KR101500703B1 - manufacturing method of iron nano fluid using liquid phase plasma reaction - Google Patents

Abstract

The present invention relates to a method for producing iron nanofluids using a liquid-phase plasma reaction, and more particularly, to a method for producing iron nanoparticles in a liquid containing iron ions by continuously producing and dispersing iron nanoparticles in a liquid. The present invention relates to a method for producing an iron nanofluid.
The method for preparing iron nanofluid using the liquid-phase plasma reaction of the present invention comprises the steps of preparing a precursor solution for dissolving iron chloride in water to prepare a precursor solution containing iron ions, adding a surfactant to the precursor solution, And a liquid phase plasma reaction step of generating plasma in the precursor solution to which the surfactant is added to produce iron nanoparticles.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a manufacturing method of an iron nanofluid using a liquid-phase plasma reaction,

The present invention relates to a method for producing iron nanofluids using a liquid-phase plasma reaction, and more particularly, to a method for producing iron nanoparticles in a liquid containing iron ions by continuously producing and dispersing iron nanoparticles in a liquid. The present invention relates to a method for producing an iron nanofluid.

Nanoparticles have been studied in recent years because of their optical, electrical, and catalytic properties, which are different from bulk materials. The properties of the nanofluids are determined by various factors such as the size and shape of the nanoparticles and the dispersibility. Because of the nature of these nanoparticles, they are used in many applications. For example, when nanoparticles are dispersed in a common fluid, the thermal conductivity and convective heat transfer effect are increased.

The concept of nanofluids was first introduced by the American ANL (Argonne National Laboratory). Nanofluids have a high thermal conductivity that conventional liquids do not have due to the uniform dispersion of solid nanoparticles with thermal conductivity of several hundred to several tens of times greater than liquids.

 A conventional nanofluid manufacturing method uses a two step method in which two steps are sequentially performed. The two step method is a method of manufacturing a nanofluid by performing a process of producing nanoparticles in a gas phase and a process of dispersing the produced nanoparticles in a liquid.

The two-step method is a domestic nanofluid-related research project that is designed and developed for the reactor design and safety analysis of a nuclear power plant. It is a technology to develop a fluid mixed with nanoparticles for improving the heat transfer coefficient in the cooling furnace. (Supporting institution: Ministry of Science and Technology, Basic Research Project, 2002.10 - 2003.09). In this study, the basic fluid was water and mechanical dispersion using ultrasonic wave was applied for dispersion stability of nanoparticles.

A method for producing a nanoparticle compound with a patented technique, a method for manufacturing a nanoparticle dispersion, and a device therefor are disclosed in Patent Publication No. 2010-0019599. The patented technique involves suspending the prepared nanoparticles with a carrier gas, subjecting the suspended nanoparticles to hydrophilization by atmospheric plasma treatment, mixing the nanoparticles with a liquid material, stirring the nanoparticles, and filtering the nanoparticles to produce a nanoparticle dispersion.

Thus, the conventional techniques use a two step method for producing nanofluids through a separate process of dispersing the nanoparticles produced after the process of manufacturing nanoparticles in a gas phase.

However, the conventional two-step method has advantages in that it can be mass-produced. However, since each step needs to be carried out in a separate process and apparatus, the production efficiency is low, and when the surface properties and fluid characteristics of the nanoparticles are different from each other, There are disadvantages.

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a nanofluid by simply producing a nanofluid in a single process by continuously producing and dispersing iron nanoparticles in a liquid by generating plasma in a liquid containing iron ions There is a purpose in providing a method.

According to another aspect of the present invention, there is provided a method for preparing iron nanofluid using a liquid-phase plasma reaction, comprising the steps of: preparing a precursor solution containing iron ions by dissolving iron chloride in water; A surfactant addition step of adding a surfactant to the precursor solution; And a liquid-phase plasma reaction step of generating plasma in the precursor solution to which the surfactant is added to produce iron nanoparticles.

Wherein the surfactant in the surfactant addition step is a cationic surfactant.

The cationic surfactant is cetyltrimethyl ammonium bromide.

The iron chloride in the precursor solution is 3.3 mM and the surfactant addition step is characterized by adding 30 to 50% of the cationic surfactant to the precursor solution in molar ratio with respect to the iron chloride.

The liquid-phase plasma reaction step is characterized in that the power supplied to the electrode exposed to the precursor solution is a voltage of 250 V, a pulse width of 1 to 5 μs, and a frequency of 30 kHz.

The solvent is characterized in that ethanol and distilled water are mixed.

As described above, the plasma is generated in the precursor solution containing the precursor, and the production and dispersion of the iron nanoparticles are continuously performed in the liquid, so that the nanofluid can be easily manufactured by one process.

In addition, the present invention can produce nano-sized particles by reducing iron metal in water using a liquid-phase plasma reaction.

In addition, the size and shape of the iron nanoparticles can be controlled using the concentration of the precursor, the discharge condition, and the surfactant.

FIG. 1 is a schematic view showing a liquid-phase plasma reactor applied to an embodiment of the present invention,
2 is a graph showing OES analysis results measured in pure distilled water,
FIG. 3 is a photograph of iron nanofluid prepared by different kinds of solvents,
FIG. 4 is a TEM photograph of iron nanoparticles prepared by varying the concentration of surfactant,
5 is a TEM photograph showing an electron diffraction pattern of iron nanoparticles prepared by different kinds of solvents.

Hereinafter, a method of manufacturing an iron nanofluid using a liquid-phase plasma reaction according to a preferred embodiment of the present invention will be described.

The method for producing iron nanofluids using the liquid-phase plasma reaction of the present invention provides iron nanofluids in which iron nanoparticles are uniformly dispersed in a liquid. The iron nanoparticles may have an average particle size of 1 to 100 nm.

A method for preparing iron nanofluid using a liquid-phase plasma reaction according to an embodiment of the present invention includes the steps of preparing a precursor solution for preparing a precursor solution containing iron ions, adding a surfactant to the precursor solution, And a liquid phase plasma reaction step of generating a plasma in the precursor solution to produce iron nanoparticles. Hereinafter, each step will be described in detail.

1. Preparation of precursor solution

A precursor solution containing iron ions is prepared in the step of preparing the precursor solution. As an example of the precursor solution, iron chloride (FeCl ₂ Or FeCl ₃ ). The iron chloride dissolved in the solvent is a precursor of iron nanoparticles. Therefore, the precursor solution means that the precursor, iron chloride, is dissolved in the solvent. And water or a mixture of ethanol and water may be used as the solvent. Preferably the solvent is a mixture of ethanol and water. When a mixture of ethanol and water is used as a solvent, oxidation of the resulting iron nanoparticles can be suppressed.

Iron is present in the form of cations in the precursor solution obtained by dissolving iron chloride in a solvent. The ferric chloride may be dissolved in the precursor solution at a concentration of 0.5 to 10.0 mM. The electric conductivity of the precursor solution changes depending on the molar concentration of the dissolved iron chloride. Electrical conductivity can affect the properties of the resulting iron nanoparticles.

When the precursor solution is prepared, the next step, the liquid-phase plasma reaction step, may be performed immediately, but preferably a surfactant addition step of adding a surfactant to the precursor solution is performed.

2. Add surfactant step

By adding a surfactant to the precursor solution, it is possible to manufacture highly dispersed nanoparticles having a smaller particle size more efficiently.

When the solid particles (1 μm or less) are dispersed in an aqueous solution to form a suspension, the surface of the particles is positively or negatively charged. The mechanism of generating charges on the surface of such particles is not clearly defined not.

If the charge value of the metal nanoparticle has a negative sign, it can be judged that it is charged with a negative charge such as a negative charge or a hydroxide ion. If the metal nanoparticles produced in solution are negatively charged, use a cationic surfactant. If the metal nanoparticles are charged positively, use an anionic surfactant to disperse the metal nanoparticles in solution. .

In the present invention, it is experimentally confirmed that iron nanoparticles can be dispersed using a cationic surfactant.

As the cationic surfactant, cetyltrimethyl ammonium bromide (CTAB) can be used. In addition, benzoalkonium chloride, miristalkonium chloride, cetylpyridinium chloride, and cetyltrimethyl ammonium chloride can be used, but cetyltrimethylammonium bromide is effective.

The concentration of the surfactant may be from 5 to 50% (molar ratio of surfactant to iron chloride dissolved in water).

3. Liquid Phase Plasma Reaction Step

Plasma is generated in the precursor solution after addition of the surfactant to produce iron metal particles.

The liquid phase plasma (LPP) reaction applied to the present invention is a technique for synthesizing and dispersing nanoparticles in a single process by generating a high-density, high-energy plasma in a liquid, which is economical and secures productivity, Dispersed iron nanoparticles can be produced.

The flow of ions and electrons in response to the application of electrical energy in the liquid generates a plasma in the liquid. When the liquid is water, the main generating elements of the plasma are hydrogen and oxygen. As the amount of electric energy applied increases, the flow of ions and electrons increases, and the plasma intensity can be increased. Plasma generation is related to the flow of electrons, so that electrons are provided to the iron ions present in the liquid to generate iron nanoparticles.

An example of a liquid-phase plasma reactor for generating a plasma in a liquid phase is shown in Fig.

The illustrated liquid-phase plasma reactor includes a cylindrical reactor 10, a cooling tank 40 for circulating the precursor solution in the reactor 10 to maintain a constant temperature, a circulation pump 50, And an electric power supply (bipolar pulse power supply) 20 for supplying electric power to the electrode 30. The electrode 30 is made of tungsten, and the outside of the electrode 30 is covered with an insulator 35 made of a ceramic material. The distance between the two electrodes 30 can be maintained at about 0.7 mm.

When power is supplied to the electrode 30 through the power supply 20, a plasma is formed in the liquid by electric discharge to synthesize nanoparticles. In order to prevent the temperature of the precursor solution due to the high temperature from rising when the plasma is generated by the electric discharge, the circulation pump 50 is used to circulate the precursor solution to the cooling bath 40 to adjust the temperature of the precursor solution to 20 to 25 캜 . The reactor (10) and the cooling bath (40) are connected to circulation lines (45) and (55).

It is preferable to supply pulses (pulse width 1 to 5)) rather than supplying power continuously to the electrodes at the time of power supply. Supplying the power as a pulse suppresses the dissolution of the electrode exposed to the precursor solution, thereby greatly reducing the elution of the electrode component into the precursor solution.

The power supply condition supplied to the electrode for generating the plasma may be 250 V, a pulse width of 1 to 5 μs, and a frequency of 30 kHz. The discharge time can be maintained for 1 to 120 minutes.

When the plasma is generated in the liquid, the iron ions in the precursor solution are reduced, and the iron nanofluids in which the iron nanoparticles are uniformly dispersed in the liquid can be produced. As described above, the present invention can produce and disperse iron nanoparticles in a continuous process by generating plasma in the precursor solution. Nanofluids can be used in a variety of industrial applications, such as local heating fluid transport fluids, industrial heat exchangers, and automotive engine cooling systems. In addition, iron nanoparticles dispersed in a nanofluid can be used for manufacturing various high-tech materials by supporting carbon nanotubes (activated carbon, carbon nanotubes, graphene, fullerene) or TiO ₂ particles.

Hereinafter, a method for producing the iron nanofluid of the present invention will be described by way of examples. However, the following experimental examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited to the following experimental examples.

≪ Production test of iron nanofluid >

In this experiment, the characteristics of iron nanoparticles prepared after nanoparticles dispersed with iron nanoparticles were analyzed.

1. Preparation of precursor solution

Chloride as a precursor in a solvent to prepare a precursor solution of ferrous _{(FeCl 2 · 4H 2 O,} Junsei Chemical Co.Ltd) was stirred for 10 minutes followed by the addition of the cationic surfactant _{CTAB (cetyltrimethyl ammonium bromide, CH 3} (CH 2 _{) 15 N (CH 3) 3} Br, and the Daejung Metals & Chemicals Co.Ltd) was added from 0 to 50% (surfactant / ferrous chloride molar ratio) to prepare a precursor solution is stirred for 10 minutes.

In the preparation of the precursor solution, the molar concentration of the ferrous chloride was adjusted to 2 mM, and the conductivity of the precursor solution was 1000 μS / cm. The solvent was prepared by using two kinds of solvents. One was distilled water as a solvent and the other was a mixture of ethanol and distilled water at the same weight ratio (hereinafter, ethanol + distilled water) as a solvent.

2. Experimental apparatus

The schematic structure of the liquid-phase plasma reactor used in this experiment is shown in Fig. A high-frequency bipolar pulse power supply (NTI-500W) was used as a power supply to induce the liquid-phase plasma reaction. The generated power was supplied to a pair of cylindrical reactors (outer diameter 40 mm, height 80 mm) Tungsten electrode (diameter 2 mm, purity 99.95%, TTM Korea Co.). The outside of the tungsten electrode inside the reactor was covered with a ceramic insulator, and the distance between the two electrodes was maintained at 0.7 mm.

In order to prevent the temperature rise of the precursor solution due to the high temperature when the liquid plasma was generated by electric discharge, the precursor solution was circulated to the cooling bath at a rate of 200 cc / min by using a circulation pump, and the temperature was maintained at 20 to 25 ° C.

After the precursor solution was charged into the reactor, power was supplied to the electrode under conditions of 250V, 30KHz, and 5μs to conduct the experiment. In one experiment, the amount of the precursor solution was adjusted to 300 mL.

3. Experimental Results

(1) Optical Emission Spectrum (OES)

In order to analyze the type and intensity of the material that emits the light when the plasma is generated, the spectrum of the light source generated in the plasma was measured in the range of 200 nm to 900 nm using Optical Emission Spectroscopy (AvaSpec - 3648, Avantes).

FIG. 2 is a graph showing OES analysis results when plasma is generated in pure distilled water. Although the difference in magnitude of the element-by-element ionized while the plasma is generated, the main generating elements as in FIG. 2 is _{OH (309nm), H β (} 486.1 nm), H α (656.3 nm), O Ι (777.1, 844.34 nm) Respectively. The active species OH, H _β , H _α , It seems that iron nanoparticles are produced by the excellent reactivity of O _Ⅰ .

(2) Characteristics of nanoparticles according to the type of solvent

In order to investigate the characteristics of the nanoparticles according to the type of solvent, nanofluids were prepared by varying the discharge time using a precursor solution having a surfactant concentration of 30%. A photograph of the manufactured nanofluid is shown in Fig.

FIG. 3 (a) is a photograph showing a nanofluid produced by discharging a precursor solution made by using ethanol + distilled water as a solvent for 10, 20, and 30 min, respectively, This is a photograph of a nanofluid produced by discharging a precursor solution made by using pure distilled water for 10, 20, and 30 min, in parallel with a nanofluid that has not been discharged.

Referring to FIG. 3, when the ethanol + distilled water was used as the solvent, the color change of the prepared nano solution was hardly observed even when the discharge time was increased. On the other hand, when distilled water was used as the solvent, the color of the nano solution changed to dark brown as discharge time increased, because the iron particles produced in the nano solution were oxidized and turned brown. As the discharge time (plasma treatment time) was increased, the amount of iron oxide particles was increased. As the discharge time was increased, the color became darker. When ethanol + distilled water is used as a solvent, the generation of iron oxide particles is suppressed and the color of the nanofluid does not seem to change.

(3) Characterization of nanoparticles by addition of surfactant

In order to analyze the characteristics of iron nanoparticles according to the addition of the surfactant, a precursor solution using ethanol and distilled water as a solvent was discharged for 30 minutes to prepare a nanofluid. HR-TEM (JEM 2100F, JEOL) Were observed. For analysis, nanofluid was dropped on microgird B type 150-Cu (Japan) and dried.

4 (a) is a photograph of the case where no surfactant is added, (b) is 10% of surfactant, (c) is 30% of surfactant, and (d) is 50% of surfactant.

Referring to FIG. 4, it was confirmed that the shape of the iron nanoparticles was influenced by the surfactant concentration. When the surfactant was not added, it was confirmed that the iron particles were aggregated. When 10% surfactant was added, aggregated particles and dispersed particles were observed at the same time. When the concentration of surfactant was 30 ~ 50%, it was confirmed that spherical nanoparticles of small size were well dispersed.

FIG. 5 also shows electron diffraction patterns and photographs of the iron nanoparticles prepared using the two solvents. In FIG. 5 (a), distilled water is used as a solvent, and (b) is obtained by using ethanol + distilled water as a solvent.

5, spherical particles having a size of about 10 to 15 nm were generated in both solvents. When iron nanoparticles were prepared using distilled water and ethanol + distilled water as solvents through an electron diffraction pattern, a polycrystalline structure was formed, .

(4) Analysis of components of nanoparticles

To analyze the chemical composition of the prepared iron nanoparticles, the components were analyzed using EDX attached to HR-TEM (JEM 2100F, JEOL).

The results showed that 67.18% (Fe) and 32.82% (O) were distilled water and 88.62% (Fe) and 11.38% (O) respectively when using ethanol and distilled water as solvents. Nanoparticles prepared by using distilled water as a solvent showed relatively high oxygen content, which can be predicted to be produced together with iron oxide. This corresponds to the result that the color of the nanofluid changes to brown as the plasma treatment time increases in the nano-solution photograph of Fig. On the other hand, when ethanol + distilled water was used as a solvent, the content of oxygen was detected to be low because of inhibition of the formation of iron oxide particles. Therefore, the nano solution in Fig. 3 shows little change in the nano solution.

These results indicate that when distilled water is used as a solvent, dissolved oxygen in water and oxidizing agents such as atomic oxygen, OH radicals, and H ₂ O ₂ produced by plasma discharge easily oxidize iron particles to iron oxide do. When ethanol + distilled water is used as a solvent, it is considered that ethanol is consumed as an oxidizing agent to inhibit oxidation of iron particles to iron oxide particles.

Through the above experimental results, it was possible to produce nano-sized iron particles in the liquid by generating plasma in the precursor solution. Further, it was confirmed that the production and dispersion of iron nanoparticles in a liquid can be continuously performed in one process. In addition, it was confirmed that the size and shape of iron nanoparticles can be controlled by using a surfactant. In particular, iron nanoparticles of very small size could be prepared at a concentration of 30 to 50% by using a cationic surfactant.

In the case of producing iron nanoparticles by using liquid-phase plasma reaction, when the distilled water alone is used as the solvent in the preparation of the precursor solution, the generated iron particles are oxidized by iron oxide. However, when ethanol + distilled water is used as a solvent, It can be confirmed that it can be suppressed.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various modifications and equivalent embodiments may be made by those skilled in the art. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.

The iron nanofluid produced by the present invention can be applied to various industrial fields such as a heat transfer fluid for a local district, an industrial heat exchanger, an engine cooling system for a vehicle, and the like, and is excellent in economy due to energy efficiency improvement.

The prepared nanoparticles can be formed by various carbon materials (activated carbon, carbon nanotubes, graphene, fullerene), TiO ₂ It is very useful for developing high-tech materials having various functions.

10: reactor 20: power supply
30: electrode 40: cooling tank
50: circulation pump

Claims (6)

delete delete delete Dissolving iron chloride in a solvent in which ethanol and distilled water are mixed at the same weight ratio to prepare a precursor solution containing iron ions;
A surfactant addition step of adding a surfactant to the precursor solution;
And a liquid phase plasma reaction step of circulating the precursor solution to which the surfactant is added in a cooling bath to generate plasma in the precursor solution for 30 minutes while maintaining the temperature of the precursor solution at 20 to 25 ° C to produce iron nanoparticles In addition,
Wherein the surfactant in the surfactant addition step is a cationic surfactant,
The cationic surfactant is cetyltrimethyl ammonium bromide,
The iron chloride in the precursor solution is 2.0 mM, the conductivity of the precursor solution is 1000 μS / cm,
Wherein the surfactant addition step comprises adding the cationic surfactant to the precursor solution in a molar ratio of 30 to 50% to the iron chloride. 5. The method of claim 4, wherein in the liquid-phase plasma reaction step, the power supplied to the electrode exposed to the precursor solution is a voltage of 250 V, a pulse width of 1 to 5 μs, and a frequency of 30 kHz. Gt; delete

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