CN113319289B - Preparation method of FeCoNiCu high-entropy magnetic nano powder for magnetic thermotherapy - Google Patents
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Abstract
The invention belongs to the technical field of nano material production, and particularly relates to a preparation method of FeCoNiCu high-entropy magnetic nano powder for magnetic thermotherapy 2 ·4H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CuCl 2 ·2H 2 And synthesizing FeCoNiCu high-entropy magnetic nano powder with an fcc structure by using O as a raw material through a polyol method. The invention has the beneficial effects that: the method has the advantages of simple operation, simple and convenient synthesis method, fine and uniform powder, high crystallinity and excellent magnetocaloric property. The high-entropy magnetic nano powder can be used as a magnetic thermal therapeutic agent for tumor cells, when an alternating magnetic field with the intensity of 46Oe and the frequency of 266kHz is applied, the specific power loss of the high-entropy magnetic nano powder under the concentration of magnetic fluid of 2mg/ml is up to 321W/g, and the high-entropy magnetic nano powder is a low-cost high-performance magnetic thermal therapeutic material and can be applied to the biomedical fields of tumor magnetic thermal therapy and the like.
Description
Technical Field
The invention belongs to the field of biomedical application of nano materials, and particularly relates to a preparation method of FeCoNiCu high-entropy magnetic nano powder for magnetic thermotherapy.
Background
Malignant tumors are a serious threat to human health and life, and are one of the leading causes of human death. Recent data from the international agency for research on cancer (IARC) show that over 1900 million new cancer cases are released worldwide in 2020. The treatment of cancer remains one of the main challenges in modern medicine, and the current clinical malignant tumor treatment methods mainly comprise surgical therapy, drug chemotherapy and radiotherapy, but the therapies have the defects of large toxic and side effects, high recurrence, poor specificity and the like. With the rapid development of scientific technology, the thermal therapy of tumor has attracted great attention of researchers, and is becoming one of the important means of tumor treatment following surgery, radiotherapy and chemotherapy. Magnetic thermotherapy based on magnetic nano powder is a novel tumor targeted therapy means which is developed rapidly in recent years, and becomes a research hotspot of current tumor therapy due to the advantages of obvious curative effect, high safety, small side effect and the like.
Under the action of an external magnetic field, the magnetic material can convert magnetic loss energy into heat and is applied to the field of cancer treatment. Because the sensitivity of tumor cells to temperature is stronger than that of normal cells, the nano powder suspension is injected into tumor tissues, and the absorbed energy can be converted into heat energy under the action of an alternating magnetic field to increase the temperature of the tumor tissues in a living body, so that the cancer cells are killed. At present, the therapeutic effect of Magnetic Particle Hyperthermia (MPH) has been proved in vitro experiments and clinical trials, although there are many biomedical magnetic nano materials developed at present, the biggest challenges as magnetic hyperthermia agent are high cost of synthesis process and low magnetic-thermal conversion efficiency, such as widely used Fe in medical treatment 3 O 4 Powder, which exhibits superparamagnetism at the nano-scale, generates heat in an alternating magnetic field only by relaxation behavior, and is difficult to break through 100W/g than Specific Loss Power (SLP). Literature (Ibarra-S-nchez J, carrillo K, ceja-Fdz A, et al size control, chemical kinetics, and the analytical analysis for the production of Fe3O4 nanoparticles with a high specific adsorption rate [ J ]].Industrial&Engineering Chemistry Research,2020,59 (38), 16669-16683.) use of Fe 3 O 4 The powder simulates the tumor treatment process under the magnetic field condition with the frequency of 153kHz and the strength of 220Oe, the temperature rise of the magnetic heat is slow, and the temperature (42 ℃) required by the treatment can not be reached within 30 minutes, so the treatment time is prolonged, and the magnetic heat curative effect is greatly reduced. Therefore, the development of the magnetic nano material with high magnetocaloric efficiency and low cost has important scientific significance and practical application value.
Disclosure of Invention
Aiming at the practical problems that the heat production performance of the magnetic thermotherapy agent in the prior art is not well improved, the invention aims to provide the medical magnetic thermotherapy high-entropy magnetic nano powder which is simple in preparation process, can rapidly produce heat in an alternating magnetic field and retains the characteristic of good biocompatibility and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme: a preparation method of Fe-Co-Ni-Cu series high-entropy magnetic nano powder for magnetic thermal therapy is characterized by taking chloride salt crystals of Fe, co, ni and Cu as raw materials, simultaneously heating polyalcohol solution dissolved with the raw materials and alkaline solid particle-polyalcohol solution, mixing and reacting the two solutions at a reaction temperature to obtain a colloidal mixture, washing the colloidal mixture by deionized water and absolute ethyl alcohol, and centrifugally drying to obtain the FeCoNiCu series high-entropy magnetic nano powder.
Further, the preparation method specifically comprises the following steps:
s1) taking chloride salt raw materials of Fe, co, ni and Cu as the nominal component Fe of the alloy powder a Co b Ni c Cu d Respectively weighing the materials after converting the materials into mass according to atomic percentage,
s2) dividing the polyalcohol solution into a polyalcohol solution I and a polyalcohol solution II, and putting the alkaline solid particles and the polyalcohol solution I into a container A according to a certain proportion to obtain an alkaline solid particle-polyalcohol solution;
placing the polyalcohol solution II in a container B, mixing the raw materials weighed in the step S1), adding the mixture into the container B, placing a magnetic rotor, stirring uniformly to obtain a mixed solution,
s3) heating the obtained mixed solution, simultaneously carrying out magnetic stirring, adding the alkaline solid particle-polyalcohol solution into the mixed solution for reaction when the mixed solution is heated to a certain temperature, turning off a heater after the mixed solution is blackened, cooling to obtain a colloidal mixture,
and S4) respectively cleaning the colloidal mixture obtained in the step S3) with deionized water and absolute ethyl alcohol, centrifuging to obtain a black precipitate, drying in a vacuum drying oven, and grinding to obtain FeCoNiCu-series high-entropy magnetic nano powder.
Further, the concentration of the alkaline solid particle-polyalcohol solution obtained in the step S2) is 20-25%; the volume ratio of the polyalcohol solution I to the polyalcohol solution II is 2;
further, the alkaline solid particles are NaOH, KOH or Mg (OH) 2 One of (1);
the polyalcohol is one of propylene glycol, ethylene glycol or 1, 2-hexadecanediol, and the purity is not lower than 99.8%.
Further, the magnetic heating time in the S4) is 2-6min, the rotating speed of the magnetic stirring heater is 300-500rpm, and the heating temperature is 120-190 ℃.
Further, in the step S5), the centrifugal rotating speed is 9000-11000rpm, the centrifugal time is 3-6min, the drying temperature is 50-60 ℃, and the drying time is 10-12h.
Further, the FeCoNiCu system is the nominal component Fe of the high-entropy magnetic nano powder a Co b Ni c Cu d Wherein a is more than or equal to 25 and less than or equal to 50, b is more than or equal to 15 and less than or equal to 35, c is more than or equal to 15 and less than or equal to 35, d is more than or equal to 5 and less than or equal to 20, and a +, b +, c +, d=100, and the marked components are in atomic percentage.
Furthermore, the FeCoNiCu high-entropy magnetic nano powder has an fcc structure, and the average particle size is 60-100nm.
Furthermore, the specific power loss SLP value of the aqueous dispersion of the high-entropy magnetic nano powder can reach 321W/g.
Compared with the existing magnetic thermotherapy agent material, the magnetic thermotherapy agent has the following beneficial effects:
(1) Based on the alloy design concept of high-entropy alloy multi-principal element, the invention breaks through the traditional use of low-principal-element magnetic nano alloy material as a magnetic thermal therapeutic agent, and develops FeCoNiCu-series high-entropy magnetic nano powder with high specific loss power value by using cheap and easily-obtained raw materials such as metal chloride and the like.
(2) The polyol method adopted by the invention is a general and simple chemical method, and the polyol solution used in the preparation process is used as a reaction solvent and a reducing agent and also used as a stabilizer to control the growth of FeCoNiCu high-entropy magnetic nano powder and prevent powder agglomeration. Therefore, the preparation process can be carried out in a basic medium, the process of each part of the experiment can be well controlled, and meanwhile, the experiment operation is simple and convenient, the uncontrollable factors are few, and the preparation process is suitable for mass production.
(3) The heat generating capacity of the FeCoNiCu high-entropy magnetic nano powder prepared by the invention is obviously enhanced compared with that of the traditional magnetic nano material. The prepared nano powder with the average particle size of 60-100nm is dispersed in an aqueous solution, and the temperature rise can exceed 42 ℃ only within 5 min. The magnetic fluid concentration of 2mg/mL high entropy magnetic nano powder has maximum SLP value of 321W/g under lower magnetic field intensity (46 Oe). Therefore, the high-entropy magnetic nano powder prepared by the invention is an ideal high-performance magnetic thermal therapeutic agent material and has great market application potential.
Drawings
FIG. 1 is Fe 30 Co 30 Ni 30 Cu 10 、Fe 40 Co 25 Ni 25 Cu 10 、Fe 50 Co 22 Ni 22 Cu 6 And Fe 50 Co 18 Ni 18 Cu 14 X-ray diffraction pattern of high entropy magnetic nanopowder.
FIG. 2 is a scanning electron microscope image of the surface morphology of the high-entropy magnetic nanopowder, wherein FIG. 2 (a) is Fe 30 Co 30 Ni 30 Cu 10 Sample, FIG. 2 (b) is Fe 40 Co 25 Ni 25 Cu 10 Sample, FIG. 2 (c) is Fe 50 Co 22 Ni 22 Cu 6 Sample, FIG. 2 (d) is Fe 50 Co 18 Ni 18 Cu 14 And (3) sampling.
FIG. 3 is Fe 50 Co 22 Ni 22 Cu 6 Transmission electron microscope image of surface morphology of high entropy magnetic nanopowder, wherein FIG. 3 (a) is Fe 30 Co 30 Ni 30 Cu 10 Transmission Electron microscopy images of the samples, FIG. 3 (b) is Fe 50 Co 22 Ni 22 Cu 6 Elemental distribution image of the sample.
FIG. 4 is Fe at a concentration of 2mg/ml 30 Co 30 Ni 30 Cu 10 、Fe 40 Co 25 Ni 25 Cu 10 、Fe 50 Co 22 Ni 22 Cu 6 And Fe 50 Co 18 Ni 18 Cu 14 Heat generation rate image of high entropy magnetic nano powder under alternating magnetic field with intensity of 46Oe and frequency of 266 kHz.
FIG. 5 is Fe at a concentration of 2mg/ml 30 Co 30 Ni 30 Cu 10 、Fe 40 Co 25 Ni 25 Cu 10 、Fe 50 Co 22 Ni 22 Cu 6 And Fe 50 Co 18 Ni 18 Cu 14 SLP value under an alternating magnetic field of intensity 46Oe and frequency 266 kHz.
FIG. 6 is Fe at a concentration of 5mg/ml 30 Co 30 Ni 30 Cu 10 、Fe 40 Co 25 Ni 25 Cu 10 、Fe 50 Co 22 Ni 22 Cu 6 And Fe 50 Co 18 Ni 18 Cu 14 Heat generation rate image of high entropy magnetic nano powder under alternating magnetic field with intensity of 46Oe and frequency of 266 kHz.
FIG. 7 is Fe at a concentration of 5mg/ml 30 Co 30 Ni 30 Cu 10 、Fe 40 Co 25 Ni 25 Cu 10 、Fe 50 Co 22 Ni 22 Cu 6 And Fe 50 Co 18 Ni 18 Cu 14 SLP value of high-entropy magnetic nano-powder under the condition of alternating magnetic field with strength of 46Oe and frequency of 266 kHz.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
The invention relates to a preparation method of Fe-Co-Ni-Cu series high-entropy magnetic nano powder for magnetic thermal therapy, which takes chloride crystals of Fe, co, ni and Cu as raw materials, simultaneously heats a polyalcohol solution dissolved with the raw materials and an alkaline solid particle-polyalcohol solution, mixes and reacts the two solutions at a reaction temperature to obtain a colloidal mixture, washes the colloidal mixture by deionized water and absolute ethyl alcohol, and centrifugally dries to finally obtain FeCoNiCu series high-entropy magnetic nano powder.
The preparation method specifically comprises the following steps:
s1) taking chloride salt raw materials of Fe, co, ni and Cu as the nominal component Fe of the alloy powder a Co b Ni c Cu d Respectively weighing the materials after converting the materials into mass according to atomic percentage,
s2) dividing the polyalcohol solution into a polyalcohol solution I and a polyalcohol solution II, and putting the alkaline solid particles and the polyalcohol solution I into a container A according to a certain proportion to obtain an alkaline solid particle-polyalcohol solution;
placing the polyalcohol solution II in a container B, mixing the raw materials weighed in the step S1), adding the mixture into the container B, placing a magnetic rotor, uniformly stirring to obtain a mixed solution,
s3) heating the obtained mixed solution, simultaneously carrying out magnetic stirring, adding the alkaline solid particle-polyalcohol solution into the mixed solution for reaction when the mixed solution is heated to a certain temperature, closing a heater after the mixed solution turns black, cooling to obtain a colloidal mixture,
and S4) respectively cleaning the colloidal mixture obtained in the step S3) with deionized water and absolute ethyl alcohol, centrifuging to obtain a black precipitate, drying in a vacuum drying oven, and grinding to obtain FeCoNiCu-series high-entropy magnetic nano powder.
The concentration of the alkaline solid particle-polyalcohol solution in the S2) is 20-25%;
the volume ratio of the polyalcohol solution I to the polyalcohol solution II is 2;
the alkaline solid particles are NaOH, KOH or Mg (OH) 2 One of (1);
the polyalcohol is one of propylene glycol, ethylene glycol or 1, 2-hexadecanediol, and the purity is not lower than 99.8%.
And in the step S3), the magnetic heating time is 2-6min, the rotating speed of the magnetic stirring heater is 300-500rpm, and the heating temperature is 120-190 ℃.
The centrifugal speed in the S4) is 9000-11000rpm, the centrifugal time is 3-6min, the drying temperature is 50-60 ℃, and the drying time is 10-12h.
Nominal composition Fe of said FeCoNiCu-based black alloy powder a Co b Ni c Cu d Wherein a is more than or equal to 25 and less than or equal to 50, b is more than or equal to 15 and less than or equal to 35, c is more than or equal to 15 and less than or equal to 35, d is more than or equal to 5 and less than or equal to 20, and a + b + c + d =100, and the marked components are atomic percent.
The obtained FeCoNiCu high-entropy magnetic nano powder has an fcc structure, and the average grain size is 60-100nm.
The specific loss power SLP value of the aqueous dispersion of the high-entropy magnetic nano powder can reach 321W/g.
Example 1: with Fe 30 Co 30 Ni 30 Cu 10 As a nominal component of the high-entropy magnetic nano-powder, metal salt (FeCl) required by the alloy 2 ·4H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CuCl 2 ·2H 2 O) is weighed according to the atom percent conversion into mass, 4g of granular KOH and 20mL of propylene glycol solution with the purity of 99.8 percent are weighed and put into a beaker, 30mL of propylene glycol solution with the purity of 99.8 percent are weighed and put into another beaker, and metal salt is added and put into a magnetic stirring rotor. And then, putting the propylene glycol solution dissolved with the metal salt and the KOH-propylene glycol solution into a magnetic stirring heater for heating, mixing the propylene glycol solution dissolved with the metal salt and the KOH-propylene glycol solution when the temperature is raised to 170 ℃, stopping heating after reacting for 3min, and cooling to obtain a colloidal mixture. The colloidal mixture was washed three times with deionized water and absolute ethanol, respectively, and centrifuged at 10000rpm for 5min to obtain a black precipitate. Drying the black precipitate in a vacuum drying oven at 50 deg.C for 12h, and grinding to obtain Fe 40 Co 25 Ni 25 Cu 10 High entropy magnetic nanopowder.
For prepared Fe 40 Co 25 Ni 25 Cu 10 The high-entropy magnetic nano powder is subjected to X-ray diffraction spectrum test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, fe can be seen 30 Co 30 Ni 30 Cu 10 The high-entropy magnetic nano powder is of an fcc structure, and a characteristic peak becomes relatively sharp, which indicates that the crystallinity of the sample is high. In FIG. 2, (a) is Fe 40 Co 25 Ni 25 Cu 10 Of samplesIn the scanning electron micrograph, it can be seen that the powder of the sample is spherical and has an average particle diameter of about 81nm.
Example 2: with Fe 40 Co 25 Ni 25 Cu 10 As a nominal component of the high-entropy magnetic nano-powder, metal salt (FeCl) required by the alloy 2 ·4H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CuCl 2 ·2H 2 O) is weighed according to the atom percent conversion into mass, 4g of granular KOH and 20mL of propylene glycol solution with the purity of 99.8 percent are weighed and put into a beaker, 30mL of propylene glycol solution with the purity of 99.8 percent are weighed and put into another beaker, and metal salt is added and put into a magnetic stirring rotor. And then placing the ethylene glycol solution dissolved with the metal salt and the KOH-ethylene glycol solution in a magnetic stirring heater for heating, mixing the propylene glycol solution dissolved with the metal salt and the KOH-ethylene glycol solution when the temperature is raised to 170 ℃, stopping heating after reacting for 3min, and cooling to obtain a colloidal mixture. The colloidal mixture was washed three times with deionized water and absolute ethanol, respectively, and centrifuged at 10000rpm for 5min to obtain a black precipitate. Drying the black precipitate in a vacuum drying oven at 50 deg.C for 12h, and grinding to obtain Fe 40 Co 25 Ni 25 Cu 10 High entropy magnetic nanopowder.
For the prepared Fe 40 Co 25 Ni 25 Cu 10 The high-entropy magnetic nano powder is subjected to X-ray diffraction spectrum test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, fe can be seen 40 Co 25 Ni 25 Cu 10 The high-entropy magnetic nano powder is of an fcc structure, and a characteristic peak becomes relatively sharp, which indicates that the crystallinity of the sample is high. In FIG. 2, (b) is Fe 40 Co 25 Ni 25 Cu 10 In the SEM image of the sample, it can be seen that the powder of the sample is spherical and has an average particle size of about 72nm.
Example 3: with Fe 50 Co 22 Ni 22 Cu 6 As a nominal component of the high-entropy magnetic nano-powder, metal salt (FeCl) required by the alloy 2 ·4H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CuCl 2 ·2H 2 O) is weighed according to the atom percent conversion into mass, 4g of granular NaOH and 20mL of propylene glycol solution with the purity of 99.8% are weighed and put into a beaker, 30mL of propylene glycol solution with the purity of 99.8% is weighed and put into another beaker, and metal salt is added and put into a magnetic stirring rotor. And then, putting the propylene glycol solution dissolved with the metal salt and the NaOH-propylene glycol solution into a magnetic stirring heater for heating, mixing the propylene glycol solution dissolved with the metal salt and the NaOH-propylene glycol solution when the temperature is raised to 170 ℃, stopping heating after reacting for 3min, and cooling to obtain a colloidal mixture. The colloidal mixture was washed three times with deionized water and absolute ethanol, respectively, and centrifuged at 10000rpm for 5min to obtain a black precipitate. Drying the black precipitate in a vacuum drying oven at 50 deg.C for 12h, and grinding to obtain Fe 50 Co 22 Ni 22 Cu 6 High entropy magnetic nanopowders.
For prepared Fe 50 Co 22 Ni 22 Cu 6 The high-entropy magnetic nano powder is subjected to X-ray diffraction spectrum test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, fe can be seen 50 Co 22 Ni 22 Cu 6 The high-entropy magnetic nanopowder is of fcc structure. In FIG. 2, (c) is Fe 50 Co 22 Ni 22 Cu 6 In the SEM image of the sample, it can be seen that most of the powder of the sample is spherical and has an average particle size of about 77nm. In FIG. 3, (a) is Fe 50 Co 22 Ni 22 Cu 6 And in the transmission electron microscope image of the sample, the observed appearance of the nano powder is the same as that of a scanning electron microscope. In FIG. 3, (b) is Fe 50 Co 22 Ni 22 Cu 6 The element distribution image of the sample shows that the elements of Fe, co, ni and Cu are uniformly distributed in the powder sample. Next, fe will be produced 50 Co 22 Ni 22 Cu 6 The high-entropy magnetic nano powder is set with two groups of sample concentrations of 2mg/mL and 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field intensity is 46Oe, and the magnetic field frequency is 266 kHz) to carry out an in-vitro magnetic-thermal temperature rise test. FIG. 4 andFIG. 6 shows the temperature rising rate curves of samples with concentrations of 2mg/mL and 5mg/mL, respectively, and Fe can be found 50 Co 22 Ni 22 Cu 6 All had the fastest rate of temperature rise, and the temperature rise exceeded 42 ℃ in as little as 5 min. The initial slope (taking the first 30s temperature gradient) was measured from the temperature rise curve, and the specific power loss was calculated for the samples at concentrations of 2mg/mL and 5mg/mL in FIGS. 5 and 7, respectively, from which it can be seen that Fe at concentrations of 2mg/mL and 5mg/mL 50 Co 22 Ni 22 Cu 6 The specific power loss values of the samples are 321W/g and 238W/g respectively, which shows that the samples have excellent magnetocaloric properties and are expected to be applied to the research and development of high-performance magnetic thermal therapeutic agents.
Example 4: with Fe 50 Co 18 Ni 18 Cu 14 As a nominal component of the high-entropy magnetic nano-powder, metal salt (FeCl) required by the alloy 2 ·4H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CuCl 2 ·2H 2 O) is weighed according to the atom percent conversion into mass, 4g of granular NaOH and 20mL of propylene glycol solution with the purity of 99.8% are weighed and put into a beaker, 30mL of propylene glycol solution with the purity of 99.8% is weighed and put into another beaker, and metal salt is added and put into a magnetic stirring rotor. And then, putting the propylene glycol solution dissolved with the metal salt and the NaOH-propylene glycol solution in a magnetic stirring heater for heating, mixing the propylene glycol solution dissolved with the metal salt and the NaOH-propylene glycol solution when the temperature is raised to 150 ℃, reacting for 3min, stopping heating, and cooling to obtain a colloidal mixture. The colloidal mixture was washed three times with deionized water and absolute ethanol, respectively, and centrifuged at 10000rpm for 5min to obtain a black precipitate. Drying the black precipitate in a vacuum drying oven at 50 deg.C for 12h, and grinding to obtain Fe 50 Co 18 Ni 18 Cu 14 High entropy magnetic nanopowder.
For prepared Fe 50 Co 18 Ni 18 Cu 14 The high-entropy magnetic nano powder is subjected to X-ray diffraction spectrum test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, fe can be seen 50 Co 18 Ni 18 Cu 14 The high-entropy magnetic nano powder has an fcc structure, and a characteristic peak becomes relatively sharp, which indicates that the crystallinity of a sample is high. In FIG. 2, (d) is Fe 50 Co 18 Ni 18 Cu 14 In the SEM image of the sample, it can be seen that most of the powder of the sample is spherical and has an average particle size of about 65nm. Next, fe will be produced 50 Co 18 Ni 18 Cu 14 The high-entropy magnetic nano powder is set with two groups of sample concentrations of 2mg/mL and 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field intensity is 46Oe, and the magnetic field frequency is 266 kHz) to carry out in-vitro temperature rise test. FIG. 5 shows the temperature rise rate curve of a sample having a concentration of 2mg/mL, and Fe can be found 50 Co 22 Ni 22 Cu 6 The sample (A) has a fast temperature rise rate, and the temperature rise exceeds 42 ℃ in as short as 5 min. FIGS. 5 and 7 calculate the specific power loss of the samples at concentrations of 2mg/mL and 5mg/mL, respectively, from which it can be seen that Fe at concentrations of 2mg/mL and 5mg/mL 50 Co 22 Ni 22 Cu 6 The specific power loss values of the samples are respectively 216W/g and 132W/g, and the magnetocaloric property of the samples is superior to that of Fe commonly used in the medical field at present 3 O 4 The powder is expected to be applied to the research and development of high-performance magnetic thermal therapy agents.
The preparation method of the FeCoNiCu high-entropy magnetic nano powder for magnetic thermal therapy provided by the embodiment of the application is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As some terms are used throughout the description and claims to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. The present specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, that a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrases "comprising one of \8230;" does not exclude the presence of additional like elements in an article or system comprising the element.
It should be understood that the term "and/or" as used herein is merely a relationship that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (4)
1. A method for preparing FeCoNiCu high-entropy magnetic nano powder for magnetic thermotherapy is characterized in that chloride salts of Fe, co, ni and Cu are used as raw materials, a polyol solution dissolved with the raw materials and an alkaline solid particle-polyol solution are heated simultaneously, mixed and reacted at a certain temperature to obtain a colloidal mixture, the colloidal mixture is washed by deionized water and absolute ethyl alcohol, and centrifugally dried to finally obtain the FeCoNiCu high-entropy magnetic nano powder, and the preparation method specifically comprises the following steps:
s1) taking chloride salt raw materials of Fe, co, ni and Cu as the nominal component Fe of the alloy powder a Co b Ni c Cu d Converting into mass according to atomic percentage and then weighing respectively;
s2) dividing the polyalcohol solution into a polyalcohol solution I and a polyalcohol solution II, and putting the alkaline solid particles and the polyalcohol solution I into a container A according to a certain proportion to obtain an alkaline solid particle-polyalcohol solution; placing the polyalcohol solution II in a container B, mixing the raw materials weighed in the step S1), adding the mixture into the container B, placing a magnetic rotor, and uniformly stirring to obtain a mixed solution;
the concentration of the alkaline solid particle-polyalcohol solution is 20-25%; the volume ratio of the polyalcohol solution I to the polyalcohol solution II is 2;
s3) heating the obtained mixed solution, simultaneously carrying out magnetic stirring, adding the alkaline solid particle-polyalcohol solution into the mixed solution for reaction when the mixed solution is heated to a certain temperature, closing a heater after the mixed solution turns black, and cooling to obtain a colloidal mixture;
s4) respectively cleaning the colloidal mixture obtained in the step S3) with deionized water and absolute ethyl alcohol, centrifuging to obtain a black precipitate, drying in a vacuum drying oven, and grinding to obtain FeCoNiCu high-entropy magnetic nano powder;
s4), magnetically heating for 2-6min at 120-190 ℃ at a rotating speed of 300-500rpm of a magnetic stirring heater;
the nominal component Fe of the FeCoNiCu high-entropy magnetic nano powder a Co b Ni c Cu d Wherein a is more than or equal to 25 and less than or equal to 50, b is more than or equal to 15 and less than or equal to 35, and c is more than or equal to 15D is less than or equal to 35,5 is less than or equal to 20, a +, b +, c + d =100, and the marked components are in atom percentage;
the obtained FeCoNiCu high-entropy magnetic nano powder has an fcc structure, and the average grain size is 60-100nm.
2. The method of claim 1, wherein the alkaline solid particles are NaOH, KOH, or Mg (OH) 2 One of (1); the polyalcohol is one of propylene glycol, ethylene glycol or 1, 2-hexadecanediol, and the purity is not lower than 99.8%.
3. The preparation method of claim 1, wherein the centrifugation speed in S4) is 9000-11000rpm, the centrifugation time is 3-6min, the drying temperature is 50-60 ℃, and the drying time is 10-12h.
4. The preparation method of any one of claims 1 to 3, wherein the FeCoNiCu-based high-entropy magnetic nanopowder has a specific power loss SLP value up to 321W/g.
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