CN110137346B - Manganese-doped holmium ferrite HoMn x Fe 1-x O 3 Preparation method of magnetoelectric material - Google Patents
Manganese-doped holmium ferrite HoMn x Fe 1-x O 3 Preparation method of magnetoelectric material Download PDFInfo
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- 229910052689 Holmium Inorganic materials 0.000 title claims abstract description 44
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000012086 standard solution Substances 0.000 claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
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- 238000005406 washing Methods 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000005690 magnetoelectric effect Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
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- 238000005054 agglomeration Methods 0.000 description 1
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Abstract
The invention discloses manganese-doped holmium ferrite HoMn x Fe 1‑ x O 3 Taking a holmium-containing compound, an iron-containing compound and a manganese-containing compound, respectively preparing a holmium-containing standard solution, an iron-containing standard solution and a manganese-containing standard solution, uniformly mixing the holmium-containing solution, the iron-containing solution and the manganese-containing solution under magnetic stirring to obtain a first mixed solution, adding solid KOH with the same mass as the first mixed solution into the first mixed solution at room temperature, fully dissolving the solid KOH until the solid KOH is fully dissolved, and cooling the mixture to the room temperature to obtain a second mixed solution; transferring the second mixed solution into a hydrothermal reaction kettle with a p-polyphenyl lining, placing the hydrothermal reaction kettle in a reaction furnace, heating to 200-260 ℃, preserving heat for 1-4 days, cooling the hydrothermal reaction kettle to obtain a first product, washing and drying the first product to obtain HoMn x Fe 1‑x O 3 A magnetoelectric material; the invention can prepare the material at a lower temperature at one time, and the product has uniform particles and regular crystal form, thereby overcoming the defects of high time consumption and high energy consumption of a solid phase method.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of magnetic memory materials, and particularly relates to manganese-doped holmium ferrite HoMn x Fe 1-x O 3 A preparation method of a magnetoelectric material.
[ background of the invention ]
Performance of magnetic memory is mainlyDepending on the magnetoelectric effect of the magnetoelectric material, hoMn x Fe 1-x O 3 The magnetic material has excellent magnetoelectric effect, and shows extremely sensitive magnetization effect under applied electric field. This allows the magnetic properties to be manipulated at extremely small electric fields, and thus the magnetic properties are critical to the response of the electric field when designing the memory element.
The solid phase method is the main means for preparing the rare earth composite oxide magnetic material at present, the reaction mechanism of the solid phase reaction is a thermodynamic diffusion process, reactants of the traditional solid phase method need to be subjected to solid phase diffusion at the temperature of more than 1000 ℃, and the reactants need to be repeatedly sintered for more than 3 times. It has the problems that: because the reaction is a solid-phase migration diffusion process, the reaction can be carried out only at extremely high reaction temperature, and repeated sintering treatment is needed, the preparation process is complex and high in cost, and meanwhile, the growth and agglomeration of product particles are difficult to control, the particles are uneven, the particle size distribution range is wide, the crystal form is irregular, and the properties of the material are seriously influenced.
[ summary of the invention ]
The invention aims to provide manganese-doped holmium ferrite HoMn x Fe 1-x O 3 The preparation method of the magnetoelectric material can prepare the magnetoelectric material at a lower temperature at one time, and the product has uniform particles and regular crystal form, thereby overcoming the defects of high time consumption and high energy consumption of a solid phase method.
The invention adopts the following technical scheme: manganese-doped holmium ferrite HoMn x Fe 1-x O 3 The preparation method of the magnetoelectric material comprises the following steps:
according to the preparation of HoMn x Fe 1-x O 3 Weighing a holmium-containing compound, an iron-containing compound and a manganese-containing compound according to the mass ratio of substances of the elements, respectively preparing a holmium-containing standard solution, an iron-containing standard solution and a manganese-containing standard solution, uniformly mixing the holmium-containing solution, the iron-containing solution and the manganese-containing solution under magnetic stirring to obtain a first mixed solution, adding solid KOH with the same mass as the first mixed solution into the first mixed solution at room temperature, fully dissolving, and cooling to room temperature to obtain a second mixed solution;
transferring the second mixed solution toPutting the mixture into a hydrothermal reaction kettle with a polyphenyl lining, keeping the filling degree at 70-80%, putting the hydrothermal reaction kettle into a reaction furnace, heating to 200-260 ℃, keeping the temperature for 1-4 days, cooling the hydrothermal reaction kettle to obtain a first product, putting the first product into cold water, quickly cooling to room temperature, washing and drying to obtain HoMn x Fe 1-x O 3 A magnetoelectric material.
Further, the iron-containing compound is Fe (NO) 3 ) 3 ·9H 2 O、Fe 2 (SO 4 ) 3 Or FeX 3 And X is a halogen ion.
Further, the manganese-containing compound is Mn (NO) 3 ) 2 ·4H 2 O、Mn 2 (SO 4 ) 3 Or MnX 2 And X is a halogen ion.
Further, the holmium-containing compound is Ho (NO) 3 ) 3 ·6H 2 O or Ho 2 (SO 4 ) 3 ·8H 2 O。
Further, the method comprises the following steps:
preparing a standard solution Ho (NO) 3 ) 3 、MnCl 2 And Fe (NO) 3 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、2mL MnCl 2 And 8mL Fe (NO) 3 ) 3 Magnetically stirring in a beaker, slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a p-polyphenyl lining, wherein the filling degree is 80%, carrying out hydrothermal reaction at 200 ℃ for 1 day, putting the reaction kettle into cold water at 25 ℃ for cooling, washing the cooled product with deionized water for 4 times, then washing with absolute ethyl alcohol for 4 times, and drying at 80 ℃ to obtain HoMn 0.2 Fe 0.8 O 3 And (3) powder.
Further, the method comprises the following steps:
preparing a standard solution Ho (NO) 3 ) 3 、Mn(NO 3 ) 2 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、4mL Mn(NO 3 ) 2 And 6mL FeCl 3 Magnetically stirring in a beaker, slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a polyphenyl lining, wherein the filling degree is 74%, carrying out hydrothermal reaction at 260 ℃ for 3 days, putting the reaction kettle into cold water at 28 ℃, washing the cooled product with deionized water for 4 times, then washing the product with absolute ethyl alcohol for 4 times, and drying the product at 80 ℃ to obtain HoMn 0.4 Fe 0.6 O 3 And (3) powder.
Further, the method comprises the following steps:
preparing a standard solution Ho 2 (SO 4 ) 3 、MnCl 2 And Fe 2 (SO 4 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
measuring 5mL Ho 2 (SO 4 ) 3 、6mL MnCl 2 And 4mL of Fe 2 (SO 4 ) 3 Magnetically stirring in a beaker, and slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a lining of p-polyphenyl, wherein the filling degree is 70%, carrying out hydrothermal reaction at 225 ℃ for 2.5 days, putting the reaction kettle into cold water at 20 ℃, washing the cooled product with deionized water for 4 times, then washing with absolute ethyl alcohol for 4 times, and drying at 80 ℃ to obtain HoMn 0.6 Fe 0.4 O 3 And (3) powder.
Further, the method comprises the following steps:
preparing a standard solution Ho (NO) 3 ) 3 、Mn 2 (SO 4 ) 3 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、8mL Mn 2 (SO 4 ) 3 And 2mL FeCl 3 Magnetically stirring in a beaker, and slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a p-polyphenyl lining, wherein the filling degree is 78%, performing hydrothermal reaction at 255 ℃ for 4 days, putting the reaction kettle into cold water at 15 ℃, washing the cooled product with deionized water for 4 times, then washing the product with absolute ethyl alcohol for 4 times, and drying the product at 80 ℃ to obtain HoMn 0.8 Fe 0.2 O 3 And (3) powder.
The other technical scheme of the invention is as follows: manganese-doped holmium ferrite HoMn x Fe 1-x O 3 The manganese-doped holmium ferrite magnetoelectric material has a chemical formula of HoMn x Fe 1-x O 3 And x has a value range of 0<x<1。
Furthermore, the material is of a perovskite structure.
The invention has the beneficial effects that: the invention takes part in the mixing of the reaction ions before the reaction and the diffusion of the ions in the reaction process are carried out in the liquid phase, because the water plays the role of a medium, the whole reaction process is carried out in a uniformly dispersed system, the ion diffusion is easy to carry out, the reaction time is greatly shortened, and the HoMn with excellent magnetoelectric property is prepared x Fe 1-x O 3 。
[ description of the drawings ]
FIG. 1 is an XRD pattern of the procedure of example 1 of the present invention;
FIG. 2 is an XRD pattern of the procedure of example 2 of the present invention;
FIG. 3 is an XRD pattern of the procedure of example 3 of the invention
Figure 4 is an XRD pattern of the process of example 4 of the invention.
[ detailed description ] embodiments
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a simple and efficient preparation method of manganese-doped holmium ferrite HoMn x Fe 1-x O 3 The preparation method of the magnetoelectric material comprises the following steps:
the method comprises the following steps: according to the preparation of HoMn x Fe 1-x O 3 Calculating the mass of each element according to the ratio of the mass of each element in the material and the total preparation amount, and calculating the mass of each elementAnd (2) calculating the total mass of the required raw materials according to the mass of each raw material and the content of elements in the holmium-containing compound, the iron-containing compound and the manganese-containing compound, weighing the holmium-containing compound, the iron-containing compound and the manganese-containing compound according to the calculated total mass of each raw material, and preparing the compounds into standard solutions.
The holmium-containing compound can be Ho (NO) 3 ) 3 ·6H 2 O or Ho 2 (SO 4 ) 3 ·8H 2 O, due to the mixed use of Ho (NO) 3 ) 3 ·6H 2 O and Ho 2 (SO 4 ) 3 ·8H 2 The reaction of the raw material O is complicated and the product cannot be produced, so that only one of the holmium-containing compounds is selected. The iron-containing compound may be Fe (NO) 3 ) 3 ·9H 2 O、Fe 2 (SO 4 ) 3 Or FeX 3 X is a halogen ion, and the manganese-containing compound may be Mn (NO) 3 ) 2 ·4H 2 O、MnSO 4 Or MnX 2 And X is a halogen ion.
The holmium-containing compound used in this example is Ho (NO) 3 ) 3 The iron-containing compound is FeCl 3 The manganese-containing compound is MnCl 2 The solvent is deionized water, so that a standard solution is prepared to obtain Ho (NO) with a concentration of 0.2M 3 ) 3 Standard solution, 0.1M MnCl 2 Standard solution and FeCl with concentration of 0.1M 3 And (4) standard solution.
Step two: ho (NO) 3 ) 3 Standard solution, mnCl 2 Standard solution and FeCl 3 The standard solution is uniformly mixed under magnetic stirring to obtain a first mixed solution, and the first mixed solution is mixed at room temperature and rapidly stirred, wherein the speed of the first mixed solution can be 600-1000 revolutions per minute.
The reaction can be carried out at room temperature, the reaction can be carried out without heating, electric energy consumption is avoided, and the economy is good. Since KOH acts as a mineralizer during the reaction, it can convert Mn to 2+ Oxidation to Mn 3+ . The product can be prepared only under the same conditions, but not a little and not a lot, but the resource waste is caused.
After the reaction solution is fully dissolved and cooled to room temperature, the reaction is heated because the reaction is exothermic, and the heat release stops after the reaction is finished, so the reaction solution is cooled to room temperature until the experimental process is finished. Because the mixture of the reaction is a strong alkaline solution, the heating needs to be carried out at a certain temperature, and only the reaction kettle with the lining can meet the experimental requirements, the mixed solution is moved into the hydrothermal reaction kettle with the p-polyphenyl lining for hydrothermal reaction, because the KOH needs to be reinforced in the reaction process, the KOH is completely mixed with the solution in a beaker and can be transferred into the reaction kettle, the filling degree is 70-80%, the pressure generated when the reaction kettle is kept warm is a necessary condition for preparing the product, because the reaction needs to be heated up, the hydrothermal reaction kettle is placed in a reaction furnace and is heated to 200-260 ℃ (the reaction temperature range can provide necessary energy for the reaction), the heat is kept for 1-4 days, and multiple experiments prove that: the reaction time is short, the product cannot be prepared, the reaction time is long, but the time is wasted, and the hydrothermal reaction kettle is cooled to obtain the first product.
The first product was put into cold water and rapidly cooled to room temperature. The step is an important step in the method, is similar to 'quenching' in metal casting, so that the temperature of the first product is quickly reduced to room temperature, the reaction process is quickly terminated, the product is ensured to be in an instantaneous state during synthesis, the product prepared by the method is uniform in particle and regular in crystal form, and the magnetoelectric effect of the prepared material can be obviously improved. The cold water in this step is actually water at room temperature, i.e. water at 15-30 ℃ relative to the reaction kettle.
Compared with the traditional natural cooling process, the cooling process is slow, the consumed time is long, the prepared product can be eroded by strong base of the system in the long cooling process, and the prepared product becomes broken and irregular, so that the magnetic performance of the product can be greatly weakened. Therefore, compared with the traditional natural cooling, the rapid cooling not only can greatly improve the preparation efficiency, but also can prepare more uniform powder particles and has more excellent magnetic property.
Washing the first product with deionized water, washing with anhydrous ethanol, and drying at 80 deg.C to remove residual water and ethanol (to obtain the desired magnetoelectric material HoMn) x Fe 1-x O 3 And (3) powder. The water washing can remove Cl in the solution after the reaction 1- 、NO 3- 、K + And removing the deionized water by using the absolute ethyl alcohol.
When x =0.2, 5mL Ho (NO) was measured 3 ) 3 、2mL MnCl 2 And 8mL FeCl 3 A standard solution;
when x =0.4, 5mL Ho (NO) was measured 3 ) 3 、4mL MnCl 2 And 6mL FeCl 3 A standard solution;
when x =0.6, 5mL of Ho (NO) is measured 3 ) 3 、6mL MnCl 2 And 4mL FeCl 3 A standard solution;
when x =0.8, 5mL Ho (NO) was measured 3 ) 3 、8mL MnCl 2 And 2mL FeCl 3 And (4) standard solution.
The method can avoid long-range migration of ions which are necessary to participate in the reaction in the solid-phase reaction, and greatly reduce the activation energy of the reaction, so the required reaction temperature is lower, the preparation process is simple, the reaction is easy to carry out, and the method is suitable for large-scale production. The invention takes part in the mixing of the reaction ions before the reaction and the diffusion of the ions in the reaction process are carried out in the liquid phase, because the water plays the role of a medium, the whole reaction process is carried out in a uniformly dispersed system, so the ion diffusion is easy to carry out, the reaction time is greatly shortened, and the HoMn with excellent magnetoelectric property is prepared x Fe 1-x O 3 . The invention has wide application range: the method is not only suitable for preparing the manganese-doped holmium ferrite magnetoelectric material, but also can be used for preparing other manganese-doped rare earth ferrite composite oxides, and is beneficial to the research and application of novel manganese-doped rare earth iron oxide magnetoelectric materials.
The invention also discloses manganese-doped holmium ferrite HoMn x Fe 1-x O 3 A magnetoelectric material of which 0<x<1, preferably x =0.2, 0.4, 0.6, 0.8, the material is of a perovskite type structure and has the same structure as holmium ferrite HoFeO 3 With similar crystal structure, the space group is changed from the orthorhombic phase Pbnm 62 point group to the hexagonal phase P63cm 185 point group along with the gradual increase of the doping ratio.
In the following examples, the mass percentages of the holmium source, the manganese source and the iron source are not less than 99.99%).
Example 1:
the method is utilized to prepare the manganese-doped holmium ferrite magnetoelectric material HoMn 0.2 Fe 0.8 O 3 The method sequentially comprises the following steps:
first, a standard solution Ho (NO) is prepared 3 ) 3 、MnCl 2 And Fe (NO) 3 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M; next, 5mL of Ho (NO) was measured 3 ) 3 (0.2M)、2mL MnCl 2 (0.1M) and 8mL Fe (NO) 3 ) 3 (0.1M), the standard solution was magnetically stirred in a 25mL beaker, and 18g of solid KOH was added slowly with stirring, rapidly, specifically at 600r/min, until the final mixture was cooled to room temperature.
Then transferring the mixture into a hydrothermal reaction kettle with a para-polyphenyl lining, wherein the filling degree is 80%, carrying out hydrothermal reaction for 1 day at 200 ℃, putting the reaction kettle into cold water at 25 ℃ to rapidly cool the reaction kettle, washing the cooled product with deionized water for 4 times, then washing the product with absolute ethyl alcohol for 4 times, and finally drying the product at 80 ℃ to obtain HoMn 0.2 Fe 0.8 O 3 。
Example 2:
the method is utilized to prepare the manganese-doped holmium ferrite magnetoelectric material HoMn 0.4 Fe 0.6 O 3 The method sequentially comprises the following steps:
first, a standard solution Ho (NO) is prepared 3 ) 3 、Mn(NO 3 ) 2 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M; next, 5mL of Ho (NO) was measured 3 ) 3 (0.2M)、4mL Mn(NO 3 ) 2 (0.1M) and 6mL FeCl 3 (0.1M), the standard solution was magnetically stirred in a 25mL beaker, and 18g of solid KOH was added slowly with stirring, rapidly, specifically at 600r/min, until the final mixture was cooled to room temperature. Then, the mixture is moved into a hydrothermal reaction kettle with a para-polyphenyl lining, the filling degree is 74%, the hydrothermal reaction is carried out for 3 days at the temperature of 260 ℃, the reaction kettle is put into cold water at the temperature of 28 ℃, the temperature of the reaction kettle is rapidly reduced, the obtained product after temperature reduction is washed for 4 times by deionized water and then washed for 4 times by absolute ethyl alcohol, and finally the product is dried at the temperature of 80 ℃ to obtain HoMn 0.4 Fe 0.6 O 3 。
Example 3:
the method is utilized to prepare the manganese-doped holmium ferrite magnetoelectric material HoMn 0.6 Fe 0.4 O 3 Sequentially comprises the following steps:
first, a standard solution Ho is prepared 2 (SO 4 ) 3 、MnCl 2 And Fe 2 (SO 4 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M; then, 5mL of Ho was measured 2 (SO 4 ) 3 (0.2M)、6mL MnCl 2 (0.1M) and 4mL Fe 2 (SO 4 ) 3 (0.1M), the standard solution was magnetically stirred in a 25mL beaker, and 18g of solid KOH was added slowly with stirring, rapidly, specifically at 600r/min, until the final mixture was cooled to room temperature.
Then, the mixture is moved into a hydrothermal reaction kettle with a para-polyphenyl lining, the filling degree is 70 percent, the hydrothermal reaction is carried out for 2.5 days at 225 ℃, the reaction kettle is put into cold water at 20 ℃ to be rapidly cooled, the product obtained after the temperature reduction is firstly washed by deionized water for 4 times and then by absolute ethyl alcohol for 4 times, and finally the product is dried at 80 ℃ to obtain HoMn 0.6 Fe 0.4 O 3 。
Example 4:
the method is utilized to prepare the manganese-doped holmium ferrite magnetoelectric material HoMn 0.8 Fe 0.2 O 3 The method sequentially comprises the following steps:
first, a standard solution Ho (NO) is prepared 3 ) 3 、Mn 2 (SO 4 ) 3 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M; next, 5mL of Ho (NO) was measured 3 ) 3 (0.2M)、8mL Mn 2 (SO 4 ) 3 (0.1M) and 2mL FeCl 3 (0.1M) Standard solution was magnetically stirred in a 25mL beaker, 18g of solid KOH was added slowly with stirring, and stirring was rapid, specifically set at 600r/min, until the final mixture was cooled to room temperature.
Then, the mixture is moved into a hydrothermal reaction kettle with a para-polyphenyl lining, the filling degree is 78 percent, the hydrothermal reaction is carried out for 4 days at 255 ℃, the reaction kettle is put into cold water at 15 ℃ to be rapidly cooled, the obtained product after the temperature reduction is firstly washed by deionized water for 4 times and then by absolute ethyl alcohol for 4 times, and finally the product is dried at 80 ℃ to obtain the HoMn 0.8 Fe 0.2 O 3 。
To test the products prepared in the examples of the invention, the XRD tests were carried out on them in accordance with the invention, referring to FIGS. 1, 2, 3 and 4 for the products of examples 1 to 4, respectively, from which it can be seen that the product HoMn 0.2 Fe 0.8 O 3 、HoMn 0.4 Fe 0.6 O 3 、HoMn 0.6 Fe 0.4 O 3 、HoMn 0.8 Fe 0.2 O 3 The structure is a typical perovskite structure, the space group is changed from an orthorhombic phase Pbnm 62 point group to a hexagonal phase P63cm 185 point group along with the gradual increase and change of the doping proportion, the peak type in the figure is sharp, no impurity peak appears, the crystallization of the product is good, no impurity exists, and the manganese-doped holmium ferrite magnetoelectric material can be prepared by the method.
As can be seen from the figure, the material obtained in example 1 is the most effective. In addition, it can be found that Mn is contained in the alloy due to Mn 3+ And Fe 3+ Having different ionic radii, and two ions with O 2- The difference of the ionic action ability is along with the difference of Mn in HoFeO 3 The increase of the doping amount of B causes the process of converting Fe-O-Fe into Mn-O-Fe and then into Mn-O-Mn bonds, and brings FeO in unit cells 6 Polyhedral MnO 6 The octahedral transformation shows that the change is reflected by the change trend of the peak pattern near 25 degrees in the figure.
Claims (5)
1. Manganese-doped holmium ferrite HoMn x Fe 1-x O 3 The preparation method of the magnetoelectric material is characterized by comprising the following steps:
according to the preparation of HoMn x Fe 1-x O 3 Weighing a holmium-containing compound, an iron-containing compound and a manganese-containing compound according to the mass ratio of the elements in the holmium-containing compound to respectively prepare a holmium-containing standard solution, an iron-containing standard solution and a manganese-containing standard solution, wherein x is more than 0 and less than 1, uniformly mixing the holmium-containing standard solution, the iron-containing standard solution and the manganese-containing standard solution under magnetic stirring to obtain a first mixed solution, adding solid KOH with the same mass as the first mixed solution into the first mixed solution at room temperature until the solid KOH is fully dissolved and cooled to room temperature to obtain a second mixed solution;
transferring the second mixed solution into a hydrothermal reaction kettle with a p-polyphenyl lining, wherein the filling degree is 70-80%, placing the hydrothermal reaction kettle in a reaction furnace, heating to 200-260 ℃, keeping the temperature for 1-4 days, cooling the hydrothermal reaction kettle to obtain a first product, putting the first product into cold water at the temperature of 15-30 ℃, quickly cooling to room temperature, washing and drying to obtain HoMn x Fe 1-x O 3 A magnetoelectric material;
the iron-containing compound is Fe (NO) 3 ) 3 ·9H 2 O、Fe 2 (SO 4 ) 3 Or FeX 3 X is a halide ion;
the manganese-containing compound adopts Mn (NO) 3 ) 2 ·4H 2 O、Mn 2 (SO 4 ) 3 Or MnX 2 X is a halide ion;
the holmium-containing compound adopts Ho (NO) 3 ) 3 ·6H 2 O or Ho 2 (SO 4 ) 3 ·8H 2 O。
2. The manganese-doped holmium ferrite HoMn of claim 1 x Fe 1-x O 3 The preparation method of the magnetoelectric material is characterized by comprising the following steps of:
preparing a standard solution Ho (NO) 3 ) 3 、MnCl 2 And Fe (NO) 3 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、2mL MnCl 2 And 8mL Fe (NO) 3 ) 3 Magnetically stirring in a beaker, slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a p-polyphenyl lining, wherein the filling degree is 80%, carrying out hydrothermal reaction at 200 ℃ for 1 day, putting the reaction kettle into cold water at 25 ℃ for cooling, washing the cooled product with deionized water for 4 times, then washing with absolute ethyl alcohol for 4 times, and drying at 80 ℃ to obtain HoMn 0.2 Fe 0.8 O 3 And (3) powder.
3. The manganese-doped holmium ferrite HoMn of claim 1 x Fe 1-x O 3 The preparation method of the magnetoelectric material is characterized by comprising the following steps:
preparing a standard solution Ho (NO) 3 ) 3 、Mn(NO 3 ) 2 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、4mL Mn(NO 3 ) 2 And 6mL FeCl 3 Magnetically stirring in a beaker, slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a polyphenyl lining, wherein the filling degree is 74%, carrying out hydrothermal reaction at 260 ℃ for 3 days, putting the reaction kettle into cold water at 28 ℃, washing the cooled product with deionized water for 4 times, then washing the product with absolute ethyl alcohol for 4 times, and drying the product at 80 ℃ to obtain HoMn 0.4 Fe 0.6 O 3 And (3) powder.
4. The manganese-doped holmium ferrite HoMn of claim 1 x Fe 1-x O 3 The preparation method of the magnetoelectric material is characterized by comprising the following steps of:
preparing a standard solution Ho 2 (SO 4 ) 3 、MnCl 2 And Fe 2 (SO 4 ) 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
measuring 5mL Ho 2 (SO 4 ) 3 、6mL MnCl 2 And 4mL of Fe 2 (SO 4 ) 3 Magnetically stirring in a beaker, and slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a lining of p-polyphenyl, wherein the filling degree is 70%, carrying out hydrothermal reaction at 225 ℃ for 2.5 days, putting the reaction kettle into cold water at 20 ℃, washing the cooled product with deionized water for 4 times, then washing with absolute ethyl alcohol for 4 times, and drying at 80 ℃ to obtain HoMn 0.6 Fe 0.4 O 3 And (3) powder.
5. The manganese-doped holmium ferrite HoMn of claim 1 x Fe 1-x O 3 The preparation method of the magnetoelectric material is characterized by comprising the following steps:
preparing a standard solution Ho (NO) 3 ) 3 、Mn 2 (SO 4 ) 3 And FeCl 3 The concentrations of (A) and (B) are respectively 0.2M, 0.1M and 0.1M;
5mL Ho (NO) was measured 3 ) 3 、8mL Mn 2 (SO 4 ) 3 And 2mL FeCl 3 Magnetically stirring in a beaker, slowly adding 18g of solid KOH while stirring at the stirring speed of 600r/min until the mixture is cooled to room temperature;
transferring the mixture into a hydrothermal reaction kettle with a p-polyphenyl lining, wherein the filling degree is 78%, performing hydrothermal reaction at 255 ℃ for 4 days, putting the reaction kettle into cold water at 15 ℃, washing the cooled product with deionized water for 4 times, then washing the product with absolute ethyl alcohol for 4 times, and drying the product at 80 ℃ to obtain HoMn 0.8 Fe 0.2 O 3 And (3) powder.
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