ferroelectricity and parasitic weak ferromagnetism at ambient temperature simultaneously.BiFeO
3This special property make it have important application prospects aspect emerging material with memory.As far back as the sixties in 20th century, people have just successfully prepared ferrous acid bismuth BiFeO
3(BFO) block materials, but it is quite narrow to generate the monophasic TR of BFO, very easily produces dephasign, therefore secular a, process has slowly been passed through in the preparation of single-phase BFO bulk and research.1997, Teowee, people such as G obtained the BFO film on the Si substrate and have obtained saturated ferroelectric hysteresis loop with sol-gel method first.Between 1997 to 2002, since the development of laser pulse technology and universal, Palkar, and human PLD (pulsed laser deposition) methods such as V.R. are successfully prepared the BFO film with saturated ferroelectric hysteresis loop on the Si substrate.2003, J.Wang utilized the PLD method, on the Si substrate with SrTiO
3Be transition layer, SrRuO
3For lower conducting dome has successfully prepared epitaxially grown BFO film, through test, this film has extraordinary ferroelectric and ferromegnetism, is a kind of multi-iron material that has wide application prospects.In recent years, people adopt different methods to prepare the BFO material of excellent property, and the spontaneous polarization strength of BFO film is equally matched with ferroelectric material PZT, so BFO becomes one of important candidate material of non-plumbum ferroelectric storer.Present traditional solid sintering technology prepares the ferrous acid bismuth, need be heated to then between 750 ℃ to 850 ℃ and obtain product 600 ℃ of pre-burnings usually, and the ferrous acid bismuth particle that obtains is big and be difficult to regulate size.Through adding that though organic ignition dope can reduce temperature but the higher industrial production that is unfavorable for of cost.Finding a kind of novel method simple and that can reduce ferrous acid bismuth granule footpath is the challenge that chemical field faces.
Tradition solid state reaction idea think under the room temperature between the solid or solid intravital diffusion too slow, the carrying out of having limited chemical reaction.Write in its " Solid statechemistry and its applications " book as Englishize scholar West in 1984: " at room temperature experiencing one period reasonable time; generally can not react to each other between solid; desire to make reaction to take place; must they be heated to very high temperature, normally 1000～1500 ℃ " with remarkable speed.Up to 1993; Still point out in " Teaching General Chemistry; AMaterials Science Companion " book that people such as Americanized scholar Arthur Bellis write: " solid state reaction will must at high temperature carry out reasonably accomplishing in the time ".New spring professor of Xin of coordination chemistry institute of Nanjing University and group thereof; Since 1986 the research of the inorganic solid-solid reaction under the low-heat condition: the solid-phase coordination chemical reaction under room temperature or the nearly room temperature has been carried out systematically exploring, has inquired into the mechanism of low heating temperature solid-solid reaction; Propose and with experiment confirm the four-stage of solid state reaction, i.e. diffusion-reaction-nucleation-growth, each step all might be the deciding step of speed of reaction; Summed up the distinctive rule that solid state reaction is followed, promptly solid state reaction has latent period, and there is stepwise reaction phenomenon etc. in no chemical equilibrium; Utilize the low-heat solid state reaction; A series of Mo (W)-Cu (Ag)-S cluster compounds have been synthesized with superior third-order nonlinear optical character; Admittedly synthesized the metastabilization compound that other method of a series of usefulness can not obtain-join compound; Having synthesized some has the material of special purpose, like off-color material, nano material etc.Jia Dian such as has given at the successful development of people, and a kind of novel method---the room temperature solid reaction process is used to prepare nano material, utilizes this method to synthesize nano materials such as simple oxide, composite oxides, sulfide, phosphoric acid salt, carbonate, oxalate and polyoxometallate.Domestic and international increasing inorganic chemist, organic chemist, solidification scholar, materials chemistry man, high molecular scholar, physical chemist have explored this field together from different perspectives, have obtained a large amount of infusive new results.Two single-step solid phase reaction methods utilize the room temperature solid state reaction to obtain the higher raw material of reactive behavior of nano level particle diameter earlier, under relatively low temperature, obtain final product then, and this method obtains the material that particle diameter is even, pattern is special and controlled easily.
Summary of the invention
The object of the present invention is to provide a kind of two single-step solid phase reactions to prepare the method for ferrous acid bismuth material, is the method that under relatively lower temp, prepares the even particulate of ferrous acid bismuth.This method the first step: raw material generation room temperature solid state reaction obtains having than bigger serface, high reaction activity and high, the less reactant of particle diameter; Second step: the temperature heating through relatively low can obtain product ferrous acid bismuth.This method is compared with prior art: it is relatively low to have a synthesis temperature, and technology is simple, efficient, with low cost, is easy to amplify advantages such as the product particle diameter that obtains is little, uniform particles.
A kind of two single-step solid phase reactions of the present invention prepare the method for ferrous acid bismuth material, follow these steps to carry out:
A, be that raw material adds sodium hydroxide with Bismuth trinitrate and iron nitrate, mixed grinding or ball milling 0.5-2 hour at ambient temperature, wherein the mol ratio of Bismuth trinitrate, iron nitrate and sodium hydroxide was Bi: Fe: NaOH=1-4: 1: 1-10;
The room temperature solid state reaction takes place in b, raw materials mix immediately, becomes congee pasty state reactant by powder stock, and afterreaction finished in 30 minutes, obtained powdered product;
C, the powder of step b is washed after remove by product SODIUMNITRATE, drying, temperature 400-700 ℃ of heating is 1-6 hour again, obtains the required product ferrous acid of part bismuth;
D, again with unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash again, drying can obtain whole required product ferrous acid bismuths.
The mol ratio of step a Bismuth trinitrate, iron nitrate and sodium hydroxide is Bi: Fe: NaOH=1-2: 1: 6-8.
Step b raw material in the room temperature solid state reaction becomes tawny congee shape reactant by white powder, and it is the tawny powder that reaction finishes the back.
Step c Heating temperature is 500-650 ℃, and the time is 1-3 hour.
Description of drawings
Final product and powder x-ray diffraction peak shape comparison diagram ferrous acid bismuth standard card that Fig. 1 obtains after through 550 ℃ of heating for the present invention.As can be seen from the figure two single-step solid phase reaction methods are the ferrous acid bismuth of pure phase at 550 ℃ of products that obtain with regard to reaction only, are lower than about 200 ℃ of traditional method.
The stereoscan photograph figure of the reactant that Fig. 2 obtains through the room temperature solid state reaction for the present invention.As can be seen from the figure reactant is the reactant enwrapped granule reactant below a large amount of 200 nanometers.Compare with the macrobead raw material, the less raw material of particle diameter has bigger specific surface area, high reaction activity and high.
The transmission electron microscope photo figure of the reactant that Fig. 3 obtains through the room temperature solid state reaction for the present invention.As can be seen from the figure reactant is the reactant enwrapped granule reactant below a large amount of 200 nanometers.Compare with the macrobead raw material, the less raw material of particle diameter has bigger specific surface area, high reaction activity and high.
The stereoscan photograph figure of the final product that Fig. 4 obtains after through 550 ℃ of heating for the present invention, as can be seen from the figure the reaction product particle size is comparatively even, and particle diameter is less than 500 nanometers.
The transmission electron microscope photo figure of the final product that Fig. 5 obtains after through 550 ℃ of heating for the present invention, as can be seen from the figure the reaction product particle particle diameter is less than 500 nanometers.
Embodiment
Embodiment 1
In molar ratio for Bi: Fe: NaOH=1: took by weighing Bismuth trinitrate, iron nitrate and sodium hydroxide mixed grinding at 1: 1 0.5 hour;
The room temperature solid state reaction promptly takes place in reactant, becomes tawny congee pasty state reactant by white powder, and afterreaction finished in 30 minutes, obtained the tawny powdered product;
Powder is washed after remove by product SODIUMNITRATE, and drying 400 ℃ of heating of temperature 1 hour, obtains the required product ferrous acid of part bismuth;
Again with unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, washing, drying can obtain final product, and yield is 55.2%.
Embodiment 2
Bi: Fe: NaOH=2.5 in molar ratio: took by weighing Bismuth trinitrate, iron nitrate and sodium hydroxide mixed grinding at 1: 51 hour;
The room temperature solid state reaction promptly takes place in reactant, becomes tawny congee pasty state reactant by white powder, and afterreaction finished in 30 minutes, obtained the tawny powdered product;
Powder is washed after remove by product SODIUMNITRATE, and drying 550 ℃ of heating of temperature 3 hours, obtains the required product ferrous acid of part bismuth;
With unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash, drying can obtain whole final products again again, and yield is 62.1%.
Embodiment 3
Bi: Fe: NaOH=4 in molar ratio: took by weighing Bismuth trinitrate, iron nitrate and sodium hydroxide mixed grinding at 1: 10 2 hours;
The room temperature solid state reaction promptly takes place in reactant, becomes tawny congee pasty state reactant by white powder, and afterreaction finished in 30 minutes, obtained the tawny powdered product;
Powder is washed after remove by product SODIUMNITRATE, and drying obtained the required product ferrous acid of part bismuth in 6 hours in 700 ℃ of heating of temperature;
With unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash, drying can obtain whole final product ferrous acid bismuths again again, and yield is 66.8%.
Embodiment 4
Bi: Fe: NaOH=3 in molar ratio: took by weighing Bismuth trinitrate, iron nitrate and sodium hydroxide mixed grinding at 1: 8 1.5 hours;
The room temperature solid state reaction promptly takes place in reactant, becomes tawny congee pasty state reactant by white powder, and afterreaction finished in 30 minutes, obtained the tawny powdered product;
Powder is washed after remove by product SODIUMNITRATE, and drying obtained the required product ferrous acid of part bismuth in 1 hour in 500 ℃ of heating of temperature;
With unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash, drying can obtain whole final product ferrous acid bismuths again again, and yield is 63.6%.
Embodiment 5
Bi: Fe: NaOH=2 in molar ratio: took by weighing Bismuth trinitrate, iron nitrate and sodium hydroxide mixed grinding at 1: 81 hour;
The room temperature solid state reaction promptly takes place in reactant, becomes tawny congee pasty state reactant by white powder, and afterreaction finished in 30 minutes, obtained the tawny powdered product;
Powder is washed after remove by product SODIUMNITRATE, and drying obtained the required product ferrous acid of part bismuth in 3 hours in 650 ℃ of heating of temperature;
With unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash, drying can obtain whole final product ferrous acid bismuths again again, and yield is 65.5%.
Claims (4)
1. a single-step solid phase reaction prepares the method for ferrous acid bismuth material, it is characterized in that following these steps to carrying out:
A, be that raw material adds sodium hydroxide with Bismuth trinitrate and iron nitrate, mixed grinding or ball milling 0.5-2 hour at ambient temperature, wherein the mol ratio of Bismuth trinitrate, iron nitrate and sodium hydroxide was Bi: Fe: NaOH=1-4: 1: 1-10;
The room temperature solid state reaction takes place in b, raw materials mix immediately, becomes congee pasty state reactant by powder stock, and afterreaction finished in 30 minutes, obtained powdered product;
C, the powder of step b is washed after remove by product SODIUMNITRATE, drying temperature 400-700 ℃ of heating 1-6 hour, obtains the required product ferrous acid of part bismuth;
D, again with unreacted raw material in 1: 1 by volume lysate of concentrated nitric acid, wash again, drying can obtain whole required product ferrous acid bismuths.
2. method according to claim 1, the mol ratio that it is characterized in that step a Bismuth trinitrate, iron nitrate and sodium hydroxide is Bi: Fe: NaOH=1-2: 1: 6-8.
3. method according to claim 2 is characterized in that step b raw material in the room temperature solid state reaction becomes tawny congee pasty state reactant by white powder, and it is the tawny powder that reaction finishes the back.
4. method according to claim 3 is characterized in that step c Heating temperature is 500-650 ℃, and the time is 1-3 hour.
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| CN102817067B (en) * | 2012-08-30 | 2015-08-19 | 安徽理工大学 | A kind of molten-salt growth method prepares the method for rhombohedron monocrystalline bismuth ferrite powder |
| CN102826610A (en) * | 2012-09-28 | 2012-12-19 | 中国科学院新疆理化技术研究所 | Preparation method of chlorine-doped bismuth ferrite powder |
| CN102826609B (en) * | 2012-09-28 | 2014-06-18 | 中国科学院新疆理化技术研究所 | Method for preparing ferromagnetism bismuth ferrite nano powder by room-temperature solid-phase reaction auxiliary combustion method |
| CN103936070A (en) * | 2014-05-05 | 2014-07-23 | 新疆大学 | Method for preparing bismuth oxyhalide nanosheet through solid-state chemical reaction at room temperature |
| CN104671666A (en) * | 2015-02-27 | 2015-06-03 | 陕西科技大学 | Preparation method of bismuth ferrite microcrystalline glass |
| CN104961162B (en) * | 2015-06-30 | 2017-03-08 | 电子科技大学 | A kind of method that single pure phase bismuth ferric material is prepared based on Lithium ions compensation |
| CN108975899B (en) * | 2018-09-17 | 2020-10-27 | 电子科技大学 | Preparation method of scandate for dipping diffusion cathode |
| CN109019647B (en) * | 2018-10-09 | 2020-12-29 | 电子科技大学 | Preparation method of aluminate for dipping diffusion cathode |
| CN113943882B (en) * | 2021-11-15 | 2022-09-30 | 上海海事大学 | Ag/BiFeO 3 Metal ceramic, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3694361A (en) * | 1971-09-07 | 1972-09-26 | Ampex | Lithium titanium bismuth cobalt ferrites |
| CN101654283A (en) * | 2009-09-17 | 2010-02-24 | 陕西科技大学 | Method for preparing bismuth ferrite powder by microwave hydrothermal method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3694361A (en) * | 1971-09-07 | 1972-09-26 | Ampex | Lithium titanium bismuth cobalt ferrites |
| CN101654283A (en) * | 2009-09-17 | 2010-02-24 | 陕西科技大学 | Method for preparing bismuth ferrite powder by microwave hydrothermal method |
Non-Patent Citations (2)
| Title |
|---|
| Matjaz Valant,et.al..Peculiarities of a Solid-State Synthesis of Multiferroic Polycrystalline BiFeO3.《Chemistry of Materials》.2007,第19卷(第22期),第5431-5436页. * |
| 杨彧等.低热固相反应制备无机纳米材料的方法.《无机化学学报》.2004,第20卷(第8期),第881-888页. * |
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