CN106801160B - Blacker-than-black nanoporous Fe and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of preparation methods of blacker-than-black nanoporous Fe, belong to technical field of nanometer material preparation, including：1) for synthesis Mn contents in 68 90at%, Cu contents are less than the FeMnCu prealloy melts within the scope of 0.3at%, and carry out fast quenching in 1,240 1700 degrees Celsius of melt and obtain single-phase alloy；2) by under 4 25 degrees celsius, FeMnCu prealloys is placed in and stands 30 60 minutes in the hydrochloric acid solution that volumetric concentration is 1% 5% and carries out taking off alloy treatment；3) the complete product of de- alloy is taken out, difference is successively 0.1% in volumetric concentration, is rinsed in 0.01% hydrochloric acid solution, and the time is no more than 10 seconds, then is rinsed in ultra-pure water, and the time is no more than 30s；Product after rinsing is taken out, is dried under the conditions of inert gas shielding and can be obtained blacker-than-black nanoporous Fe materials.

Description

Ultra-black nanoporous Fe and its preparation method

technical field

The invention belongs to the technical field of nanomaterial preparation, and in particular relates to ultra-black nanoporous Fe and a preparation method thereof.

Background technique

Ultra-black material is a material with a reflectivity of less than 1% and an absorption rate of more than 99% for incident light within a certain range. In many optical devices, sensors, and solar energy converters, there is an urgent need for ultra-black materials in such devices because unnecessary reflection of incident light by the interface will have many adverse effects on performance. At the same time, due to the excellent stealth performance of the ultra-black material itself, it is also of great use in the military.

In view of this, ultra-black materials have been extensively studied and applied in recent years. At present, the most outstanding performance is Vantablack developed by Surrey Nanosystems, which is mainly composed of vertically arranged carbon nanotubes, but the production cost is very high. Other commonly used materials also include non-metallic materials such as amorphous carbon and polycrystalline black silicon, nickel-phosphorus master alloy materials, and pure metal ultra-black materials have not been reported yet. Its morphology includes nanotube arrays, micro-convex arrays and roughened irregular surfaces. Ultra-black devices with three-dimensional connected nanoporous structures have not been reported yet. The preparation methods mainly include chemical vapor deposition, biological template method and so on. Most of these methods have the disadvantages of high cost and inability to carry out large-scale production. However, the present invention adopts the dealloying method to prepare the ultra-black material, and the preparation method is simple and feasible. The obtained product is nano-porous structure Fe with three-dimensional connected structure, and has the advantages of low price of finished product and wide range of light absorption.

Contents of the invention

Technical problem: the purpose of the present invention is to provide a kind of preparation method of ultra-black nano-porous Fe, and this preparation method is simple, adopts the ultra-black nano-porous Fe of its preparation to have the pore channel structure of three-dimensional connection; Another purpose of the present invention is to provide the The ultra-black nanoporous Fe prepared by the method has the advantage of wide light absorption range.

Technical solution: In order to achieve the above-mentioned purpose of the invention, the present invention adopts the following technical solutions:

The preparation method of ultra-black nanoporous Fe comprises the steps:

1) Mix Fe, Mn and Cu pure metals with a purity of more than 99%, and then obtain a uniform metal melt by induction heating, and then perform rapid quenching to obtain a FeMnCu pre-alloy with a single-phase structure; wherein, the atomic percentage of the pure metal of the raw material is the Mn content 68-90at%, Cu content 0-0.3at%; induction heating temperature not higher than 1700 degrees Celsius, heating time not longer than 20 minutes, heating times not less than 2 times; homogeneous metal melt rapid quenching temperature 1240-1700 degrees Celsius , obtaining a FeMnCu pre-alloy with a single-phase structure;

2) under the condition of 4-25 degrees Celsius, place the FeMnCu alloy in a hydrochloric acid solution with a volume concentration of 1%-5% and let it stand for 30-60 minutes for dealloying treatment;

3) The dealloyed product is taken out, rinsed successively in hydrochloric acid solutions with a volume concentration of 0.1% and 0.01%, respectively, for no more than 10 seconds,

4) Rinse the sample after pickling in ultrapure water for no more than 30s;

5) The product after rinsing is taken out and dried under the protection condition of an inert gas, the oxygen content of the inert gas is less than 1/10,000, and the drying temperature does not exceed 30 degrees Celsius, and the ultra-black nanoporous Fe material can be obtained.

Beneficial effects: compared with the prior art, the method for preparing the ultra-black material of the present invention is simple to operate, and the ultra-black material prepared by the method is Fe with a nanoporous structure. Studies have shown that the ultra-black materials prepared by the dealloying method have good wave-absorbing properties in the wavelength range of 350-1000nm.

Detailed ways

The present invention will be further described below through specific embodiments.

The preparation method of ultra-black nanoporous Fe comprises the steps:

1) Mix Fe, Mn and Cu pure metals with a purity of more than 99%, and then obtain a uniform metal melt by induction heating, and then perform rapid quenching to obtain a FeMnCu pre-alloy with a single-phase structure; wherein, the atomic percentage of the pure metal of the raw material is the Mn content 68-90at%, Fe content 31.7-9.7at%, Cu content less than 0.3at%; induction heating temperature not higher than 1700 degrees Celsius, heating time not longer than 20 minutes, heating times not less than 2 times; uniform molten metal The rapid quenching temperature is 1240-1700 degrees Celsius to obtain a FeMnCu pre-alloy with a single-phase structure;

2) under the condition of 4-25 degrees Celsius, place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 1%-5% and let it stand for 30-60 minutes for dealloying treatment;

3) The dealloyed product is taken out, rinsed successively in hydrochloric acid solutions with a volume concentration of 0.1% and 0.01%, respectively, for no more than 10 seconds,

4) Rinse the sample after pickling in ultrapure water for no more than 30s;

5) The product after rinsing is taken out and dried under the protection condition of an inert gas, the oxygen content of the inert gas is less than 1/10,000, and the drying temperature does not exceed 30 degrees Celsius, and the ultra-black nanoporous Fe material can be obtained. The material has good absorbing performance in the wavelength range of 350-1000nm.

Example 1

Fe and Mn pure metals with a purity of more than 99% are mixed according to the ratio of 32at%: 67.9at%, and then melted twice at 1700 degrees Celsius by induction heating for 10 minutes each time to obtain a uniform metal melt and then quickly quenched at 1240 degrees Celsius. A FeMnCu prealloy with a single phase structure is obtained. Place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 1% and let it stand for 60 minutes for dealloying treatment; the dealloyed product is taken out, and then rinsed in the hydrochloric acid solution with a volume concentration of 0.1% and 0.01% for 10 seconds respectively , and then rinsed in ultrapure water for 30s; the product after rinsing was taken out and dried at 30 degrees Celsius under inert gas protection conditions to obtain an ultra-black nanoporous Fe material. The nanopore is between 10-30nm, the oxygen content is 16-19at%, and the reflectance of the material is 0.5-0.8% in the wavelength range of 350-1000nm.

Example 2

Fe, Mn and Cu pure metals with a purity above 99% are mixed according to the ratio of 31.7at%: 68at%: 0.3at%, and then melted twice at 1500 degrees Celsius by induction heating for 10 minutes each time to obtain a uniform metal melt Rapid quenching at 1500 degrees Celsius to obtain FeMnCu pre-alloy with single phase structure. Place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 1% and let it stand for 60 minutes for dealloying treatment; the dealloyed product is taken out, and then rinsed in the hydrochloric acid solution with a volume concentration of 0.1% and 0.01% for 10 seconds respectively , and then rinsed in ultrapure water for 30s; the product after rinsing was taken out and dried at 30 degrees Celsius under inert gas protection conditions to obtain an ultra-black nanoporous Fe material. The nanopore is between 30-50nm, the oxygen content is 12-17at%, and the reflectance of the material is 0.7-0.9% in the wavelength range of 350-1000nm.

Example 3

Fe, Mn and Cu pure metals with a purity of more than 99% are mixed according to the ratio of 9.7at%: 90at%: 0.3at%, and then melted twice at 1240 degrees Celsius by induction heating for 10 minutes each time to obtain a uniform metal melt Rapid quenching at 1240 degrees Celsius to obtain a FeMnCu pre-alloy with a single-phase structure. Place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 1% and let it stand for 60 minutes for dealloying treatment; the dealloyed product is taken out, and then rinsed in the hydrochloric acid solution with a volume concentration of 0.1% and 0.01% for 5 seconds , and then rinsed in ultrapure water for 10s; the product after rinsing was taken out and dried at 30 degrees Celsius under inert gas protection conditions to obtain an ultra-black nanoporous Fe material. The nanopore is between 70-100nm, the oxygen content is 12-17at%, and the reflectance of the material is 0.9-0.1% in the wavelength range of 350-1000nm.

Example 4

Fe and Mn pure metals with a purity of more than 99% are mixed according to the ratio of 32at%: 68at%, and then melted twice at 1500 degrees Celsius by induction heating for 5 minutes each time to obtain a uniform metal melt and then quickly quenched at 1500 degrees Celsius to obtain FeMnCu prealloy with single phase structure. Place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 5% and let it stand for 30 minutes for dealloying treatment; the dealloyed product is taken out, and then rinsed in a hydrochloric acid solution with a volume concentration of 0.1% and 0.01% for 5 seconds , and then rinsed in ultrapure water for 10s; the rinsed product was taken out, and dried at 30 degrees Celsius under inert gas protection conditions to obtain an ultra-black nanoporous Fe material. The nanopore is between 10-20nm, the oxygen content is 8-10at%, and the reflectivity of the material is 0.5-0.7% in the wavelength range of 350-1000nm.

Example 5

Fe, Mn and Cu pure metals with a purity above 99% are mixed according to the ratio of 31.7at%: 68at%: 0.3at%, and then melted twice at 1500 degrees Celsius by induction heating for 5 minutes each time to obtain a uniform metal melt Rapidly quenched at 1700 degrees Celsius to obtain a single-phase FeMnCu pre-alloy. Place the FeMnCu pre-alloyed in a hydrochloric acid solution with a volume concentration of 5% and let it stand for 30 minutes for dealloying treatment; the dealloyed product is taken out, and then rinsed in a hydrochloric acid solution with a volume concentration of 0.1% and 0.01% for 5 seconds , and then rinsed in ultrapure water for 10s; the rinsed product was taken out, and dried at 30 degrees Celsius under inert gas protection conditions to obtain an ultra-black nanoporous Fe material. The nanopore is between 20-30nm, the oxygen content is 5-8at%, and the reflectance of the material is 0.6-0.8% in the wavelength range of 350-1000nm.

Claims (6)

1. A preparation method of ultra-black nano-porous Fe is characterized by comprising the following steps:

1) mixing pure metals of Fe, Mn and Cu, carrying out induction heating to obtain uniform molten metal, and then carrying out rapid quenching to obtain a FeMnCu prealloy with a single-phase structure;

2) placing the FeMnCu prealloy obtained in the step 1) in a hydrochloric acid solution for standing, and performing dealloying treatment;

3) pickling the product obtained in the step 2) in a dilute hydrochloric acid solution;

4) rinsing the product obtained in the step 3) in ultrapure water;

5) drying the product obtained in the step 4) in an inert atmosphere to obtain the ultra-black nano porous iron;

wherein,

in the step 1), the purity of the pure metal is more than 99 percent, and the atomic percentage is that the Mn content is 67 to 90at percent, the Cu content is less than 0.3at percent, and the Fe content is 31.7 to 9.7at percent; the induction heating temperature is lower than 1700 ℃, the heating time is lower than 20 minutes, and the heating times are more than 2 times; and performing rapid quenching on the uniform molten metal within the range of 1240-1700 ℃ to obtain the FeMnCu prealloy with a single-phase structure.

2. The method of preparing ultra-black nanoporous Fe according to claim 1, wherein: in the step 2), the dealloying is carried out under the free corrosion condition, the temperature is 4-30 ℃, the volume concentration of the hydrochloric acid solution is 1% -5%, and the dealloying time is 30-60 minutes.

3. The method of preparing ultra-black nanoporous Fe according to claim 1, wherein: in the step 3), the dilute hydrochloric acid washing is to rinse the products obtained in the step 2) in a hydrochloric acid solution with the volume concentration of 0.1 percent and the volume concentration of 0.01 percent in sequence, and the time of each time is not more than 10 seconds.

4. The method of preparing ultra-black nanoporous Fe according to claim 1, wherein: rinsing in ultrapure water in the step 4) for no more than 30 s.

5. The method of preparing ultra-black nanoporous Fe according to claim 1, wherein: in the step 5), the oxygen content of the inert gas is lower than one ten thousandth, and the drying temperature is not higher than 30 ℃.

6. A nano-porous Fe prepared by the method of any one of claims 1 to 5, wherein the method comprises the following steps: the pore diameter of the nano-pore is between 10 and 100 nanometers, the oxygen content is below 20at percent, and the reflectivity is below 1 percent in the wavelength range of 350-1000 nm.