KR101583752B1

KR101583752B1 - Method of high-speed dispersing beta-type capacious nanoparticles within epoxy resin

Info

Publication number: KR101583752B1
Application number: KR1020140042303A
Authority: KR
Inventors: 박종만; 권동준; 왕작가; 장기욱; 정삼태; 김제준
Original assignee: 경상대학교 산학협력단; 주식회사티비카본
Priority date: 2014-04-09
Filing date: 2014-04-09
Publication date: 2016-01-08
Also published as: KR20150117057A

Abstract

The present invention relates to a method for dispersing nanoparticles in a polymer resin, and more particularly, to a high-speed dispersing method of a high-capacity beta-type nanoparticle in an epoxy resin capable of dispersing a high-capacity nanoparticle added in an epoxy resin at high speed will be.
The high-speed dispersion method of a high-capacity beta-type nanoparticle in the epoxy resin has an elliptical flow when the epoxy mixture containing the beta-type nanoparticles is stirred, and when ultrasonic waves are applied to the upper end of the elliptical flow, The particles can be dispersed at high speed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high-speed dispersing method of high-speed dispersing beta-type capacitive nanoparticles in an epoxy resin,

The present invention relates to a method for dispersing nanoparticles in a polymer resin, and more specifically, to a method for dispersing a high-capacity beta-type nanoparticles added in an epoxy resin at a high speed, .

Nanoparticles are particles with diameters ranging from 1 nm to 100 nm. They have a surface area that is larger than the volume of particles, and thus exhibit different electrical, optical, and magnetic properties from those of bulk materials.

By adding nanoparticles having various characteristics to the polymer resin, nanocomposites having various functions such as mechanical, chemical and optical properties can be produced.

However, such nanoparticles have a tendency to form agglomerates because of their large cohesion force between the particles, which results in the problem that the nanoparticles can not exhibit the physical properties of the nanoparticles as the particles aggregate.

Recently, as the technology related to composite materials with nanoparticles added has been developed, there has been a plan to improve the problems of nanoparticles and to have a high dispersibility in various polymer resins.

Conventionally, in order to improve the dispersion of nanoparticles in the polymer resin, agglomeration of the nanoparticles by stirring using an agitator has been tried to be prevented. However, when the nanoparticles are mixed, There is a problem.

In addition, Korean Patent Laid-Open No. 10-2010-111454, for example, has proposed the effect of simultaneously performing stirring and ultrasonic treatment to improve the dispersion of nanoparticles in polymer resin, but it takes a long time to disperse the nanoparticles, Is limited.

As a result of various efforts to improve the dispersibility of the beta-type nanoparticles in the epoxy resin, the present inventors have found that an epoxy mixture containing the beta-type nanoparticles is placed in an elliptical flow, The present inventors completed the present invention by confirming that a high-capacity beta-type nanoparticle has a high dispersibility at high speed when an ultrasonic wave is applied.

Accordingly, it is an object of the present invention to provide a high-speed dispersing method of a large amount of beta-type nanoparticles in an epoxy resin capable of dispersing a high-capacity added beta-type nanoparticles at high speed.

In order to solve the above-mentioned object, the present invention provides a method of manufacturing a composite material, comprising: adding 400 to 600 g of an epoxy resin and 50 to 200 g of a beta type nanoparticle to a mixing container; placing the stirrer in the mixing container so that the epoxy mixture has an elliptical flow And stirring the mixture at a speed of 400 to 600 rpm for 1 to 3 hours, wherein ultrasonic waves are applied to the upper part of the elliptical flow during the stirring, thereby providing a high-speed dispersion method of a high-capacity beta type nanoparticle in an epoxy resin .

The dispersion method of the present invention allows high-capacity and high-dispersibility nanoparticles of high capacity to be added in a polymer resin. Accordingly, the composite material produced by the dispersing method of the present invention has properties of high bending, compression, and tensile strength.

1 is a schematic view showing a state where an agitator is positioned such that an epoxy mixture has an elliptical flow according to an embodiment of the present invention;
Figure 2 is a schematic view showing a state in which a mixing vessel is positioned such that an epoxy mixture has an elliptical flow according to another embodiment of the present invention;
FIG. 3 illustrates a process of dispersing the aggregated nanoparticles according to the ultrasonic treatment in the epoxy mixture according to the present invention.
4 is a graph showing flexural strength results of an epoxy mixture prepared according to the present invention and a comparative epoxy mixture prepared by a conventional ultrasonic treatment.
5 is a graph showing compressive strength results of an epoxy mixture prepared according to the present invention and a comparative epoxy mixture prepared by a conventional ultrasonic treatment.
6 is a graph showing tensile strength results of an epoxy mixture prepared according to the present invention and a comparative epoxy mixture prepared by a conventional ultrasonic treatment.
Fig. 7 is an image showing a fractured section of a material made from an epoxy mixture according to an embodiment of the present invention. Fig.
Fig. 8 is an image showing the fracture cross-section of a material made of a comparative example epoxy mixture manufactured by a conventional ultrasonic treatment method. Fig.

Hereinafter, the present invention will be described in detail.

In the present invention, it is possible to disperse a large amount of the beta-type nanoparticles added in the epoxy resin at a high speed, and to prevent the phenomenon that the powder is blown by the mixing of the beta-type nano-particles and the phenomenon of floating on the epoxy resin, We propose a rapid dispersion method of beta-type nanoparticles.

The present invention provides a method for dispersing a large amount of beta-type nanoparticles in an epoxy resin, comprising the steps of: adding an epoxy resin and beta-type nanoparticles to a mixing vessel;

Placing and stirring the stirrer in the mixing vessel such that the epoxy mixture has an elliptical flow

And applying ultrasound to the upper end of the elliptical flow during the stirring.

Describing each step in detail,

First, an epoxy resin and a beta type nanoparticle are added into a mixing vessel.

The epoxy resin refers to a resin material having two or more epoxy groups in a molecule and a thermosetting resin produced by polymerization of an epoxy group. The epoxy resin is characterized by strong adhesion, high chemical / thermal stability, high strength, impact resistance, and abrasion resistance.

The epoxy resin used in the present invention is not limited, and those generally well known in this field can be used. Specifically, the epoxy resin may be at least one selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a Novolac Type Fpoxy, a glycidyl ester type epoxy resin, a Brominated Epoxy, a halogenated epoxy resin, Resins, etc. These epoxy resins may be used singly or in combination of two or more.

Nanoparticles are micrometer-sized particles having a diameter of 1 nm to 100 nm. When the nanoparticles are added to a polymer resin, composite materials having various and complex functions are formed.

The nanoparticles may be variously divided into metal, magnetic, organic, semiconductor, polymer nanoparticles and the like, and it is preferable to select nanoparticles suitable for the desired physical properties depending on the case. Nanoparticles are classified into hexagonal and cubic according to a crystal axis, and hexagonal and hexagonal are generally classified into an alpha (alpha) type and a cubic (Cubic) type beta Type).

In one embodiment of the present invention, by adding silicon carbide (nano-particles), more preferably beta-type silicon carbide, into the epoxy resin and dispersing it, the mechanical properties such as the strength and stiffness of the epoxy mixture are improved .

Silicon Carbide (SiC) is a material in which silicon (Si) and carbon (C) are bonded at a ratio of 1: 1 and has excellent electrical, mechanical, thermal and mechanical stability.

In one embodiment of the present invention, beta-type hydrocarbon (SiC) nanoparticles are added to an epoxy resin to prepare an epoxy mixture. In this case, 50 to 200 g of beta-type nanoparticles per 400 to 600 g of epoxy resin are added to disperse .

When the amount of the beta-type nanoparticles is less than 50 g, the amount of the beta-type nanoparticles to be added is insufficient, so that the effect of improving the physical properties of the epoxy resin due to the addition of the nanoparticles can not be expected. And the problem of floating or aggregation occurs.

Next, an agitator is placed and stirred so that the epoxy mixture containing the beta-type nanoparticles has an elliptical flow in the mixing vessel.

In the present invention, as shown in FIGS. 1 and 2, the epoxy mixture has an elliptical flow by locating and stirring the mixing vessel containing the epoxy mixture or the stirrer at a certain angle from the ground.

More specifically, as shown in FIG. 1, in an embodiment of the present invention, the stirrer 30 is placed in the mixing vessel 10 so as to have an inclination of 15 to 30 degrees from the vertical direction of the paper, , Such that the epoxy mixture 20 has an elliptical flow.

The stirrer 30 is composed of a swinging blade 32 formed at an angle of 30 to 60 ° with the swinging 31 on one side of the swinging 31 and the swinging 31.

The stirrer 30 is placed in the mixing vessel 10 so that it has an inclination of 15 to 30 degrees from the vertical direction of the paper surface and then agitated so that the rotary vane 32 of the stirrer 30 is mixed with the epoxy mixture 20) It generates a whirl on the surface. As a result, the epoxy mixture 20 has an elliptical flow, and the added nanoparticles are dispersed.

Further, as shown in FIG. 2, in another embodiment of the present invention, a mixing vessel containing an epoxy mixture is placed and agitated at a constant slope from the ground so as to have an elliptical flow in the epoxy mixture.

2, the mixing vessel 10 containing the epoxy mixture 20 is positioned to have an inclination of 15 to 30 degrees from the ground, and stirring is performed through the stirrer 30, The rotor blades 32 of the rotor 30 generate a whirl on the surface of the epoxy mixture 20. As a result, the epoxy mixture 20 has an elliptical flow, and the added nanoparticles are dispersed.

As shown in FIGS. 1 and 2, the epoxy mixture 20 is stirred using an agitator 30, so that the epoxy mixture 20 has an elliptical flow, The nanoparticles are dispersed. At this time, it is preferable that the stirrer located in the epoxy mixture 20 is stirred for 1 to 3 hours at a speed of 400 to 600 rpm.

Particularly, in the present invention, the step of applying ultrasonic waves to the upper end of the elliptical flow of the epoxy mixture during the stirring step is simultaneously performed to disperse the beta-type nano particles at a high speed, Ultrasonic waves are applied and stirring and ultrasonic treatment are simultaneously carried out to generate strong stirring.

Ultrasonic processing creates bubbles within the epoxy mixture due to the energization of the ultrasonic waves, causing growth and explosive collapse. By energizing such an ultrasonic wave into the epoxy mixture, the expansion cycle exerts a negative pressure on the liquid, pulling the epoxy mixture molecules away from each other. Further, the growth and strong collapse of the bubbles cause a strong stirring action of the epoxy mixture, and the ultrasonic wave energized in the epoxy mixture generates asymmetric high velocity jet of the epoxy mixture, so that the effect of stirring the epoxy mixture further I have.

The upper portion of the elliptical flow refers to a portion of the elliptical flow having a certain distance from the stirrer located in the epoxy mixture, as shown in Figs. 1 and 2, in which the flow is large.

This is because when the mixing vessel 10 containing the epoxy mixture or the stirrer 30 is positioned at a certain angle from the ground and then the stirring operation of the stirrer 30 is performed, And is rotated at a predetermined angle from the ground. The epoxy mixture 20 thus has a constantly oblique flow of ellipses. Here, the portion of the elliptical flow that is the farthest from the surface of the elliptical flow by the stirrer 30 is formed with the largest flow, which is referred to as the upper portion 100 of the elliptical flow.

Accordingly, in the present invention, the ultrasonic wave 40 is applied to the upper part 100 of the elliptic flow in which the flow of the epoxy mixture is most generated in the mixing vessel, and the stirring and the ultrasonic treatment are simultaneously performed, The nanoparticles can be dispersed evenly at high speed.

FIG. 3 shows a process of dispersing the aggregated beta-type nanoparticles in the epoxy mixture according to the present invention by ultrasonic treatment.

As shown in FIG. 3 (a), when ultrasonic waves are applied to an epoxy resin floating and flocculating the beta-type nanoparticles, the aggregated beta-type nanoparticles start dispersing as shown in FIG. 3 (b) . At this time, if the ultrasonic wave is continuously applied for a predetermined period of time, as shown in FIG. 3 (c), the beta type nanoparticles are visibly dispersed and mixed with the epoxy resin.

The step of applying the ultrasonic waves is not limited, but is preferably performed under the condition of a speed cycle of 50 to 70% in amplitude, 40 to 60 W in output size, and 0.1 to 1 s.

This is because, if the intensity of the energizing ultrasonic energy is small, the dispersion of the nanoparticles is not affected, and if the intensity of the ultrasonic energy is too high, the properties of the epoxy mixture are lowered.

As described above, the high-speed dispersion method of a high-capacity beta-type nanoparticle in an epoxy resin according to the present invention allows an elliptical flow when the epoxy mixture is stirred, and an ultrasonic treatment is applied to the upper end of the elliptical flow, It is possible to disperse the high-capacity nanoparticles at high speed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example: Beta type SiC Manufacture of epoxy mixture containing nanoparticles

An example epoxy mixture containing a high-dose of beta type SiC nanoparticles was prepared by the following procedure.

1. Add 100 g of beta type SiC nanoparticles having a size of 55 nm to 500 g of epoxy resin in a mixing vessel.

2. Place the mixing vessel at an angle of 30 degrees from the ground.

3. Place the agitator in the mixing vessel with a four-blade rotary blade at an angle of 45 degrees with the support and stir at 500 rpm for 2 hours.

4. An ultrasonic wave applying device was placed at the upper end of the elliptical flow formed at the stirring stage to conduct simultaneously ultrasonic waves at an output size of 50 W, a 60% output size, and a 1 s cycle condition to obtain an epoxy mixture containing a beta SiC nanoparticle .

Comparative Example : Ultrasonic Beta type SiC Manufacture of epoxy mixture containing nanoparticles

A comparative epoxy mixture containing a high-dose of beta-SiC nanoparticles was prepared by the same procedure as described below.

2. Place the ultrasonic applicator in the epoxy mixture and apply ultrasonic waves for 3 days at an output size of 50W, a 60% output size, and a 1 s cycle condition to produce a comparative epoxy mixture containing beta SiC nanoparticles.

Experimental Example 1: Flexural strength evaluation

The flexural strength of the comparative epoxy mixture prepared by the conventional ultrasonic treatment and the flexural strength of the epoxy mixture prepared in the example of the present invention were evaluated. The results are shown in FIG.

As shown in FIG. 4, it can be seen that the epoxy mixture prepared in the manufacturing method according to the present invention has higher flexural strength than the comparative epoxy mixture prepared by the conventional ultrasonic treatment. It can be seen that, in the case of the epoxy mixture of the example, the dispersibility of the added beta type SiC nanoparticles is better than that of the comparative example epoxy mixture, and the physical properties are improved.

Experimental Example 2: Evaluation of compressive strength

The compressive strength of the epoxy mixture prepared in the preparation process according to the present invention and the epoxy mixture prepared in the conventional ultrasound process were evaluated. The results are shown in FIG.

As shown in FIG. 5, it can be seen that the compressive strength of the epoxy mixture of the example prepared by the process according to the present invention is higher than that of the comparative epoxy mixture. It can be seen that the epoxy mixture prepared according to the present invention has a better dispersion of the added beta type SiC nanoparticles than the epoxy mixture prepared by the method of the comparative example, thereby improving the physical properties of the epoxy mixture.

Experimental Example 3: Evaluation of tensile strength

The tensile strength of the epoxy mixture prepared in the preparation process according to the present invention and the epoxy mixture prepared in the conventional ultrasound process were evaluated. The results are shown in FIG.

As shown in FIG. 6, it can be seen that the tensile strength of the epoxy mixture of the example prepared by the production method according to the present invention is higher than the tensile strength of the comparative example epoxy mixture produced by the conventional ultrasonic treatment. This indicates that the dispersibility of the beta type SiC nanoparticles added to the epoxy mixture prepared in the manufacturing method of the present invention is well dispersed, thereby improving the physical properties of the epoxy mixture and improving the tensile strength.

Experimental Example 4: Beta type For the evaluation of nanoparticle dispersion Fracture plane analysis

EXAMPLES Prepared by the Manufacturing Process According to the Present Invention The fracture profiles of the epoxy mixture materials were observed to evaluate the dispersity of the beta-SiC nanoparticles added to the epoxy mixture and the comparative epoxy mixture prepared by the conventional ultrasonic treatment. The results of the dispersion evaluation through the fractured surface are shown in Figs.

Fig. 7 shows an image of a fractured surface of a material made of an epoxy mixture according to an embodiment of the present invention, and Fig. 8 shows an image of a fractured surface of a material made of a comparative epoxy mixture prepared by a conventional ultrasonic treatment to be.

Comparing the fractured surface images of FIGS. 7 and 8, it can be seen that cracks appearing in white in the image are nonuniform in the case of the material made of the comparative example epoxy mixture of FIG. 8, Examples prepared by the manufacturing method In the case of the material made of the epoxy mixture, it is possible to confirm a relatively stable and uniform fracture surface.

Accordingly, it can be confirmed that the beta-SiC nanoparticles added in the case of the epoxy mixture prepared in the production process according to the present invention are uniformly dispersed in comparison with the epoxy mixture in the comparative example.

Mixing vessel: 10 Epoxy mixture: 20
Stirrer: 30 Opposite: 31
Rotating blades: 32 Ultrasound: 40
Upper part of oval flow: 100

Claims

Adding 400 to 600 g of an epoxy resin and 50 to 200 g of a beta type nanoparticle to a mixing vessel,
Placing the mixing vessel at an angle of 15 to 30 DEG from the stirrer or the ground so as to have an inclination of 15 to 30 DEG from the vertical direction of the paper so that the epoxy mixture has an elliptical flow in the mixing vessel, Lt; / RTI > for 1 to 3 hours,
Wherein the elliptical flow is performed while applying ultrasonic waves to the upper end of the elliptic flow which is the farthest from the ground in the elliptic flow during the stirring.

The method of claim 1, wherein the beta-nanoparticles have a size of 40 to 60 nm.

2. The method of claim 1, wherein the agitator has a rotating blade at an angle of 30 to 60 with respect to the transverse direction.

2. The method of claim 1, wherein the ultrasonic wave is applied to the ultrasonic wave at an amplitude of 50 to 70%, an output size of 40 to 60 W, and a speed cycle of 0.1 to 1 s.

delete

The method of any one of claims 1 to 4, wherein the beta type nanoparticles are beta type SiC nanoparticles.