CN112499691B - Self-temperature-control magnetic nanowire and preparation method thereof - Google Patents
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Abstract
The invention relates to a self-temperature-control magnetic nanowire and a preparation method thereof, belonging to the technical field of tumor magnetic induction thermotherapy. In order to solve the problems of low heat generation rate and agglomeration of magnetic nanoparticles, the invention provides a preparation method of a self-temperature-control magnetic nanowire. The self-temperature-control magnetic nanowire prepared by the method has the advantages of 5-45 nm in diameter, 5-30 microns in length and 42-45 ℃ in Curie point, is stable in chemical performance, excellent in magnetic property, high in Curie point temperature meeting the requirements of magnetic thermal therapy, high in heat yield, not easy to agglomerate, good in performance consistency and good in biocompatibility, and can be used for manufacturing magnetic nano media and magnetic thermal seeds for magnetic thermal therapy in batches.
Description
Technical Field
The invention belongs to the technical field of tumor magnetic induction thermotherapy, and particularly relates to a temperature self-control magnetic nanowire and a preparation method thereof.
Background
The main treatment means for tumor at home and abroad still mainly adopts operation and adopts radiotherapy and chemotherapy as assistance, and with the progress of the medical level, the treatment means for tumor is continuously expanded, and new treatment methods are developed. In recent years, tumor thermotherapy technology has been developed rapidly, clinical application has achieved significant effects, the toxic and side effects are relatively small, and patient pain is slight, which has attracted great attention from researchers and clinician workers. The research shows that: in a high-temperature thermal environment, blood in a tumor tissue flows slowly, resistance is large, heat dissipation is difficult, heat is easy to accumulate, temperature rise is high relative to that of a normal tissue, the normal tissue around the tumor can expand blood vessels under the action of high temperature, blood flow speed is increased, heat dissipation is rapid, and temperature rise is slow, so that the temperature difference between the normal tissue and the tumor can reach 5-7 ℃. The high temperature heat effect has the function of selectively killing tumor tissue cells.
The thermotherapy for tumor is the method of generating heat by RF alternating electric field, ultrasonic wave, microwave and other physical fields and wave-induced tumor, and has 2 treatment modes in vitro and in vivo.
Another method for hyperthermia of tumours is magnetic hyperthermia. The magnetic thermotherapy is a thermotherapy method for selectively killing tumor cells by using the magnetic thermotherapy effect generated by the magnetic nano-particle material introduced into the tumor part in vivo under the action of an in vitro alternating magnetic field. In the magnetic thermotherapy, magnetic nanoparticles can be introduced into or around tumor by injection and targeted introduction, and medium-frequency alternating magnetic field is adopted to make the magnetic nanoparticles generate heat and act on the tumor, so that the tumor can be programmed to die due to overheating.
With the development of nanotechnology, the magnetic nanoparticle material for tumor thermotherapy has been developed from traditional simple magneto-induced heating to intelligent magnetic nanoparticle material with self-temperature-control function, and this technology has greatly promoted the development of tumor thermotherapy. Accurate temperature control is the key for improving the clinical effect of tumor magnetic induction thermotherapy.
The self-temperature-control theory is that the magnetic nano-particle material can be heated and heated in an alternating magnetic field, when the temperature reaches the Curie temperature point, the magnetic nano-particle material can be converted into a paramagnetic material so as not to be heated and heated any more, and when the temperature is lower than the Curie temperature point, the magnetic nano-particle material can be converted into a ferromagnetic material so as to be heated and heated by the alternating magnetic field. The self-temperature-control performance of the magnetic nano-particle material can be realized by utilizing the Curie temperature point characteristic of the magnetic nano-particle material, and the intellectualization of the magnetic nano-particle is further realized.
The research of the magnetic nano-particles for the low Curie point magnetic thermotherapy is mainly divided into two types, one is alloy magnetic nano-particles, and the other is ferrite magnetic nano-particles. The former is represented by copper-nickel alloy nano particles and the like, and the Curie temperature point can be controlled within the range of 40-60 ℃; the latter is a zinc-cobalt-chromium ferrite magnetic nano particle, the Curie temperature can be controlled between 40-45 ℃, and the magnetic nano particle is an ideal magnetic nano material for magnetic thermotherapy.
The invention patent application with the application number of 201810048766.5 discloses a preparation method of self-temperature-control magnetic nanoparticles, wherein the problems that the sizes of product particles are increased and the product particles are easy to agglomerate and the like are caused by the fact that the concentrations of a precipitator NaOH aqueous solution and a metal ion solution are too high and the treatment temperature of a high-pressure reaction kettle is too high, and the problems that the particle sizes of the product particles are too small and the heat generation rate is low and the like are caused by the fact that the concentrations of the NaOH aqueous solution and the metal ion solution are too low are solved.
Therefore, the magnetic nano particle material has two technical problems at present, namely, the magnetic thermal effect of the existing magnetic nano particles only has a magnetic hysteresis effect and a relaxation effect, so that the heat generation rate of the magnetic nano particles is low, and the requirement of magnetic thermal therapy cannot be met; secondly, the magnetic material can cause the particle agglomeration problem due to the magnetic property of the nano particles, thereby not only affecting the heating efficiency, but also causing the capillary embolism problem of normal tissues due to overlarge particles and generating adverse effects in the treatment process.
Disclosure of Invention
The invention provides a self-temperature-control magnetic nanowire and a preparation method thereof, aiming at solving the problems of low heat generation rate and agglomeration of magnetic nanoparticles.
The technical scheme of the invention is as follows:
a preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice;
depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
and step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
Further, the two-time anodic oxidation specific method in the step one comprises the following steps: immersing the aluminum foil in H 2 SO 4 In the water solution, primary anodic oxidation is carried out under primary oxidation voltage, after a certain time of oxidation, the aluminum foil is immersed into the mixed solution of phosphoric acid and chromic acid to remove the primary oxidation film on the surface of the aluminum foil, and then the aluminum foil is immersed into H again 2 SO 4 In the water solution, carrying out secondary anodic oxidation under a secondary oxidation voltage, taking out after oxidizing for a certain time, cleaning and drying to prepare the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels arranged in an array manner.
Further, the purity of the aluminum foil is more than or equal to 99.95%, and the thickness of the aluminum foil is 0.05-0.1 mm; said H 2 SO 4 The molar concentration of the aqueous solution is 0.1-0.5 mol/L; the mass concentration of phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 4-8 wt%, and the mass concentration of chromic acid is 1.2-2.8 wt%; the primary oxidation voltage is 24-57V, the primary oxidation time is 5-20 min, the secondary oxidation voltage is 35-45V, and the secondary oxidation time is 50-180 min; the pore diameter of the micro-channel is 10-100 nm.
Further, the chemical coprecipitation method in the second step specifically comprises the following steps: preparing CoCl according to a certain mole ratio 2 、FeCl 3 、CrCl 3 And ZnCl 2 The aluminum anodic oxidation micro-channel template prepared in the step one is immersed in the metal salt mixed solution, heating to 60-80 ℃, vacuum pumping to remove gas in the micro-channel to make the metal salt mixed solution fill in the micro-channel, dripping 0.5-2.0 mol/L ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate zinc-cobalt-chromium-iron-oxide hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until no precipitate is generated, taking out the aluminum anode to oxidize the micro-channel template, treating the template at 500-550 ℃ for 0.5-1.5 h, and then, immersing the aluminum anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to finish chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.2-1.0h to form zinc cobalt.Ferrochrome ferrite magnetic nanowires.
Further, the CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 The molar ratio of (0.10-0.22), (0.11-0.23), (0.10-0.16), (0.45-0.60).
Further, the metal salt mixed solution is doped with FeCl 2 And NiCl 2+X Wherein CoCl 2 、FeCl 2 、NiCl 2+X 、ZnCl 2 、FeCl 2 And NiCl 2+X The molar ratio of (0.10-0.22), (0.11-0.23), (0.10-0.16), (0.45-0.60), (0.11-0.23) and (0.10-0.16).
Further, the specific method for removing the aluminum anodic oxidation micro-channel template by corrosion and performing surface hydrophobization treatment comprises the following steps: immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment in the second step into a NaOH aqueous solution with the mass concentration of 10-25%, corroding 90% of the aluminum anodic oxidation micro-channel template to expose the zinc-cobalt-chromium-ferrite magnetic nanowires, soaking the exposed zinc-cobalt-chromium-ferrite magnetic nanowires by using a fluorine-containing surface ion complexing agent perfluoroalkyl sulfonate solution or tetraethoxysilane to finish surface hydrophobization treatment, completely corroding the rest aluminum anodic oxidation micro-channel template to release the zinc-cobalt-chromium-ferrite magnetic nanowires, and centrifuging at 5000-12000 r/min to obtain the self-temperature-control magnetic nanowires.
Further, the fluorine-containing surface ion complexing agent solution is perfluoroalkyl sulfonate, the molar concentration is 0.2-1.0 mol/L, and the dipping time is 0.1-0.5 h.
Further, the concentration of the tetraethoxysilane is 0.2-0.5 mol/L, the dipping time is 0.1-0.3 h, and the temperature for dipping the tetraethoxysilane is 120-200 ℃.
The temperature self-control magnetic nanowire prepared by the temperature self-control magnetic nanowire provided by the invention has the diameter of 5-45 nm, the length of 5-30 mu m and the Curie temperature of 42-45 ℃.
The invention has the beneficial effects that:
the temperature self-control magnetic nanowire provided by the invention has a linear structure with the diameter of 5-45 nm and the length of 5-30 mu m, can generate a hysteresis effect and a relaxation effect under the action of an alternating magnetic field, can also generate an eddy current effect, can remarkably improve the heat production rate of the magnetic nanowire by exerting the effect of the three magnetocaloric effects together, and can relatively reduce the dosage of the magnetic nanowire used in the application of magnetocaloric therapy, thereby reducing the potential toxic and side effects in the clinical treatment process.
The surface of the self-temperature-control magnetic nanowire provided by the invention is provided with the hydrophobic film, so that the agglomeration of the magnetic nanowire can be prevented, the problem of capillary embolism of a normal tissue caused by the agglomeration of a magnetic nano material is solved, the self-temperature-control magnetic nanowire can be directly used as a magnetic medium material to be introduced or intervened in a human body, and the self-temperature-control magnetic nanowire has better biocompatibility and no toxicity.
According to the preparation method of the self-temperature-control magnetic nanowire, the zinc-cobalt-chromium-iron-oxide magnetic nanowire with the Curie temperature of 42-45 ℃ is prepared through reasonable proportioning of the metal salts, the chemical property is stable, the magnetic property is excellent, and the Curie temperature meets the requirements of self-temperature-control magnetic thermotherapy. By adding FeCl to metal salts 2 And NiCl 2+X And further doping modification can be carried out, so that the magnetic characteristics and the Curie temperature point of the material can be adjusted, and the Curie temperature point of the magnetic nanowire is further accurate to 42-44 ℃.
The preparation method of the self-temperature-control magnetic nanowire is suitable for batch manufacturing, has controllable quality and good consistency of the performance of the magnetic nanowire, and can be used for batch manufacturing of magnetic nano media and magnetic heat seeds for magnetic thermal therapy.
Drawings
FIG. 1 is a schematic view of an aluminum anodized microchannel template prepared according to the present invention;
FIG. 2 is a schematic diagram of a temperature self-controlling magnetic nanowire prepared according to the present invention.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice;
depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
and step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
Example 2
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, wherein the thickness of the thin aluminum foil is 0.05-0.1 mm, polishing the surface of the thin aluminum foil, cutting the thin aluminum foil into square blocks with the thickness of 50mm multiplied by 50mm, and immersing the cut thin aluminum foil into H with the molar concentration of 0.1-0.5 mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24-57V, and the oxidation time is 5-20 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of the phosphoric acid and the chromic acid is 4-5 wt%, and the mass concentration of the chromic acid is 1.2-1.4 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 35-45V, the oxidation time is 50-180 min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
and step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
The embodiment adopts the secondary anodic oxidation to prepare the aluminum anodic oxidation micro-channel template, and has the advantages that: the oxide film formed by the first anodic oxidation has uneven micropore distribution and poor aperture consistency. Dissolving the oxide film formed for the first time, storing corrosion points for the growth of alumina on an aluminum substrate, uniformly distributing, and implementing secondary anodic oxidation to form an oxide film with uniform and ordered micropore distribution and good aperture consistency, thereby being convenient for providing a template with a gauge for the subsequent magnetic nanowire manufacture.
Example 3
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, wherein the thickness of the thin aluminum foil is 0.05-0.1 mm, polishing the surface of the thin aluminum foil, cutting the thin aluminum foil into square blocks with the thickness of 50mm multiplied by 50mm, and immersing the cut thin aluminum foil into H with the molar concentration of 0.1-0.5 mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24-57V, and the oxidation time is 5-20 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 4.5-5.5 wt%, and the mass concentration of the chromic acid is 1.3-1.5 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 35-45V, the oxidation time is 50-180 min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
according to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 Soaking an aluminum anodic oxidation micro-channel template into a metal salt mixed solution prepared from (0.10-0.22), (0.11-0.23), (0.10-0.16) and (0.45-0.60), heating to 60-80 ℃, vacuum-pumping to remove gas in the micro-channel, filling the metal salt mixed solution into the micro-channel, dripping 0.5-2.0 mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate a zinc-cobalt-chromium-oxygen hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 500-550 ℃ for 0.5-1.5 hours;
and then, immersing the aluminum anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.3h to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
And step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
The stable zinc-cobalt-chromium ferrite magnetic nanowire is formed by high-temperature sintering, the Curie temperature point of the nanowire is 42-45 ℃, the chemical property is stable, the magnetic property is excellent, and the Curie temperature point meets the self-temperature-control magnetic thermal therapy requirement.
Example 4
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, wherein the thickness of the thin aluminum foil is 0.05-0.1 mm, polishing the surface of the thin aluminum foil, cutting the thin aluminum foil into square blocks with the thickness of 50mm multiplied by 50mm, and immersing the cut thin aluminum foil into H with the molar concentration of 0.1-0.5 mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24-57V, and the oxidation time is 5-20 min; immersing the aluminum foil after the primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove the aluminum foilThe mass concentration of phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 5.0-6.0 wt%, and the mass concentration of chromic acid is 1.4-1.6 wt% of the primary oxide film on the surface.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 35-45V, the oxidation time is 50-180 min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
doping FeCl with a certain proportion in metal salt solution 2 And NiCl 2+X According to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 、FeCl 2 And NiCl 2+X The method comprises the following steps of (0.10-0.22) mixing (0.11-0.23) and (0.10-0.16) mixing (0.45-0.60) and (0.11-0.23) mixing (0.10-0.16) metal salt mixed liquor, immersing an aluminum anodic oxidation micro-channel template into the metal salt mixed liquor, heating to 60-80 ℃, vacuum-pumping to remove gas in the micro-channel, enabling the metal salt mixed liquor to be filled in the micro-channel, dripping 0.5-2.0 mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed liquor to generate zinc-cobalt-ferrite-chromium-iron hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 500-550 ℃ for 0.5-1.5 hours;
and then, immersing the aluminum anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.4h to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
And step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
This example adds FeCl to a metal salt solution 2 And NiCl 2+X And further doping modification can be carried out, so that the magnetic characteristics and the Curie temperature point of the material can be adjusted, and the Curie temperature point of the magnetic nanowire is further accurate to 42-44 ℃.
Example 5
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, wherein the thickness of the thin aluminum foil is 0.05-0.1 mm, polishing the surface of the thin aluminum foil, cutting the thin aluminum foil into square blocks with the thickness of 50mm multiplied by 50mm, and immersing the cut thin aluminum foil into H with the molar concentration of 0.1-0.5 mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24-57V, and the oxidation time is 5-20 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 5.5-6.5 wt%, and the mass concentration of the chromic acid is 1.5-1.7 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 35-45V, the oxidation time is 50-180 min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-iron-oxide hydroxide in the micro-channels of the aluminum anode oxidation micro-channel template by using a chemical coprecipitation method, and sintering to form zinc-cobalt-chromium-iron-oxide magnetic nanowires;
according to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 The metal salt mixed solution is prepared by (0.10-0.22) to (0.11-0.23) to (0.10-0.16) to (0.45-0.60), the aluminum anodic oxidation micro-porous channel template is immersed into the metal salt mixed solution, heated to 60-80 ℃, and vacuumed to remove the gas in the micro-porous channel, so that the metal salt mixed solution is filled in the micro-porous channel, and the temperature is 0.5 DEG2.0mol/L of ammonia water is dripped into the micro-channel, the ammonia water and the metal salt mixed solution are subjected to chemical coprecipitation to generate a zinc-cobalt-chromium-iron-oxide hydroxide precipitate in the micro-channel, the ammonia water is continuously dripped until no precipitate is generated, the aluminum anode is taken out to oxidize the micro-channel template, and the micro-channel template is treated for 0.5 to 1.5 hours at the temperature of between 500 and 550 ℃;
and then, immersing the aluminum anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.5h to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
Corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium ferrite magnetic nanowire:
immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment into a NaOH aqueous solution with the mass concentration of 10-25%, corroding 90% of aluminum anodic oxidation micro-channel mold, exposing directional array arrangement zinc-cobalt-chromium-iron-oxide magnetic nanowires, soaking the exposed zinc-cobalt-chromium-iron-oxide magnetic nanowires for 0.1-0.5 h by using perfluoroalkyl sulfonate with the molar concentration of 0.2-1.0 mol/L, completing surface hydrophobization treatment, completely corroding the rest aluminum anodic oxidation micro-channel mold, releasing the zinc-cobalt-chromium-iron-oxide magnetic nanowires, and centrifuging at 5000-12000 r/min to obtain the temperature self-control magnetic nanowires with the diameter of 5-45 nm and the length of 5-30 mu m.
The surface of the magnetic nanowire prepared by the embodiment is provided with a hydrophobic membrane formed by a layer of fluorine-containing silane agent, the fluorine-containing silane agent belongs to a fluorine-containing surfactant, and the magnetic nanowire is high in heat resistance stability and chemical stability, hydrophobic and oleophobic, can prevent the agglomeration of the magnetic nanowire, and solves the problem of capillary embolism of normal tissues caused by the agglomeration of the magnetic nanowire material.
Example 6
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percentThe thickness of the thin aluminum foil is 0.05-0.1 mm, the surface of the thin aluminum foil is polished and cut into 50mm multiplied by 50mm square blocks, and the cut thin aluminum foil is immersed into H with the molar concentration of 0.1-0.5 mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24-57V, and the oxidation time is 5-20 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 6.0-7.0 wt%, and the mass concentration of the chromic acid is 1.6-1.7 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 35-45V, the oxidation time is 50-180 min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-iron-oxide hydroxide in the micro-channels of the aluminum anode oxidation micro-channel template by using a chemical coprecipitation method, and sintering to form zinc-cobalt-chromium-iron-oxide magnetic nanowires;
according to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 Soaking an aluminum anodic oxidation micro-channel template into a metal salt mixed solution prepared from (0.10-0.22), (0.11-0.23), (0.10-0.16) and (0.45-0.60), heating to 60-80 ℃, vacuum-pumping to remove gas in the micro-channel, filling the metal salt mixed solution into the micro-channel, dripping 0.5-2.0 mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate a zinc-cobalt-chromium-oxygen hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 500-550 ℃ for 0.5-1.5 hours;
and then, immersing the aluminum anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.6h to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
Corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium ferrite magnetic nanowire:
immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment into a NaOH aqueous solution with the mass concentration of 10-25%, corroding 90% of the aluminum anodic oxidation micro-channel mold, exposing the zinc-cobalt-chromium-iron-oxide magnetic nanowires in a directional array arrangement, soaking the exposed zinc-cobalt-chromium-iron-oxide magnetic nanowires by using ethyl orthosilicate with the concentration of 0.2-0.5 mol/L at the soaking temperature of 120-200 ℃ for 0.4h, finishing surface hydrophobization, completely corroding the rest aluminum anodic oxidation micro-channel mold, releasing the zinc-cobalt-chromium-iron-oxide magnetic nanowires, and centrifuging at 5000-00 r/min to obtain the temperature-self-control magnetic nanowires with the diameter of 1205-45 nm and the length of 5-30 mu m.
The surface of the magnetic nanowire prepared by the method is provided with a glass modified film formed by ethyl orthosilicate, and the magnetic nanowire modified by the glass film can be directly used as a magnetic medium material to be introduced into or intervened in a human body, is not easy to agglomerate, and has good biocompatibility and no toxicity.
Example 7
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, the thickness of the thin aluminum foil is 0.05mm, the surface of the thin aluminum foil is polished and cut into blocks of 50mm multiplied by 50mm, and the cut thin aluminum foil is immersed into H with the molar concentration of 0.2mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 24V, and the oxidation time is 20 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 6.0-7.0 wt%, and the mass concentration of the chromic acid is 1.6-1.8 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 Performing secondary anodic oxidation in aqueous solution, and performing secondary oxygenThe chemical voltage is 35V, the oxidation time is 150min, the aluminum anode oxidation micro-channel template is taken out, cleaned and dried, and the aluminum anode oxidation micro-channel template is prepared and provided with micro-channels which are arranged in an array mode, and the pore diameter of each micro-channel is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
according to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 The method comprises the following steps of preparing a metal salt mixed solution according to a molar ratio of 0.10:0.11:0.10:0.45, immersing an aluminum anodic oxidation micro-channel template into the metal salt mixed solution, heating to 80 ℃, vacuum-pumping to remove gas in the micro-channel to enable the metal salt mixed solution to be full of the micro-channel, dripping 1.0mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate a zinc-cobalt-chromium-ferrite hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 500 ℃ for 1.5 hours;
then, the aluminum anodic oxidation micro-channel template is immersed in the metal salt mixed solution again, ammonia water is dripped into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, the aluminum anodic oxidation micro-channel template is taken out and dried for 1.5h at the temperature of 120 ℃, and sintered for 0.7h at the temperature of 750 ℃ to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
Corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium ferrite magnetic nanowire:
immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment into a NaOH aqueous solution with the mass concentration of 10%, corroding 90% of aluminum anodic oxidation micro-channel mold, exposing directional array arrangement zinc-cobalt-chromium-iron-oxide magnetic nanowires, soaking the exposed zinc-cobalt-chromium-iron-oxide magnetic nanowires for 0.5h by using perfluoroalkyl sulfonate with the molar concentration of 0.5mol/L, completing surface hydrophobization treatment, completely corroding the rest aluminum anodic oxidation micro-channel mold, releasing the zinc-cobalt-chromium-iron-oxide magnetic nanowires, and centrifuging at 6000r/min to obtain the temperature-controlled magnetic nanowires with the diameter of 17-36 nm and the length of 5-30 mu m.
Example 8
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, the thickness of the thin aluminum foil is 0.08mm, the surface of the thin aluminum foil is polished and cut into blocks of 50mm multiplied by 50mm, and the cut thin aluminum foil is immersed into H with the molar concentration of 0.3mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 35V, and the oxidation time is 15 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 6.5-7.5 wt%, and the mass concentration of the chromic acid is 1.7-1.9 wt%.
Then the aluminum foil is dipped into H again 2 SO 4 And (2) carrying out secondary anodic oxidation in the aqueous solution, wherein the secondary oxidation voltage is 40V, the oxidation time is 100min, taking out, cleaning and drying to obtain the aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of the micro-channels is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
according to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 The method comprises the following steps of preparing a metal salt mixed solution according to a molar ratio of 0.22:0.23:0.16:0.60, immersing an aluminum anodic oxidation micro-channel template into the metal salt mixed solution, heating to 75 ℃, vacuum-pumping to remove gas in the micro-channel to enable the metal salt mixed solution to be full of the micro-channel, dripping 1.5mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate a zinc-cobalt-chromium-ferrite hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 530 ℃ for 1.0 hour;
then, the aluminum anodic oxidation micro-channel template is immersed in the metal salt mixed solution again, ammonia water is dripped into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, the aluminum anodic oxidation micro-channel template is taken out and dried for 1.0h at the temperature of 150 ℃, and sintered for 0.8h at the temperature of 1000 ℃ to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
Corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium ferrite magnetic nanowire:
immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment into a NaOH aqueous solution with the mass concentration of 20%, corroding 90% of an aluminum anodic oxidation micro-channel mold, exposing directional array arrangement zinc-cobalt-chromium-oxygen oxide magnetic nanowires, impregnating the exposed zinc-cobalt-chromium-oxygen oxide magnetic nanowires by using tetraethoxysilane with the concentration of 0.5mol/L, wherein the impregnation temperature is 180 ℃, the impregnation time is 0.8h, finishing surface hydrophobization treatment, completely corroding the rest aluminum anodic oxidation micro-channel mold, releasing the zinc-cobalt-chromium-oxygen oxide magnetic nanowires, and centrifuging at 8000r/min to obtain the self-temperature-control magnetic nanowires with the diameter of 16-37 nm and the length of 5-30 mu m.
Example 9
A preparation method of a self-temperature-control magnetic nanowire comprises the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice:
taking a thin aluminum foil with the purity of more than or equal to 99.95 percent, the thickness of the thin aluminum foil is 0.1mm, the surface of the thin aluminum foil is polished and cut into blocks of 50mm multiplied by 50mm, and the cut thin aluminum foil is immersed into H with the molar concentration of 0.4mol/L 2 SO 4 Carrying out primary anodic oxidation in the aqueous solution, wherein the primary oxidation voltage is 57V, and the oxidation time is 10 min; and immersing the aluminum foil subjected to primary anodic oxidation into a mixed solution of phosphoric acid and chromic acid to remove a primary oxidation film on the surface of the aluminum foil, wherein the mass concentration of the phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 7.0-8.0 wt%, and the mass concentration of the chromic acid is 1.9-2.8 wt%.
Then the aluminum foil is dipped again in H 2 SO 4 Performing secondary anodic oxidation in water solution with secondary oxidation voltage of 45V and oxidation time of 80min, taking out, cleaning and drying to obtain aluminum anodic oxidation microporesThe aluminum anodic oxidation micro-channel template is provided with micro-channels which are arranged in an array manner, and the pore diameter of each micro-channel is 10-100 nm.
Depositing zinc-cobalt-chromium-ferrite hydroxide in the micro-pore of the aluminum anode oxidation micro-pore template by using a chemical coprecipitation method, and sintering to form a zinc-cobalt-chromium-ferrite magnetic nanowire;
doping FeCl with a certain proportion in metal salt solution 2 And NiCl 2+X According to CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 、FeCl 2 And NiCl 2+X The method comprises the following steps of preparing a metal salt mixed solution according to a molar ratio of 0.22:0.23:0.16:0.60:0.23:0.16, immersing an aluminum anodic oxidation micro-channel template into the metal salt mixed solution, heating to 70 ℃, vacuum-pumping and discharging gas in the micro-channel to enable the metal salt mixed solution to be full of the micro-channel, dripping 2.0mol/L of ammonia water into the micro-channel, carrying out chemical coprecipitation on the ammonia water and the metal salt mixed solution to generate a zinc-cobalt-chromium-ferrite hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, and treating the aluminum anodic oxidation micro-channel template at 550 ℃ for 0.5 h;
then the aluminum anodic oxidation micro-channel template is immersed in the metal salt mixed solution again, ammonia water is dripped into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, the aluminum anodic oxidation micro-channel template is taken out and dried for 0.5h at the temperature of 170 ℃, and sintered for 0.9h at the temperature of 1200 ℃ to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire.
Corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium ferrite magnetic nanowire:
immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment into a NaOH aqueous solution with the mass concentration of 25%, corroding 90% of aluminum anodic oxidation micro-channel mold, exposing directional array arrangement zinc-cobalt-chromium-iron-oxide magnetic nanowires, soaking the exposed zinc-cobalt-chromium-iron-oxide magnetic nanowires for 0.2h by utilizing perfluoroalkyl sulfonate with the molar concentration of 1.0mol/L, completing surface hydrophobization treatment, completely corroding the rest aluminum anodic oxidation micro-channel mold, releasing the zinc-cobalt-chromium-iron-oxide magnetic nanowires, centrifuging at 10000r/min, and obtaining the temperature-controlled magnetic nanowires with the diameter of 17-34 nm and the length of 5-30 mu m.
Measuring the curie temperature point of the magnetic nanowire prepared in the embodiment 7-9 by using an optical fiber thermometer, wrapping the magnetic nanowire around the sensitive grating of the optical fiber, placing the magnetic nanowire in a coil generating a magnetic field, gradually increasing the power of the magnetic field, starting heating the magnetic nanowire, detecting the temperature change by using the optical fiber thermometer, and starting to decrease the temperature point until the optical fiber thermometer detects the peak value of the temperature change, wherein the peak value point is the curie temperature point; the heat generation rate of the magnetic nanowires prepared in examples 7, 8 and 9, which convert magnetic field energy into heat energy, was measured using a high-frequency magnetic induction heating measurement system, and the measurement results are shown in table 1:
TABLE 1
As can be seen from the comparison of the data in the table 1, the self-temperature-control magnetic nanowire preparation method provided by the invention prepares the zinc-cobalt-chromium-iron-oxide magnetic nanowire with the Curie temperature of 42-45 ℃ through the reasonable proportion of the metal salts, and has the advantages of stable chemical performance, excellent magnetic property and the Curie temperature meeting the self-temperature-control magnetic thermotherapy requirement. By adding FeCl to metal salts 2 And NiCl 2+X And further doping modification can be carried out, so that the magnetic characteristics and the Curie temperature point of the material can be adjusted, and the Curie temperature point of the magnetic nanowire is further accurate to 42-44 ℃.
The temperature self-control magnetic nanowire provided by the invention has a linear structure with the diameter of 5-45 nm and the length of 5-30 mu m, can generate a hysteresis effect and a relaxation effect under the action of an alternating magnetic field, can also generate an eddy current effect, can remarkably improve the heat production rate of the magnetic nanowire by exerting the effect of the three magnetocaloric effects together, and can relatively reduce the dosage of the magnetic nanowire used in the application of magnetocaloric therapy, thereby reducing the potential toxic and side effects in the clinical treatment process.
Claims (6)
1. A preparation method of a self-temperature-control magnetic nanowire is characterized by comprising the following steps:
step one, preparing an aluminum anodic oxidation micro-channel template by carrying out anodic oxidation on an aluminum foil twice;
the two-time anodic oxidation method comprises the following specific steps: immersing the aluminum foil in H 2 SO 4 In the water solution, primary anodic oxidation is carried out under primary oxidation voltage, the aluminum foil is immersed into the mixed solution of phosphoric acid and chromic acid after oxidation, the primary oxidation film on the surface of the aluminum foil is removed, and then the aluminum foil is immersed into H again 2 SO 4 In the water solution, carrying out secondary anodic oxidation under a secondary oxidation voltage, taking out after oxidation, cleaning and drying to prepare an aluminum anodic oxidation micro-channel template, wherein the aluminum anodic oxidation micro-channel template is provided with micro-channels arranged in an array manner;
the purity of the aluminum foil is more than or equal to 99.95%, and the thickness of the aluminum foil is 0.05-0.1 mm; said H 2 SO 4 The molar concentration of the aqueous solution is 0.1-0.5 mol/L; the mass concentration of phosphoric acid in the mixed solution of phosphoric acid and chromic acid is 4-8 wt%, and the mass concentration of chromic acid is 1.2-2.8 wt%; the primary oxidation voltage is 24-57V, the primary oxidation time is 5-20 min, the secondary oxidation voltage is 35-45V, and the secondary oxidation time is 50-180 min; the pore diameter of the micro-channel is 10-100 nm;
depositing zinc-cobalt-chromium-iron-oxide hydroxide in the micro-channels of the aluminum anode oxidation micro-channel template by using a chemical coprecipitation method, and sintering to form zinc-cobalt-chromium-iron-oxide magnetic nanowires;
the specific method of the chemical coprecipitation method comprises the following steps: CoCl is prepared according to the molar ratio of (0.10-0.22), (0.11-0.23), (0.10-0.16), (0.45-0.60) 2 、FeCl 3 、CrCl 3 And ZnCl 2 Immersing the aluminum anodic oxidation micro-channel template prepared in the step one into the metal salt mixed solution, heating to 60-80 ℃, vacuum-pumping to remove gas in the micro-channel, enabling the metal salt mixed solution to be full of the micro-channel, dripping 0.5-2.0 mol/L of ammonia water into the micro-channel, enabling the ammonia water and the metal salt mixed solution to generate chemical coprecipitation to generate a zinc-cobalt-chromium-iron-oxide hydroxide precipitate in the micro-channel, continuously dripping the ammonia water until the precipitate is not generated, taking out the aluminum anodic oxidation micro-channel template, treating the aluminum anodic oxidation micro-channel template at 500-550 ℃ for 0.5-1.5 h, and then, putting the aluminum anodic oxidation micro-channel template into the metal salt mixed solutionImmersing the anodic oxidation micro-channel template into the metal salt mixed solution again, dripping ammonia water into the micro-channel filled with the metal salt mixed solution to complete chemical coprecipitation, taking out the aluminum anodic oxidation micro-channel template, drying at 120-170 ℃ for 0.5-1.5 h, and sintering at 750-1200 ℃ for 0.2-1.0h to form the zinc-cobalt-chromium-iron-oxide magnetic nanowire;
and step three, corroding and removing the aluminum anodic oxidation micro-channel template, and performing surface hydrophobization treatment on the zinc-cobalt-chromium-iron-oxide magnetic nanowire to obtain the self-temperature-control magnetic nanowire.
2. The method as claimed in claim 1, wherein the metal salt mixture is further doped with FeCl 2 And NiCl 2+X Wherein CoCl 2 、FeCl 3 、CrCl 3 And ZnCl 2 、FeCl 2 And NiCl 2+X The molar ratio of (0.10-0.22), (0.11-0.23), (0.10-0.16), (0.45-0.60), (0.11-0.23) and (0.10-0.16).
3. The method for preparing the self-temperature-controlling magnetic nanowire according to claim 1 or 2, wherein the specific methods of etching to remove the aluminum anodized micro-channel template and performing surface hydrophobization treatment in the third step are as follows: immersing the aluminum anodic oxidation micro-channel template subjected to sintering treatment in the second step into a NaOH aqueous solution with the mass concentration of 10-25%, corroding 90% of the aluminum anodic oxidation micro-channel template to expose the zinc-cobalt-chromium-ferrite magnetic nanowires, soaking the exposed zinc-cobalt-chromium-ferrite magnetic nanowires by using a fluorine-containing surface ion complexing agent perfluoroalkyl sulfonate solution or tetraethoxysilane to complete surface hydrophobization treatment, completely corroding the rest of the aluminum anodic oxidation micro-channel template to release the zinc-cobalt-chromium-ferrite magnetic nanowires, and centrifuging at 5000-12000 r/min to obtain the self-temperature-control magnetic nanowires.
4. The method for preparing self-temperature-controlling magnetic nanowires of claim 3, wherein the solution of the fluorine-containing surface ion complexing agent is perfluoroalkyl sulfonate, the molar concentration is 0.2-1.0 mol/L, and the dipping time is 0.1-0.5 h.
5. The method for preparing self-temperature-controlling magnetic nanowires of claim 3, wherein the concentration of the tetraethoxysilane is 0.2-0.5 mol/L, the dipping time is 0.1-0.3 h, and the temperature for dipping the tetraethoxysilane is 120-200 ℃.
6. The temperature-self-controlling magnetic nanowire prepared by the method of preparing a temperature-self-controlling magnetic nanowire according to any one of claims 1 to 5, wherein the diameter is 5 to 45nm, the length is 5 to 30 μm, and the Curie temperature is 42 to 45 ℃.
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