KR101391989B1 - Manufacturing method of basalt-whisker for reinforcement using electro spinning - Google Patents

Abstract

The present invention relates to a manufacturing method of a basalt-whisker for a reinforcing material using electro-spinning: which enables users to easily crush basalt, which is easily being prepared as a raw material and has mechanical strength and a far infrared ray emitting function, into powder with a constant particle diameter using a ball mill; easily manufactures the basalt-whisker for the reinforcing material by adding basalt powder into PVP, and electro-spinning and sintering the mixture; saves the energy by simply manufacturing the basalt-whisker for the reinforcing material; and enables the users to obtain the fibrous basalt-whisker for the reinforcing material with high far infrared ray emission rate and high intensity while remarkably saving energy by the simple manufacturing of the basalt-whisker for the reinforcing material.

Description

 BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a basalt whisker for reinforcement using electrospinning,

The present invention relates to a method of manufacturing a basalt whisker for a reinforcing material by electro spinning, and more particularly, to a method of manufacturing a basalt-based whisker for facilitating the procurement of raw materials and having mechanical strength and far- ) Can be easily and easily pulverized into a powder having a predetermined particle size through a ball-mill grinder. In particular, since basalt powder is added to PVP and electro-spinning and plastic working are performed, It is possible to easily and easily manufacture the basalt whisker for a reinforcing material and to remarkably reduce the energy by using the basalt whisker for the reinforcement. The fibrous reinforcing basalt whisker having a high far- And more particularly, to a method of manufacturing a basalt whisker for a reinforcement using electrospinning .

In general, the second material is added to the single material to improve the mechanical properties and processability of a single material such as plastic or ceramics and to impart various functions to the single material. Wherein the composite material is classified into a fiber-reinforced composite material, a particle-reinforced composite material, or a whisker-reinforced composite material according to the composition and shape of the material to be added.

FRP (fiber reinforced plastics), which is typically known as a composite material as described above, is a plastic-based composite material reinforced with a fiber and exhibits excellent moldability in addition to excellent mechanical properties and plastic corrosion resistance. In recent years, new structural materials and functional materials The application to a wider range of applications is under review.

The plastic-reinforced composite material as described above has an important position in aerospace, defense industry, automobile, industrial field (construction, machinery), and in particular, the composite material in the construction field has strength, corrosion resistance, abrasion resistance, , Insulation, insulation, lighter weight, and aesthetically pleasing appearance, the durability and safety of the facility can be ensured. Therefore, the present invention is utilized in a wide variety of ways depending on the characteristics of the facility.

On the other hand, in the case of the resin used as a binder in the plastic composite material, the resin serves to disperse the force applied to the material by bonding the added reinforcing material and has excellent corrosion resistance and heat resistance, The thermosetting resin may be polyester, epoxy, polyimide or the like. Examples of the thermoplastic resin include polyamide, polyamide, polyamide, Polycarbonate, polybutylene terephthalide, polyether sulfone, polyamide imide, and polyphenylene sulfide.

As the reinforcing material to be added to the plastic composite material, various materials are used. As materials mainly used, inorganic fibers of glass fiber (GF), bronze fiber (BF), carbon fiber (CF) There is aramid fiber (AF).

In addition, the reinforcing material may be divided into three types depending on the type of the reinforcing material added to the plastic-based composite material, and the fibrous reinforcing material can improve the mechanical properties of the composite material, Powder type reinforcing materials have excellent properties in workability, but they have weak mechanical properties.

Meanwhile, in addition to the above-mentioned fiber or powder type reinforcing materials, a whisker-type reinforcing material has been proposed as a companion type complementary thereto, and whisker reinforcing composites using various inorganic materials have been actively developed.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and disadvantages of the prior art, and it is an object of the present invention to provide a method of manufacturing a ball mill, So that it can be easily and easily pulverized into a powder having a predetermined particle size. Especially, it is possible to easily and easily manufacture the basalt whisker for reinforcing materials by electro-spinning and plastic working by adding basalt powder to PVP. A basalt whisker for a reinforcing material, and a basalt whisker for a reinforcing material can be obtained, which can remarkably save energy and can obtain a fibrous basalt whisker for a reinforcing material having a high-intensity high- And a method of manufacturing the same.

In order to accomplish the above object, the present invention provides a method of manufacturing a basalt whisker for a reinforcement using electrospinning,

 PVP (polyvinylpyrrolidone) in an ethanol solution to dissolve;

Milling a basalt gemstone to a relatively small size and then milling it to a predetermined size through a ball-mill grinder;

Mixing the basalt powder pulverized with the predetermined particle size into a mixed solution of an ethanol solution and water to uniformly disperse the basalt powder;

Mixing the basalt dispersion liquid into the PVP solution and uniformly mixing the same;

Mixing the mixed basalt / PVP mixed solution into an electro-spinning machine to spin the mixture;

Recovering the spinning basalt whisker material from the dust collector and drying the dried basalt whisker material at a constant temperature in a drier, and heat treating the dried basalt whisker material in an air atmosphere in a baking furnace to produce a basalt whisker Wherein the method comprises the steps of: preparing a basalt whisker for a reinforcing material by electrospinning;

Also, the present invention is characterized in that 60 to 70 wt% of an ethanol solution is added to and dissolved in 30 to 40 wt% of PVP (polyvinylpyrrolidone).

In addition, in the present invention, the basalt pulverized in the small size is pulverized in a ball-mill pulverizer to a particle size of 0.1 to 10 μm, and the pulverization time of the basalt pulverizer through the ball- 30 to 50 or 44 hours.

Also, the present invention is characterized in that the mixing ratio of the ethanol solution for dispersing the pulverized basalt powder to water is 1: 1.

In addition, in the present invention, it is preferable that the weight ratio of the basalt mixed with the PVP solution to the PVP solution is 5 to 30 wt% or 10 wt%

In addition, in the present invention, the mixed basalt / PVP mixed solution is applied to the electrospinner at a rate of 15 μl / min at an applied voltage of 7 kV, and the mixed basalt / PVP mixed solution is injected in a syringe- And 10 cm between the injection injector and the collector for 10 minutes.

Also, the drying temperature of the dried basalt whisker material is 60 to 80 ^° C, and the drying time of the dryer is 4 to 6 hours.

Also, the basalt whisker material is gradually heated at a temperature of 2 to 5 ^° C / min in an air atmosphere in a firing furnace, and is heat-treated at 1200 ^° C, wherein the heat treatment time is 30 to 60 minutes.

According to the method for manufacturing a basalt whisker for a reinforcing material using electrospinning, the basalt having a mechanical strength and a far-infrared radiation function can be easily and easily formed into a uniform particle size through a ball- In particular, since basalt powder is added to PVP and electrospinning and plastic working are performed, it is possible to easily and easily manufacture the basalt whisker for reinforcement, The basalt whiskers can be produced in a simple and simple manner, and energy can be saved remarkably. Thus, it is possible to obtain fibrous basalt whiskers for reinforcing materials having a high far infrared ray emissivity and high strength.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the following claims It will be understood by those skilled in the art that it is readily known.

1 is a flow chart for explaining a method of manufacturing a basalt whisker for a reinforcing material using electrospinning according to the present invention.
2 is a graph showing the particle size distribution of basalt powder pulverized for 21 hours and 44 hours in a ball-mill grinder of the present invention.
Figure 3 is a graph of XRD measurement results of PVP, basalt / PVP and basalt powder.
4A to 4D are electron micrograph (SEM) photographs of basalt crushing powder (10,000x), PVP fiber (2,000x), basalt / PVP fiber (2,000x) and basalt whisker (150x)
5A and 5B are graphs showing the far-infrared emissivity and emissivity power of a basalt whisker for reinforcement using the electrospinning of the present invention, respectively.

Hereinafter, an embodiment of a method for manufacturing a basalt whisker for a reinforcement using electrospinning according to the present invention will be described in detail.

1 is a flow chart for explaining a method of manufacturing a fine needle basalt whisker for a reinforcing material using electrospinning according to the present invention, wherein 60 to 70 wt% of an ethanol solution is added to 30 to 40 wt% of polyvinylpyrrolidone (PVP) To dissolve.

At this time, when the ethanol solution for dissolving the PVP is 60 wt% or less, the PVP is not dissolved properly and the tip of the syringe needle can be clogged during the electrospinning. When the ethanol solution for dissolving the PVP is 70 wt% The PVP dissolved in the PVP is dissolved in the ethanol solution of 60-70 wt% based on 30-40 wt% of the PVP as in the present invention. .

On the other hand, the basalt ore is crushed to a relatively small size, and the crushed basalt mass is milled for 30 to 50 hours at a size of 0.1 to 10 μm through a ball-mill crusher .

 In this case, the particle size distribution of the ground basalt powder pulverized for 21 hours and 44 hours in the ball mill mill is shown in the graph of FIG.

As shown in the graph of FIG. 2, the crushed basalt mass was milled for 21 hours through a ball-mill grinder, and the particle size distribution showed a relatively monodispersed particle size distribution in the range of 0.1 to 10 μm, At this time, the basalt grain size has a mode size of 4.2 μm and a mean size of 4.44 μm.

However, in the case of the particle size distribution after crushing the crushed basalt masses for 44 hours through a ball-mill grinder, the distribution of the polydispersed particles was observed at around 0.1, 3 and 100 μm, The mode size was 3.65 mu m. It can be seen that the particle size was reduced by about 0.6 mu m as compared with the result obtained by grinding for 21 hours. The grinding time was increased to 30 to 50 hours, And the time for milling the pulverized basalt mass through a ball-mill pulverizer is most preferably 44 hours.

The basalt powder pulverized with a particle size of 0.1 to 10 μm as described above is put into a mixed solution in which an ethanol solution and water are mixed at a ratio of 1: 1 to be evenly dispersed. To the PVP solution as described above, The mixing is carried out uniformly so that the weight ratio is 5 to 30 wt% so that the basalt powder pulverized to the particle size of 0.1 to 10 μm can be uniformly mixed with the PVP solution.

Meanwhile, the mixed basalt / PVP mixed solution as described above is injected into an injection injector so as to perform electro-spinning, so that electrospinning is performed. The electro spinning is performed under the conditions of an applied voltage The injection of the basalt / PVP mixed solution was carried out at a rate of 15 μl / min through an injection syringe in the form of a syringe for 10 minutes. At this time, the distance between the injection injector and the dust collector was 10 cm, By spinning the basalt / PVP mixed solution, a resinous basalt / PVP mixed solution is formed from the basalt / PVP fiber.

FIG. 3 is a graph of XRD measurement results of PVP fiber, basalt / PVP fiber and basalt powder, and XRD measurement of the basalt whisker material produced by electro spinning was performed as described above. An XRD pattern of a basalt powder and PVP fiber was also measured. As a result, as shown in FIG. 2, the XRD pattern of the PVP fiber and the basalt / PVP fiber shows a diffraction peak (peak 0 ) at about 2θ of about 16.9 ^° , which is understood as a diffraction due to the spacing between polymers In basalt / PVP fiber, peaks are observed at about 2, 9, 29.6 and 35.1 ^o , which is consistent with the peak positions of relative strengths 1, 2, and 3 of basalt as compared with baseline XRD peaks , And a peak derived from the basalt.

It is understood that the basalt rock / PVP fiber has a small basalt content of 10 wt% and the basalt particles are coated with the polymer, so that the relative intensity of the basalt peak on the XRD is very small and wide.

From the above results, it can be seen that PVP and basalt are mixed in the basalt / PVP fiber obtained by electrospinning the basalt / PVP mixed solution.

The basalt / PVP fiber is recovered in a dust collector and dried in a dryer at a temperature of 60 to 80 ^° C. for 4 to 6 hours. When the drying temperature of the basalt / PVP fiber is 60 ^° C. or less, PVP fiber is shrunk when the drying temperature of the basalt / PVP fiber is 80 ^° C or higher, and the basalt / PVP fiber is shrunk due to the presence of the basalt / PVP fiber. Most preferably, the fibers are dried in a dryer at a temperature of 60-80 ^° C for 4-6 hours as in the present invention.

Subsequently, the dried basalt / PVP fiber was gradually heated at a temperature of 2 to 5 ^° C / min in an air atmosphere in a firing furnace, and heat-treated at 1200 ^° C for 30 to 60 minutes to obtain a high-infrared ray emissivity So that a fibrous basalt whisker for reinforcing materials having high strength can be produced.

FIGS. 4A to 4D are graphs of electron microscopic images (SEM) and EDAX measurement results of the respective samples. FIG. 4A is basalt after 44 hours of milling, FIG. 4B is PVP fiber, FIG. 4C is PVP / And FIG. 4D is an electron micrograph (SEM) of the basalt fiber after firing at 1200 ^o C and an EDAX graph corresponding to each of them. As can be seen from the electron microscope photograph (SEM), regardless of whether or not basalt is added As can be seen from the graph of the EDAX analysis, the addition of the basalt powder resulted in the formation of Si, which is the main component of the basalt rock, And Al were detected in the fibrous samples. Therefore, it can be confirmed that the PVP fiber containing the basalt was produced.

On the other hand, as shown in FIG. 4D, it was confirmed that the basalt whisker material after firing at a temperature of 1200 DEG C produced whisker-type particles having a fiber structure disappeared and elongated and having a thickness of several tens of micrometers, (SEM) photographs of the present invention.

5A and 5B are graphs showing the far-infrared emissivity and emissivity power of the basalt whisker for reinforcement using the electrospinning of the present invention, respectively. The basalt whiskers for reinforcing materials were measured at 40 ^o C Far infrared ray emissivity and emissivity power were measured. As a result, as shown in FIGS. 4A and 4B, the basalt whisker material containing 10 wt% of basalt was increased to 0.926, and the amount of basalt was increased to about 40 wt% compared with the PVP fiber without basalt It can be seen that the far-infrared emissivity increases to 0.935 (see Table 1)

Table 1

However, when the amount of the basalt is added in an excess amount of 40 wt%, the fiber is not properly radiated due to clogging of the tip of the syringe during electro spinning.

From the above results, it can be confirmed that fibrous basalt / PVP having high far-infrared ray emissivity and radiant energy was produced by performing electro spinning by adding basalt to PVP.

Claims (15)

A method of manufacturing a basalt whisker for a reinforcement using electrospinning,
PVP (polyvinylpyrrolidone) in an ethanol solution to dissolve;
Milling a basalt gemstone to a relatively small size and then milling it to a predetermined size through a ball-mill grinder;
Mixing the basalt powder pulverized with the predetermined particle size into a mixed solution of an ethanol solution and water to uniformly disperse the basalt powder;
Mixing the basalt dispersion liquid into the PVP solution and uniformly mixing the same;
Radiating the mixed basalt / PVP mixed solution by electro-spinning in a dust collector;
Recovering the spinning basalt whisker material from the dust collector and drying the dried basalt whisker material at a constant temperature in the dryer; and heat treating the dried basalt whisker material in an air atmosphere in a baking furnace to produce a basalt whisker Wherein the method comprises the steps of: preparing a basalt whisker for a reinforcing material by electrospinning;
The method of claim 1, wherein 60 to 70 wt% of an ethanol solution is added to and dissolved in 30 to 40 wt% of PVP (polyvinylpyrrolidone).
The method of claim 1, wherein the small-sized ground basalt is pulverized to a particle size of 0.1 to 10 μm in a ball-mill grinder.
The method for manufacturing a basalt whisker for reinforcement according to claim 1 or 3, wherein the milling time of the basalt rock through the ball mill mill is 30 to 50 hours.
The method of any one of claims 1 to 3, wherein the crushing time of the basalt rock through the ball-mill grinder is 44 hours.
The method for manufacturing a basalt whisker for reinforcement using electrospinning according to claim 1, wherein the mixing ratio of the ethanol solution for dispersing the pulverized basalt powder to water is 1: 1.
The method according to claim 1, wherein the basalt mixed with the PVP solution and mixed with the PVP solution has a weight ratio of 5 to 30 wt% with respect to the PVP.
The method according to claim 1, wherein the basalt mixed with the PVP solution and mixed with the PVP solution has a weight ratio of 10 wt% with respect to the PVP.
The method of claim 1, wherein the mixed basalt / PVP mixed solution is applied by electrospinning at a rate of 15 μl / min at an applied voltage of 7 kV.
The method of claim 1, wherein the mixed basalt / PVP mixed solution is injected into a dust collector in a syringe type injector.
11. The method of claim 1 or 10, wherein the distance between the injector and the collector is set to 10 cm.
11. The method of claim 1 or 10, wherein the basalt / PVP mixed solution is spun for 10 minutes by electro-spinning in a dust collector, and the drying temperature of the dried basalt whisker is 60 to 80 < ^{0 &} Wherein the method comprises the steps of: preparing a basalt whisker for a reinforcing material by electrospinning;
The method of claim 1, wherein the drying time of the spinner finished basalt whisker material is 4 to 6 hours.
The basalt whisker material according to claim 1, wherein the basalt whisker material is gradually heated at a temperature of 2 to 5 ^° C / min in an air atmosphere in a firing furnace, and is heat-treated at 1200 ^° C. Way.
15. The method of claim 1 or 14, wherein the basalt whisker material is heat treated at a temperature of 1200 < ⁰ > C for 30 to 60 minutes in a firing furnace.

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