KR20160076135A - Organic-inorganic complex, and water-treatment filter comprising the same - Google Patents

Abstract

The present invention relates to an organic-inorganic composite and a water treatment filter including the same. The organic-inorganic composite comprises: a polymer matrix including a polymer resin; and oxidized carbon nano particles dispersed in the polymer matrix and exposed on a surface of the polymer matrix. According to the present invention, a water passing efficiency of the water-treatment filter is increased at the same pressure due to the improvement of hydrophilicity such that a water treatment efficiency is increased, and a flow rate of the water-treatment filter is increased by applying high pressure due to the improvement of mechanical strength such that the water treatment efficiency is increased. Moreover, the wettability of the water-treatment filter is increased due to the improved surface roughness.

Description

[0001] The present invention relates to an organic-inorganic hybrid material and a water treatment filter including the organic-inorganic hybrid material.

The present invention relates to an organic-inorganic hybrid material and a water treatment filter comprising the same, and more particularly, to an organic-inorganic hybrid material which improves the hydrophilicity of a water treatment filter to increase the efficiency of water treatment at the same pressure, The present invention relates to an organic-inorganic hybrid material capable of increasing the water treatment efficiency by increasing the flow rate and improving the wettability by modifying the surface roughness, and a water treatment filter including the same.

In the carbon material industry, demand is expanding in the low carbon green growth related industries such as energy efficiency, environmental protection and advanced water treatment industry, which are the most important issues in recent years. At the same time, It is a fact that is demanded.

As a result, not only the application technology of the carbon material itself but also the surrounding technology base is rapidly developed, the promotion of the fusion of the carbon material is expected to be a great energy source for the material industry and the carbon material as a key role of the new paradigm for the front- It is expected to be a source of high added value creation.

Artificial graphite, graphene, carbon fiber, carbon nanotube, activated carbon, and carbon black, which are known as the so-called six carbon materials, are widely used in industry, but the processes of manufacturing graphene and carbon nanotubes are environmentally and economically There is a difficulty in applying the blend.

It is required to develop a next-generation material which is superior in physical properties than conventional carbon materials such as graphite and carbon black, is economical and eco-friendly, and can be made into a composite material.

On the other hand, efforts have been made to develop a plastic material having a strong mechanical strength based on an extensive application of plastics.

Typically, composites and compounds representing the type of composite material are representative examples. Recently, nanocomposite materials have been actively developed to improve the properties of composite materials. Researches based on graphene and carbon nanotubes among nano-polymer composite materials are typical, but graphene and carbon nanotubes, which are applied as fillers, are expensive and have poor dispersibility. It is required to develop a filling material that can be applied to nano-polymer composite material without any post-treatment such as environment-friendly, economical, excellent dispersibility, and functionalization.

It is an object of the present invention to improve the hydrophilicity of a water treatment filter to increase the water passing efficiency at the same pressure to increase the water treatment efficiency and to increase the mechanical strength to increase the water treatment efficiency by increasing the flow rate, To thereby improve the wettability.

Another object of the present invention is to provide a water treatment filter comprising the above organic / inorganic composite.

According to an embodiment of the present invention, there is provided a polymer matrix comprising a polymer resin, and an organic-inorganic hybrid material dispersed in the polymer matrix and containing carbon nanoparticles exposed on the surface of the polymer matrix.

The polymer resin may be at least one selected from the group consisting of epoxy, polyester (PE), polyurethane (PU), polysulfone (PSF), polyimide (PI), polyamide (PA), polycarbonate Butadiene-styrene copolymer (ABS), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and mixtures thereof.

The carbon oxide nanoparticles are spherical particles of nano-sized oxidized carbon and have a carbon / oxygen element ratio (C / O atomic ratio) of 1 to 9 by X-ray photoelectron spectroscopy (XPS) The greatest oxygen fraction in line element analysis may be observed in CO (OH) bonds.

The carbon oxide nanoparticles may have C-C bonds, C-O (OH) bonds, C-O-C bonds, C═O bonds and O═C-OH bonds observed in X-ray element analysis.

The carbon oxide nanoparticles may have a fraction of C-O (OH) bonds larger than a fraction of C-O-C bonds in X-ray element analysis.

The carbon oxide nanoparticles may have a C-O (OH) bond fraction and a C-O-C bond fraction of 1: 1 to 6: 1 in X-ray element analysis.

The carbon oxide nanoparticles may have a BET specific surface area of 50 to 1500 m ² / g.

The carbon oxide nanoparticles may have a defect peak / carbon peak signal sensitivity ratio (I _D / I _G intensity ratio) of 0.004 to 0.7 by Raman analysis.

The carbon oxide nanoparticles may have a particle size of 1 to 3000 nm and an aspect ratio of 0.8 to 1.2.

The organic / inorganic hybrid material may include 0.01 to 5 parts by weight of the carbon oxide nanoparticles relative to 100 parts by weight of the polymer matrix.

The organic-inorganic hybrid material may have a surface roughness of 5 to 300 nm formed by the carbon oxide nanoparticles exposed on the surface.

The carbon oxide nanoparticles may be exposed to the surface of the polymer matrix in an amount of 20 to 80% by number based on the total amount of the carbon oxide nanoparticles.

The organic-inorganic hybrid material may include first micropores having a diameter of 1 to 100 nm and second micropores having a diameter of 1 to 100 탆.

According to another embodiment of the present invention, there is provided a water treatment filter including the organic-inorganic hybrid material.

The water treatment filter may further include a layer selected from the group consisting of a support, a reverse osmosis membrane (RO), a nanofiltration membrane (NF), an ultrafiltration membrane (UF), a microfiltration membrane (MF), and a combination thereof.

The water treatment filter according to the present invention has improved hydrophilicity and increases the water passing efficiency at the same pressure, thereby increasing the water treatment efficiency, increasing the mechanical strength and applying the high pressure, increasing the water flow rate, increasing the water treatment efficiency, And the wettability is improved.

1 is a graph showing the results of infrared spectroscopic analysis of oxidized carbon nano-particles (OCN) prepared in Production Example 1. FIG.
2 and 3 are graphs showing the results of X-ray photoelectron spectroscopy (XPS) of the carbon oxide nanoparticles prepared in Preparation Example 1 and the commercially available graphene oxide.
4 and 5 are SEM photographs of the oxidized carbon nano-particles (OCN) prepared in Preparation Example 1, and magnifications of 1 nm and 1.00 μm, respectively.
6 is a graph showing the results of Raman analysis of oxidized carbon nano-particles (OCN) prepared in Production Example 1. FIG.
Figs. 7 and 8 are graphs showing the mechanical strengths of the separator prepared in Production Example 3. Fig.
9 is a photograph of the separation membrane produced in Production Example 4, observed with a scanning electron microscope (SEM).
10 is a graph showing moisture permeability of the separation membrane produced in Production Example 3. FIG.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The term nanorang, as used herein, refers to a nanoscale and includes a size of less than 1 micron.

The carbon oxide nanoparticles according to an embodiment of the present invention are spherical particles of nano-sized oxidized carbon.

Therefore, the carbon oxide nanoparticles are different from the oxidized graphene, and the oxidized graphene refers to an oxide of graphene, which is a material having a two-dimensional planar structure in which carbon atoms are connected in a honeycomb-like hexagonal shape.

The carbon oxide nanoparticles may have a particle size of 1 to 3000 nm, preferably 10 to 600 nm. When the size of the carbon oxide nanoparticles is within the above range, dispersion is advantageous and the contact area with the organic material is wide due to the large specific surface area, which is advantageous for improving the mechanical strength.

The carbon oxide nanoparticles may be spherical particles having an aspect ratio of 0.8 to 1.2 and more specifically 0.9 to 1.1. The carbon oxide nanoparticles have a spherical shape when manufactured by the method of manufacturing carbon nanoparticles of the present invention, and thus have the same aspect ratio. In addition, the carbon oxide nanoparticles differ from the graphene oxide in that the aspect ratio of the oxidized graphene exceeds 1.1.

The carbon oxide nanoparticles have a C / O atomic ratio of 1 to 9, preferably 2 to 9, by X-ray photoelectron spectroscopy (XPS). When the carbon / oxygen element ratio is within the above range, it is easy to disperse in an organic solvent such as n-methyl pyrrolidone (NMP), and thus it is suitable for the production of an organic-inorganic hybrid material.

The carbon nanoparticles were found to have CC bonds, CO (OH) bonds, COC bonds, C═O bonds and O═C-OH bonds in the X-ray elemental analysis, ) Bonds. On the other hand, in the case of the graphene oxide, CC bond, CO (OH) bond, COC bond, C═O bond and O═C-OH bond were observed in X-ray element analysis, And is different from the above-mentioned carbon oxide nanoparticles.

Specifically, the carbon oxide nanoparticles may have a fraction of CO (OH) bond and a fraction of COC bond in an X-ray element analysis of 1: 1 to 6: 1, preferably 2: 1 to 4: 1 . When the fraction of C-O (OH) bond and the fraction of C-O-C bond are within the above range, it is easy to disperse in an organic solvent such as n-methylpyrrolidone (NMP).

The carbon oxide nanoparticles may have a BET specific surface area of 50 to 1500 m ² / g, and preferably 100 to 700 m ² / g. When the BET specific surface area of the carbon oxide nanoparticles is within the above range, the viscosity increases with the content of the carbon nano-particles when dispersed in an organic solvent or the like for the production of the organic-inorganic hybrid composite. Suitable.

The carbon oxide nanoparticles may have a defect peak / carbon peak signal sensitivity ratio (I _D / I _G intensity ratio) by Raman analysis of 0.004 to 1, preferably 0.01 to 0.5. When the defect peak / carbon peak signal sensitivity ratio is within the above range, compatibility with an organic solvent such as NMP is suitable and includes a suitable chemical group capable of interacting with an organic material when the organic-inorganic hybrid material is prepared.

According to another embodiment of the present invention, there is provided a method for preparing carbon oxide nanoparticles, comprising the steps of preparing a raw material solution by dissolving a carbon precursor in a solvent, adding an ammonium chloride catalyst to the raw material solution, .

The carbon precursor may be any one selected from the group consisting of glucose, fructose, starch, cellulose, and mixtures thereof, preferably glucose.

The solvent may be water or ethylene glycol.

The carbon precursor may be dissolved in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the solvent. When the content of the carbon precursor is less than 0.1 parts by weight based on 100 parts by weight of the solvent, the amount of the synthesized carbon oxide nanoparticles is diluted, which may be undesirable from the viewpoint of productivity. When the amount exceeds 50 parts by weight, And the dissolution of the precursor may not be smooth.

Specifically, the step of reacting is performed in a closed vessel, and the raw material solution into which the catalyst is introduced is heated to 100 to 300 ° C, and the solvent is allowed to react for 1 to 60 minutes so as to have a vapor pressure of 2 to 30 bar have.

If the heating temperature is lower than 100 ° C, the reaction may not be developed. If the heating temperature is higher than 300 ° C, the oxidized chemical functional groups may be reduced to a reduced carbon nanoparticle due to the severe reaction temperature. If the vapor pressure of the solvent is less than 2 bar, the reaction may not be initiated. If the vapor pressure is more than 30 bar, the reaction may be macerated due to severe reaction conditions. If the reaction time is less than 1 minute, the reaction may not be smoothly performed, and the particle formation and yield may be lowered. If the reaction time exceeds 60 minutes, excessive reaction may cause particle enrichment and reduction of chemical form of oxidized form The carbon / oxygen fraction can be changed to the reduced carbon nanoparticles.

The ammonium chloride catalyst may be added after raising the temperature of the raw material solution to 20 to 100 ° C, preferably 40 to 80 ° C. When the ammonium chloride catalyst is heated to the above temperature range and then charged, particles of uniform size can be synthesized.

The catalyst may be added in an amount of 0.001 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the solvent. When the content of the catalyst is less than 0.001 part by weight with respect to 100 parts by weight of the solvent, it is not preferable from the viewpoint of promoting the reaction rate, and when it exceeds 1 part by weight, it is not preferable because it can act as macromolecule and impurities.

The organic-inorganic hybrid material according to another embodiment of the present invention includes a polymer matrix including a polymer resin, and carbon oxide nanoparticles dispersed in the polymer matrix and exposed to the surface of the polymer matrix.

The carbon nano-particles dispersed in the polymer matrix have a larger size than the polymer chains of the polymer resin and act as a first-order strength stretching agent as a filler that is intertwined with the polymer chains. The hydrocarbon nanoparticles dispersed in the polymer matrix, It acts as a secondary strength stretch through the hydrogen bonding of a hydroxy group and a carboxy group. Accordingly, the organic-inorganic hybrid substance has an improved density and a mechanical strength of 10 to 30%.

In addition, the carbon oxide nanoparticles can increase water treatment efficiency by imparting hydrophilicity to the polymer matrix and increasing water passage efficiency at the same pressure. As the carbon oxide nanoparticles have a spherical or three-dimensional shape, they are exposed to the surface of the polymer matrix and protrude to modify the surface roughness of the organic / inorganic hybrid material to improve the wettability. Since the organic-inorganic hybrid material forms a complex with the polymeric resin and the carbon nanocomposite, the mechanical strength can be increased and high pressure can be applied, thereby increasing the water treatment efficiency by increasing the flow rate.

The polymer resin may be at least one selected from the group consisting of epoxy, polyester (PE), polyurethane (PU), polysulfone (PSF), polyimide (PI), polyamide (PA), polycarbonate Butadiene-styrene copolymer (ABS), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and mixtures thereof.

The organic-inorganic hybrid material may include the oxidized carbon nanoparticles in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the polymer matrix. If the content of the carbon oxide nanoparticles is less than 0.01 part by weight based on 100 parts by weight of the polymer matrix, the surface modification effect of the organic-inorganic hybrid material may be insignificant. If the amount is more than 5 parts by weight, the film quality of the water- .

20 to 80% by number of the carbon oxide nanoparticles may be exposed on the surface of the polymer matrix, and preferably 30 to 50% by number of the carbon oxide nanoparticles may be exposed. If the number of carbon nanoparticles exposed on the surface of the polymer matrix is less than 20% by number, it may be difficult to control the degree of wetting due to the surface roughness effect. When the number of carbon nanoparticles is more than 80% by number, The film quality of the water treatment filter using the organic-inorganic hybrid material may be weakened.

Accordingly, the surface roughness formed by the carbon nano-particles exposed on the surface of the organic / inorganic hybrid material may be 5 to 300 nm, and preferably 10 to 200 nm. When the surface roughness of the organic-inorganic hybrid material is less than 5 nm, it may be difficult to control the wetness due to the surface roughness effect. When the surface roughness exceeds 300 nm, the surface of the organic / inorganic hybrid material may become very rough, Can be weakened.

The organic-inorganic hybrid material may include a first micropore having a diameter of 1 to 100 nm and a second micropore having a diameter of 1 to 100 탆. The first micropore having a diameter of 5 to 50 nm and the second micropore having a diameter of 2 to 100 nm, Lt; RTI ID = 0.0 > 50 < / RTI > When the organic-inorganic hybrid material includes first micropores and second micropores having different sizes, nanofiltration can be performed and drainability can be increased through the second micropores, and the diameters of the first micropores If the diameter of the second micropores is less than 1 탆, there may be a problem in the drainage property. If the diameter of the second micropores is less than 1 탆, If it is more than 100 탆, the first microporous layer may be pushed into the second micropores to hardly support the membrane.

The method for producing an organic-inorganic hybrid material according to another embodiment of the present invention includes the steps of preparing a dispersion of carbon nano-particles by dissolving the carbon nano-particles in a solvent, adding a polymer resin to the dispersion of carbon nano- To thereby prepare a polymer dispersion.

The solvent may be selected from the group consisting of N-methyl-2-pyrrolidone, dimethylpyrrolidone, dimethylformamide (DMF), dimethylacetamide ), Dimethyl sulfoxide (DMSO), and mixtures thereof.

The carbon nanoparticle dispersion may be prepared by treating the carbon nanoparticles with ultrasound (Sonics 1500W ultrasonic disperser) at a frequency of 250 to 1500W for 0.5 to 5 hours. When dispersing the carbon oxide nanoparticles in the solvent, it is advantageous to disperse the carbon oxide nanoparticles into a primary particle state when ultrasonic waves are dispersed.

The carbon oxide nanoparticles may be dissolved in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solvent. When the carbon nano-particles are dissolved in an amount of less than 0.01 part by weight based on 100 parts by weight of the solvent, improvement of the mechanical strength of the organic / inorganic hybrid material may be insignificant. When the carbon nanoparticles are dissolved in an amount exceeding 10 parts by weight, The viscosity of the composite can be a problem.

The polymer resin may be dissolved in an amount of 1 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the solvent. When the polymer resin is dissolved in an amount of less than 1 part by weight based on 100 parts by weight of the solvent, there may be a problem in processability when the organic / inorganic hybrid material is formed into a film or a molded product, and there is a problem in workability if it is dissolved in an amount exceeding 80 parts by weight .

The organic / inorganic hybrid material may be produced in various forms such as films according to generally known methods. For example, the organic / inorganic hybrid material may be put into a Teflon mold and dried to form a film. In addition to the direct molding, a spin coating, a spray coating, a slit die coating, a floor coating, a roll coating, And the like.

As described above, the organic-inorganic hybrid material prepared in the form of a film may be formed to a thickness of 0.1 to 100 탆 and may be used alone or in a layer-by-layer manner.

The organic-inorganic hybrid material may be produced in the form of a film or a three-dimensional structure by a method such as injection molding or extrusion through a calender.

The water treatment filter according to another embodiment of the present invention includes the organic-inorganic hybrid material.

The water treatment filter is selected from the group consisting of a support, a reverse osmosis membrane (RO), a nanofiltration membrane (NF), an ultrafiltration membrane (UF), a microfiltration membrane (MF) And may further include any one of the layers.

The support material is not particularly limited as long as it is a material which is not soluble in the solvent used for producing the organic / inorganic hybrid material, and polyester, polypropylene, or woven fabric can be used.

The water treatment filter may further include various layers such as a reverse osmosis membrane (RO), a nanofiltration membrane (NF), an ultrafiltration membrane (UF), and a microfiltration membrane (MF), which are generally used in the water treatment filter.

The water treatment filter can be applied to both symmetric and asymmetric separation membranes and can be applied to conventional modules such as an external pressure type, an immersion type, a flat plate type, a spiral type, and a hollow fiber type which are conventionally used for water treatment.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example ]

( Manufacturing example  1: Preparation of carbon oxide nanoparticles)

Glucose was dissolved in 2.5 parts by weight of 100 parts by weight of water. The raw material solution thus prepared was placed in a sealed pressure vessel and heated to 80 ° C. Ammonium chloride was added to the raw material solution in an amount of 0.001 part by weight, and the mixture was heated to 160 캜 at a rate of 2 캜 for 30 minutes. The water exhibited a vapor pressure of 8 bar in the sealed pressure vessel according to the temperature elevation temperature.

After completion of the reaction, the reaction solution was put into a centrifuge and rotated at 5,000 rpm for 30 minutes to separate and clean the carbon oxide nanoparticles. This process was repeated three times and then vacuum dried at 40 DEG C to obtain a solid phase powder.

( Manufacturing example  2: Preparation of organic / inorganic hybrid)

0.5 parts by weight of the carbon oxide nanoparticles prepared in Preparation Example 1 were dispersed by ultrasonic treatment (Sonics 1500W) in an NMP solvent for 20 minutes. 9.5 parts by weight of polysulfone (182443 Aldrich, polysulfone, average Mn ~ 22,000 g / mol by MO, beads) was added to 100 parts by weight of the solvent to dissolve the organic solvent dispersion.

( Manufacturing example  3: Manufacturing 1 )

The organic-inorganic hybrid material dispersion prepared in Preparation Example 2 was slot-die-coated on a supporting nonwoven fabric to prepare a separation membrane having a thickness of 3 탆. At this time, the separation membrane contained the carbon oxide nanoparticles in an amount of 0 wt%, 0.5 wt%, 1 wt%, 2 wt%, and 3 wt%, respectively, based on the total weight of the separation membrane.

( Manufacturing example  4: Manufacturing 2 )

The organic-inorganic hybrid material dispersion prepared in Preparation Example 2 was slot-die-coated on a supporting nonwoven fabric to prepare a separation membrane having a thickness of 3 탆. At this time, using the oxidized carbon nanoparticles having particle sizes of 33 nm, 70 nm and 163 nm, the separation membrane contained 0 wt%, 0.5 wt%, 1 wt%, 2 wt% By weight and 3% by weight.

[ Experimental Example  1: Characterization of carbon oxide nanoparticles]

( Experimental Example  1-1: Infrared spectroscopic analysis of carbon oxide nanoparticles)

Oxidized carbon nano-particles (OCN) and commercially available oxidized graphene (Grapheneol GO bucky paper) prepared in Preparation Example 1 were analyzed with an infrared spectrometer (product of Bruker Vertex 70) The results are shown in Fig.

FIG. 1 is a spectrum measured from 500 to 4000 by infrared spectroscopy. The red solid line is the spectrum of the carbon oxide nanoparticles, and the solid black line is the spectrum of the oxidized graphene. As a representative chemical functional group, a hydroxy group appearing as a carboxyl group having a wavenumber of about 1700 and a wide band having a wavenumber of 3200 to 3600 was observed through infrared spectroscopic analysis.

1, the carbon oxide nanoparticles are spherical particles having a diameter ranging from 1 nm to 500 μm and contain oxygen in an amount of 10 atomic% or more. The spherical carbon nanoparticles have a carboxyl group (-COOH ), A hydroxyl group (-OH), an epoxy group (-O-), and the like.

( Experimental Example  1-2: X-ray element analysis of carbon oxide nanoparticles)

X-ray photoelectron spectroscopy (XPS) was performed on the oxidized carbon nanoparticles (OCN) prepared in Preparation Example 1 and commercially available oxidized graphene (Grapheneol GO bucky paper) And the results are shown in FIGS. 2 and 3, respectively.

2 and 3, it can be seen that the carbon oxide nanoparticles and the oxidized graphene have a CC bond, a CO (OH) bond, a COC bond, a C═O bond and an O═C-OH bond , The fraction of CO (OH) bonds in the case of the oxidized carbon nanoparticles is larger than that of COC bonds but the fraction of COC bonds in the case of the oxidized grains is larger than the fraction of CO (OH) bonds.

( Experimental Example  1-3: Scanning electron microscope observation of carbon nanoparticles)

The oxidized carbon nanoparticles (OCN) prepared in Preparation Example 1 were observed with a scanning electron microscope (SEM). The results are shown in FIGS. 4 and 5.

Referring to FIGS. 4 and 5, the carbon oxide nanoparticles are nano-sized spherical particles having a particle size of 1 to 3000 nm and an aspect ratio of 0.9 to 1.1.

( Experimental Example  1-4: Scanning electron microscope observation of carbon oxide nanoparticles)

Raman analysis of the oxidized carbon nano-particles (OCN) prepared in Preparation Example 1 was performed, and the results are shown in FIG.

Referring to FIG. 6, it can be seen that the carbon nanoparticles have a defect peak / carbon peak signal sensitivity ratio (I _D / I _G intensity ratio) of 0.004 to 0.7 by Raman analysis.

[ Experimental Example  2: Characterization of organic / inorganic composite]

( Experimental Example  2-1: Measurement of mechanical strength)

For the separation membrane prepared in Preparation Example 3, a specimen was taken with a dog-bone specimen for measurement of mechanical strength in the form of a film having a thickness of 3 to 5 탆, and the specimen was mechanically measured with a universal testing machine (UTM) The tensile strength was measured.

Figs. 7 and 8 are graphs showing the mechanical strengths of the separator prepared in Production Example 3. Fig.

7, the black line represents the mechanical strength of the pure polysulfone film, and the red line, the blue line, the green line, and the pink line represent 0.5 wt%, 1 wt%, and 1 wt%, respectively, of the oxidized carbon nanoparticles relative to the total weight of the organic- %, 2 wt% and 3 wt%, respectively.

7 and 8, the pure polysulfone film shows a strain of 27 MPa at 4 mm / mm, and the separation membrane containing the oxidized carbon nanoparticles (OCN) has a strain of 38 MPa And the mechanical strength of the separation membrane containing the carbon oxide nanoparticles is improved by up to 40%.

( Experimental Example  2-2: Contact angle  Measure)

The surface of the separation membrane prepared in Preparation Example 4 was observed with a scanning electron microscope (SEM), and the results are shown in FIG.

Referring to FIG. 9, it can be seen that the carbon nanoparticles are exposed on the surface of the separation membrane.

On the other hand, the contact angle refers to the angle formed when the liquid equilibrates thermodynamically on the solid surface. The contact angle can be measured by the sessil drop method as a measure of the wettability of the solid surface.

Distilled water was dropped on the surface of the separation membrane prepared in Preparation Example 4 to measure the contact angle. The results are shown in Table 1 below.

Size of carbon oxide nanoparticles (nm) Content of carbon oxide nanoparticles (% by weight) 0 wt% 1 wt% 2 wt% 3 wt% Contact angle (degrees) 33nm 90 83 82 80 70 nm 90 84 83 82 163 nm 90 86 85 84

Referring to Table 1, it can be seen that the smaller the particle size of the carbon oxide nanoparticles is, the more the wettability is improved due to the broad specific surface area effect. In addition, the wettability between similar membrane materials can be modified due to the geometric structure when the surface roughness is finer than that of the flat membrane. When the carbon nanotubes contain 1 wt% of the carbon oxide nanoparticles, 33 nm particles and 70 nm particles And 8% and 7%, respectively, and that the 163 nm particles exhibited an increase in wettability of 4%, indicating that the above-mentioned carbon oxide nanoparticles were exposed to the surface to increase the wettability. .

( Experimental Example  2-3: Moisture permeability  Measure)

On both sides of the separation membrane prepared in Preparation Example 3, a 125 mesh Teflon support layer was placed on both sides and fixed to a column unit having an inner diameter of 0.7 탆. The upper part of the column was filled with 20 mL of distilled water, and compressed air was kept constant at 1 atm through a regulator to give positive pressure. The weight of the distilled water discharged for 5 minutes was measured and converted into water vapor permeability (L / m ² / hr, 1 atm). The results are shown in FIG.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (15)

A polymer matrix containing a polymer resin, and
The carbon nanoparticles dispersed in the polymer matrix and exposed to the surface of the polymer matrix
/ RTI > The method according to claim 1,
The polymer resin may be at least one selected from the group consisting of epoxy, polyester (PE), polyurethane (PU), polysulfone (PSF), polyimide (PI), polyamide (PA), polycarbonate Wherein the polymer is any one selected from the group consisting of nitrile-butadiene-styrene copolymer (ABS), polyvinylidone fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose and mixtures thereof. The method according to claim 1,
The carbon oxide nanoparticles are spherical particles of nano-sized oxidized carbon,
The carbon / oxygen atom ratio (C / O atomic ratio) by X-ray photoelectron spectroscopy (XPS) is 1 to 9,
Wherein the largest oxygen fraction in the X-ray elemental analysis is observed in the CO (OH) bond. The method of claim 3,
Wherein the carbon nano-particles have a CC bond, a CO (OH) bond, a COC bond, a C═O bond and an O═C-OH bond in the X-ray element analysis. The method of claim 3,
Wherein the carbon oxide nanoparticles have a fraction of CO (OH) bonds greater than a fraction of COC bonds in an X-ray element analysis. The method of claim 3,
Wherein the carbon oxide nanoparticles have a fraction of CO (OH) bond and a fraction of COC bond in an X-ray element analysis of 1: 1 to 6: 1. The method of claim 3,
Wherein said carbon oxide nanoparticles have a BET specific surface area of 50 to 1500 m ² / g. The method of claim 3,
Wherein the carbon oxide nanoparticles have a defect peak / carbon peak signal sensitivity ratio (I _D / I _G intensity ratio) of 0.004 to 0.7 as determined by Raman analysis. The method of claim 3,
The carbon oxide nanoparticles have a particle size of 1 to 3000 nm,
Wherein the aspect ratio is 0.8 to 1.2. The method according to claim 1,
Wherein the organic / inorganic hybrid material comprises 0.01 to 5 parts by weight of the oxidized carbon nanoparticles relative to 100 parts by weight of the polymer matrix. The method according to claim 1,
Wherein the organic / inorganic hybrid material has a surface roughness of 5 to 300 nm formed by the carbon nano-particles exposed on the surface. The method according to claim 1,
Wherein 20 to 80% by number of the carbon oxide nanoparticles are exposed to the surface of the polymer matrix. The method according to claim 1,
Wherein the organic / inorganic hybrid material has first micropores having a diameter of 1 to 100 nm and
And second micropores having a diameter of 1 to 100 占 퐉. A water treatment filter comprising the organic / inorganic composite according to claim 1. 15. The method of claim 14,
Wherein the water treatment filter further comprises any one selected from the group consisting of a support, a reverse osmosis membrane (RO), a nanofiltration membrane (NF), an ultrafiltration membrane (UF), a microfiltration membrane (MF) .

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