CARBON NANOTUBE-REINFORCED NANOCOMPOSITES
Carbon nanotubes (CNTs) are so long that they cannot be penetrated inbetween carbon fibers during a prepreg preparation process, and are shortened in order for them not to be filtered out by the carbon fibers. This results in a huge improvement of the mechanical properties (flexural strength and flexural modulus) compared with neat epoxy.
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This application is a continuation-in-part of U.S. patent application Ser. No. 11/757,272, which claims priority to U.S. Provisional Patent Application Ser. Nos. 60/819,319 and 60/810,394, all of which are hereby incorporated by reference herein. This application is a continuation-in-part of U.S. patent application Ser. No. 11/693,454, which claims priority to U.S. Provisional Application Ser. Nos. 60/788,234 and 60/810,394, all of which are hereby incorporated by reference herein. This application is a continuation-in-part of U.S. patent application Ser. No. 11/695,877, which claims priority to U.S. Provisional Applications Ser. Nos. 60/789,300 and 60/810,394, all of which are hereby incorporated by reference herein.
BACKGROUND
Since the first observation in 1991, carbon nanotubes (CNTs) have been the focus of considerable research (S. Iijima, “Helical microtubules of graphitic carbon,” Nature 354, 56 (1991)). Many investigators have reported the remarkable physical and mechanical properties of this new form of carbon. CNTs typically are 0.5-1.5 nm in diameter for single wall CNTs (SWNTs), 1-3 nm in diameter for double wall CNTs (DWNTs), and 5 nm to 100 nm in diameter for multi-wall CNTs (MWNTs). From unique electronic properties and a thermal conductivity higher than that of diamond to mechanical properties where the stiffness, strength and resilience exceeds that of any current material. CNTs offer tremendous opportunity for the development of fundamental new material systems. In particular, the exceptional mechanical properties of CNTs (E>1.0 TPa and tensile strength of 50 GPa) combined with their low density (1-2.0 g/cm3) make them attractive for the development of CNT-reinforced composite materials (Eric W. Wong, Paul E. Sheehan, Charles M. Lieber, “Nanobeam Mechanics: Elasticity, Strength, and Toughness of Nanorods and Nanotubes,” Science 277, 1971(1997)). CNTs are the strongest material known on earth. Compared with MWNTs, SWNTs and DWNTs are even more promising as reinforcing materials for composites because of their higher surface area and higher aspect ratio. Table 1 lists surface areas and aspect ratios of SWNTs, DWNTs, and MWNTs.
A problem is that CNTs are usually pretty long (from several microns to over 100 Tm) when they are grown, which makes it difficult for them to be penetrated into a matrix in fiber reinforced plastics (FRP) because the distance between, the nearest fibers is so small. For instance, for a unidirectional carbon fiber or fabric reinforced epoxy composite, the content of the carbon fibers is around 60 percent by volume so that the gap between the nearest carbon fibers is around 1 micron (assuming the carbon fiber has a diameter of 7-8 Tm with a density of around 1.75-1.80 g/cm3 and the epoxy matrix to has a density of 1.2 g/cm3). The same is true for glass fibers and other types of fibers used to make composites. CNTs may reinforce the polymer resin to improve mechanical properties such as strength and modulus, however they cannot reinforce the FRP because they are filtered out by the fibers during the FRP preparation.
CNTs as short as or shorter than 2 μm can be penetrated inbetween the fibers and therefore significantly improve the mechanical properties of the FRP.
In one embodiment of the present invention, a detailed example of this embodiment is given in an effort to better illustrate the invention.
Epoxy, SWNTs, DWNTs, MWNTs, and HardenerEpoxy resin (bisphenol-A) was obtained from Arisawa Inc., Japan. The hardener (dicyandiamide) was obtained from the same company, which was used to cure the epoxy nanocomposites. SWNTs, DWNTs and MWNTs were obtained from Nanocyl, Inc., Belgium. The CNTs may be purified to >90% carbon content. However, pristine CNTs or functionalized by functional groups such as carboxylic and amion-functional groups may also work. The length of the CNTs may be around 5-20 Tm.
The above resin (epoxy/CNT/hardener) after being degassed at 70° C. for 48 hours may be also used to make a FRP using a hot-melt process. Carbon fiber (obtained from Toray Industries, Inc., model no. T700-12k) may be used for prepreg preparation. “Prepreg” (or, “pre-preg”) is a term known in the art for “pre-impregnated” composite fibers. These may take the form of a weave or are unidirectional. They contain an amount of the matrix material used to bond them together and to other components during manufacture. The pre-preg may be stored in cooled areas since activation is most commonly done by heat. Hence, composite structures build of pre-pregs will mostly require an oven or autoclave to cure out.
The CNT-reinforced epoxy resin is first coated onto a releasing paper. The prepreg is then obtained by impregnating unidirectional carbon fibers with CNT-reinforced epoxy resin thin film. The volume of the carbon fiber was controlled at 60%. The prepreg had an area weight of 180 g/m2.
Mechanical Properties of the NanocompositesTable 2 shows mechanical properties (flexural strength and flexural modulus) of the CNT-reinforced epoxy and also with the reinforcement of the unidirectional carbon fibers. It can be seen in resin form, a huge improvement of the mechanical properties (each has over 30% improvement of the flexural strength and at least 10% improvement of the flexural modulus) compared with neat epoxy. However, in the Carbon Fiber Reinforced Polymer (CFRP) form, both properties did not improve for the CNT-reinforced CFRP compared with the neat epoxy CFRP.
Scanning electron microscopy (SEM) may then be used to check the dispersion of the CNTs in both the resin and the CFRP samples. In the resin form, all the CNT-reinforced epoxy samples showed very good dispersion of CNTs (see
Because the CNTs are so long that they cannot be penetrated inbetween the carbon fibers during the prepreg preparation process, they need to be shortened in order for them not to be filtered out by the carbon fibers. The MWNTs, DWNTs, and SWNTs may be mixed with a concentrated acid mixture (HNO3:H2SO4=3:1) and stirred for 4 hours at 120° C. The CNTs are filtered using filter paper (polycarbonate filter paper with 2 micron open to filter out the acid), The CNTs may then be washed with ionized water 4-5 times and dried in vacuum over 50° C. for 12 hours.
Table 3 shows mechanical properties (flexural strength and flexural modulus) of the shortened CNT-reinforced epoxy and also with the reinforcement of the unidirectional carbon fibers. It can be seen in resin form a huge improvement of the mechanical properties (each has over 30% improvement of the flexural strength and at least 10% improvement of the flexural modulus) compared with the neat epoxy, which is similar as the long CNT-reinforced epoxy resin mentioned above. In the CFRP form, both properties improved compared with the neat epoxy CFRP. For example, flexural strength of the SWNT-reinforced CFRP improved 17% compared with that of the neat epoxy CFRP.
Scanning electron microscopy (SEM) may then be used to check the dispersion of the CNTs in the CFRP samples. As shown in
Claims
1.-7. (canceled)
8. A method for making a composite material, comprising:
- shortening carbon nanotubes to an average length of less than 2 μm;
- dispersing the shortened carbon nanotubes in a solution;
- mixing the solution of shortened carbon nanotubes with a polymer to produce a carbon nanotube reinforced polymer; and
- combining the carbon nanotube reinforced polymer with carbon fibers in a manner so that the shortened carbon nanotubes are impregnated in between individual ones of the carbon fibers to produce the composite material.
9. The method as recited in claim 8, further comprising curing the composite material.
10. The method as recited in claim 9, wherein the cured composite material has a flexural strength greater than that of a cured carbon fiber reinforced polymer not combined with carbon nanotubes.
11. The method as recited in claim 9, wherein the cured composite material has a flexural modulus greater than that of a cured carbon fiber reinforced polymer not combined with carbon nanotubes.
12. The method as recited in claim 9, wherein the cured composite material has a flexural strength greater than that of a cured carbon fiber reinforced polymer combined with carbon nanotubes with an average length greater than 2 μm.
13. The method as recited in claim 9, wherein the cured composite material has a flexural modulus greater than that of a cured carbon fiber reinforced polymer combined with carbon nanotubes with an average length greater than 2 μm.
14. The method as recited in claim 8, wherein the combining does not filter out the shortened carbon nanotubes to ends of the carbon fibers.
15. The method as recited in claim 8, wherein an average length of the carbon nanotubes is less than 2 μm.
16. The method as recited in claim 8, wherein the polymer is thermosetting or thermal plastics.
17. The method as recited in claim 16, wherein the thermosetting plastics are selected from the group consisting of polyimide, phenolics, cyanate easters, and bismalemiides.
18. The method as recited in claim 8, wherein the carbon nanotubes are not functionalized.
19. The method as recited in claim 8, wherein the carbon nanotubes are functionalized to carboxylic functional groups or amine functional groups.
20. The method as recited in claim 8, wherein the carbon nanotubes are functionalized to amine functional groups.
21. The method as recited in claim 8, wherein the carbon fibers are unidirectional carbon fibers.
Type: Application
Filed: Oct 8, 2012
Publication Date: Mar 7, 2013
Applicant: APPLIED NANOTECH HOLDINGS, INC. (Austin, TX)
Inventor: APPLIED NANOTECH HOLDINGS, INC. (Austin, TX)
Application Number: 13/647,017
International Classification: C08L 63/02 (20060101); C08K 3/04 (20060101); B82Y 30/00 (20110101);