This application claims under 35 U.S.C. §119(a) the benefit of Korean Patent Application No. 10-2007-0135267 filed Dec. 21, 2007, the entire contents of which are incorporated herein by reference.
1. Technical Field
The present invention relates to a method of encapsulating a carbon material within aluminum.
2. Background Art
Aluminum is widely used in everyday life, from foil used in a kitchen, to disposable tableware, windows, cars, airplanes, spaceships, etc. Aluminum is light in weight (about one-third the weight of iron), and has high strength by alloying with other metals. Also, aluminum is chemically stable because a chemically stable oxide layer existing on an aluminum surface inhibits development of corrosion caused by moisture or oxygen, etc.
Therefore, aluminum has been used for cars, airplanes, etc. Especially, an aluminum wheel used for cars provides two effects in that its lighter weight than a conventional iron wheel decreases its own load, which contributes to lowering the weight of a car body, as well as improving fuel efficiency. However, such aluminum has tensile strength of about 40% based on iron. Accordingly, the use of the aluminum as a structural material significantly increases the thickness of a structural aluminum pipe or panel, and thus a large amount of material is required, thereby causing a problem in that an excessive cost is required.
In order to solve the above described problems, research on preparation of a composite material of a carbon material having high tensile strength and aluminum has been actively carried out. In the preparation of a carbon material-aluminum composite, there are problems to be overcome. First, carbon materials, e.g., carbon nanotubes have high interactive cohesive force by Van der Waals force, and thus are difficult to be uniformly dispersed in aluminum matrix. Second, a carbon material and an aluminum matrix have different surface tensions. A good example showing great difference in surface tensions is water and oil, water being 2-3 times as great as oil. However, a recent research report revealed that surface tension of aluminum is 955 mN/m, and surface tension of a carbon material is 45.3 mN/m [based on J. M. Molina et al. international Journal of adhesion Adhesives 27 (2007) 394-401, S, Nuriel, L. Liu, A. H. Barber, H. D. Wagner. Direct measurement of multiwall nanotube surface tension, Chemical Physics Letters 404 (2005) 263-266]. That is, the difference in surface tensions between these two materials is about 20 times greater than the other. This result says that the two materials are hard to be mixed with each other. Also, since the density of the two materials are significantly different, they are hardly mixed with each other when they are melted.
In order to overcome such problems of a carbon material, and to prepare a carbon material-aluminum composite, a variety of attempts such as gas blending, solution dispersion, electroplating, ball mill, etc. have been made.
The gas blending is a technology on gas-mixing of metal powder and a carbon nanotube (e.g., Japanese Patent Laid-Open Publication No. 2007-16262 (2007.1.25)). In the gas mixing, various kinds of metal powder, including aluminum, can be used to uniformly mix with a carbon nanotube. However, the carbon nanotube is difficult to prepare an aluminum-carbon material composite, in which the carbon material is uniformly dispersed on the aluminum matrix, due to difficulty in penetration into an aluminum particle having an oxide layer.
In the solution dispersion, a composite is prepared by mixing a minute aluminum particle-dispersed solution with a carbon nanotube-dispersed solution, and drying a solvent (e.g., Chinese Patent Laid-Open Publication No. CN1465729A). In the mix in a solution, a carbon nanotube can be uniformly dispersed. However, in order to obtain a significant effect through the mix in a solution, a small sized aluminum particle is required, and the use of such a small sized aluminum particle may cause an explosion. Also, a carbon nanotube is difficult to penetrate into an oxide layer of an aluminum particle in this method. In this respect, there has been a problem in preparing the composite.
The electroplating means a method of preparing a composite material plating solution, applying a potential, and plating a composite material (Japanese Patent Laid-Open Publication No. 2007-070689). In this technology, a carbon nanotube and aluminum are dissolved in a plating solution so that the two materials can reach the surface of the cathode, thereby forming a composite. In this method, however, there is a disadvantage in that the binding force between aluminum and carbon material cannot be controlled and the yield decreases.
The ball mill is a technology on a mix of a carbon nanotube with aluminum through high physical impact by using a ball having high physical force (e.g., Japanese Patent Laid-Open Publication No. 2006-315893(2006.11.24)). In the ball mill method described in the patent, a cocoon-thread-like complicatedly twisted carbon nanotube is milled and dispersedly mixed with an aluminum particle. However, this method still has the disadvantage that the carbon nanotube cannot penetrate into an oxide layer of aluminum but is merely mixed with the aluminum.
The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
Therefore, the present invention has been made in view of the above-mentioned problems, and the present invention provides a method of encapsulating a carbon material within an aluminum through ball mill. In the encapsulated carbon material prepared by the method according to the present invention, the crystallinity can be maintained as it is without destruction of the structure, thereby improving the strength. In other words, it is the object of the present invention to provide a method of encapsulating a carbon material within aluminum through a ball mill while maintaining the crystallinity of the carbon material.
It is another object of the present invention to provide a method of fabricating an aluminum-carbon material composite by encapsulating a carbon material within an aluminum through a ball mill.
It is yet another object of the present invention to provide a carbon material-aluminum composite fabricated according to the above method.
According to an aspect of the present invention, there is provided a method of encapsulating a carbon material within aluminum. The term ‘Encapsulation’ used in the present invention indicates the coating of a carbon material with aluminum.
The object of the present invention is to provide a method of encapsulating a functionalized carbon material within aluminum by using a ball mill method. In other words, the present invention provides a method of encapsulating a carbon material within aluminum, the method including the steps of: (i) functionalizing a carbon material by introducing a defect therein; (ii) mixing the functionalized carbon material with aluminum; and (iii) ball milling the mixture under an inert gas atmosphere.
In the present invention, the carbon material may include at least one of the materials selected from the group including graphite, a graphite fiber, a carbon fiber, a carbon nano fiber, and a carbon nanotube.
At present, it is known that an available carbon material has a diameter of 0.4 nm to 16 μm, and a length of 10 nm to 10 cm. Specifically, based on recently reported data (Science 292, 2462 (2001)), a carbon nanotube has the smallest diameter size of 0.4 nm, and a carbon fiber (in the case of a commercialized product) has the largest diameter of 16 μm (Taiwan Carbon Technology Co). A multi-walled carbon nanotube and an NK carbon nanotube, which were used as carbon materials in the present invention, have diameters of 10 to 20 nm, and 40 to 60 nm, and lengths of 10 to 20 μm, and about 20 μm, respectively. Also, a carbon fiber (Toray) has a diameter of 7˜8 μm, and a length of 5 mm. However, the method according to the present invention is not limited to the above described sizes of a carbon material.
In step (i), in order to functionalize the carbon material by introducing a defect therein, acid treatment may be carried out. In the acid treatment, nitric acid (HNO3), sulfuric acid (H2SO4), or acid including a mixture of nitric acid and sulfuric acid may be used. A carbon nanotube includes a sp2 hybrid bond, and has a cylindrical structure. However, such a structure of the carbon nanotube has a smooth surface, and thus is difficult to be bonded with other materials. Therefore, as a carbon nanotube used for a composite, material having a defect capable of bonding with a matrix, such as a groove, is used. Also, through a functionalization process, a functional group having certain reactivity to the defect, such as —OH, —COOH, —CHO, etc. is attached to a carbon material to increase the reactivity.
In step (i), in order to functionalize the carbon material by introducing a defect therein, microwave treatment may be carried out. In the microwave treatment, as a solvent, a mixture including one or at least two kinds of materials selected from the group including ethylene glycol, nitric acid (HNO3), and sulfuric acid (H2SO4) may be used. Herein, a time for the microwave treatment may be 1 to 10 minutes.
In step (i), in order to functionalize the carbon material by introducing a defect therein, plasma treatment may be carried out. In the plasma treatment, mixed gas including one or at least two kinds of materials selected from the group including oxygen, argon, and helium may be used. Herein, electric power of 50 to 1000 W may be used, and a time for the treatment may be 1 minute to 1 hour.
Although acid/microwave/plasma treatments are described as methods for functionalizing a carbon material by introducing a defect therein in step (i), the method according to the present invention is not limited thereto.
The term “functionalize” as used herein means forming a defect in a carbon material and attaching a functional group to the defect.
In step (ii), the mixing ratio of the carbon material to aluminum may be 0.1 to 50 wt %.
In step (iii), in order to compose the inert gas atmosphere for the mixture, inert gas, such as argon, nitrogen, helium, or neon, may be used. Also, in order to encapsulate carbon material powder within aluminum, a ball mill process may be carried out at 100 to 5000 rpm, for 30 minutes to 7 days. However, the method according to the present invention is not limited to the above described rpm and time.
According to another aspect of the present invention, there is provided a method of fabricating an aluminum-carbon material composite by encapsulating a carbon material within aluminum through a ball mill. The method comprises the steps of: (i) functionalizing the carbon material by introducing a defect therein; (ii) mixing the functionalized carbon material with aluminum; and (iii) ball milling the mixture under an inert gas atmosphere, thereby encapsulating a carbon material within aluminum.
Additionally, in order to increase reactivity of a carbon material, step (i) may be performed by treatment of acid, microwave, or plasma, as described above. The condition of a ball mill and the feature of the carbon material are the same as those described above.
According to yet another aspect of the present invention, there is provided an aluminum-carbon material composite fabricated by the above method of the present invention. An encapsulated aluminum-carbon material composite according to the present invention may have a thickness of at least 0.3 nm (which is corresponding to an atomic monolayer), more preferably of 0.3 nm to 10 mm. Also, the encapsulated aluminum-carbon material composite includes at least one carbon material.
In the field of a carbon material (such as a carbon nanotube) composite, a main problem to solve is to uniformly disperse the carbon material within a metal matrix and to cause an interaction therebetween, thereby improving the properties [Carbon Nanotube/Aluminium Composites with Uniform Dispersion*, Materials Transactions, Vol. 45, No. 2 (2004) pp. 602-604]. In order to uniformly disperse a carbon material, especially, a carbon nanotube, within a metal substrate, the carbon material and the metal substrate have to have similar physical properties (molecular/atomic interaction therebetween). The above description may be explained by the separation of water from oil in everyday life, which is caused by different surface tensions of two materials, and herein, the surface tensions indicate an interaction therebetween. Water has a surface tension of 72 mN/m, which is twice or more as large as that (28.9 mN/m) of oil (benzene). Also, as described above, a surface tension of aluminum is about twenty times as large as that of a carbon nanotube. Therefore, encapsulation of a carbon material, particularly a carbon nanotube within aluminum may solve the problem, and thus cause an improved effect in uniformly dispersing the carbon material within an aluminum matrix. From the standpoint related to high physical properties, a high strength composite may be prepared [Processing and properties of carbon nanotubes reinforced aluminum composites, Materials Science and Engineering A 444 (2007) 138-45].
The foregoing and other objects, features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings in which:
The present invention provides a method of encapsulating a carbon material within aluminum by using a ball mill method. The method includes the steps of: (i) functionalizing a carbon material by introducing a defect therein; (ii) mixing the functionalized carbon material with aluminum; and (iii) ball milling the mixture under an inert gas atmosphere.
Reference will now be made in detail to the preferred embodiments of the present invention. However, the following examples are illustrative only, and the scope of the present invention is not limited thereto. The contents of documents cited in the present invention are hereby incorporated by reference.
An embodiment of the present invention is described in
1-1. Functionalization of a Carbon Material by Acid Treatment
The carbon nanotube was functionalized by an ultrasonic reaction in a water tank type reactor containing 70% nitric acid (HNO3) for 10 minutes to 3 hours. As the NK carbon nanotube, a functionalized product was used. The carbon fiber was functionalized by an ultrasonic reaction in a 1:1 mixture of sulfuric acid (H2SO4) and nitric acid (HNO3) for 2 hours.
1-2. Functionalization of a Carbon Material by Microwave Treatment
In a method of functionalization by using microwave, ethylene glycol or nitric acid (HNO3) was used as a solvent, sodium chlorate (NaClO3) was used as a oxidation agent, and the multi-walled carbon nanotube was dispersed to the solvent. The microwave treatment was carried in a microwave oven (Daewoo Electronics, KR-U20AB) for 3 minutes, and herein such a treatment time may be 1 to 6 minutes.
1-3. Functionalization of a Carbon Material by Plasma Treatment
Plasma treatment was carried out on the multi-walled carbon nanotube by using power consumption of 500 W in atmospheric pressure, and herein, as gas material, 500 sccm of oxygen and 300 sccm of helium were used. The plasma treatment was carried out by using A-tech system product for 5 minutes to functionalize through introduction of a defect.
1-4. Encapsulation of a Carbon Material within Aluminum by Ball Mill
19 g of aluminum powder and 1 g of a multi-walled carbon nanotube, an NK carbon nanotube, or a carbon fiber as a carbon material were used. The aluminum was purchased from Samchun Chemical. Each of the functionalized carbon material was mixed with aluminum powder in a ratio of 5 wt % by weight by using a ball mill, and the mixture was put into a metal jar made of steel. The ball was a zirconia ball (Daehan, DH, ML 1032) with a diameter of 0.5-10 mm. The weight ratio of the aluminum particles including a carbon nanotube or a carbon fiber to the zirconia ball was 1:4. To prevent oxidation of aluminum, the jar was filled with argon gas. After the jar, from which oxygen and moisture were sufficiently removed, was securely sealed, a ball mill process could be carried out at 50 to 400 rpm. It was possible to set a ball mill time within a range of 1 to 24 hours.
A change in colors before/after encapsulation of a carbon material within aluminum was taken by a digital camera (Nikon, koolpix-3700).
a is a photograph of a multi-walled carbon nanotube before aluminum encapsulation, and shows actual volumes before encapsulation of the multi-walled carbon nanotube within aluminum.
c is a photograph of an NK carbon nanotube before aluminum encapsulation. The NK carbon nanotube is a kind of multi-walled carbon nanotube, and has a thicker diameter than a general multi-walled carbon nanotube, and many functional groups on the surface thereof. Also, the apparent volume of the NK carbon nanotube is greater than that of aluminum powder.
e is a photograph of a carbon fiber before aluminum encapsulation. As shown in
Based on the color-change observation, electron microscopic photographs, Raman analysis, aluminum capsule removal of an aluminum encapsulated carbon material, it is determined that in an aluminum encapsulated carbon material according to the present invention, the crystallinity can be maintained as it is. A carbon material-aluminum composite according to the present invention is light and has high strength, and thus can be applied to a car component and an aluminum wheel. Accordingly, the market of aluminum wheels is expected to cover commercial vehicles and heavy duty trucks as well as cars. Also, such a composite is expected to be used for airplanes, spaceships, ships, etc., which requires high strength. In addition, the composite is expected to be applied for components of a computer, and various refrigeration machines due to high thermal conductivity.
While this invention has been described in connection with what is presently considered to be the most practical and exemplary embodiment, it is to be understood that the invention is not limited to the disclosed embodiment and the drawings, but, on the contrary, it is intended to cover various modifications and variations within the spirit and scope of the appended claims.
Number | Date | Country | Kind |
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10-2007-0135267 | Dec 2007 | KR | national |