U.S. patent application number 13/647017 was filed with the patent office on 2013-03-07 for carbon nanotube-reinforced nanocomposites.
This patent application is currently assigned to APPLIED NANOTECH HOLDINGS, INC.. The applicant listed for this patent is APPLIED NANOTECH HOLDINGS, INC.. Invention is credited to Dongsheng Mao, Zvi Yaniv.
Application Number | 20130059947 13/647017 |
Document ID | / |
Family ID | 41570534 |
Filed Date | 2013-03-07 |
United States Patent
Application |
20130059947 |
Kind Code |
A1 |
Mao; Dongsheng ; et
al. |
March 7, 2013 |
CARBON NANOTUBE-REINFORCED NANOCOMPOSITES
Abstract
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.
Inventors: |
Mao; Dongsheng; (Austin,
TX) ; Yaniv; Zvi; (Austin, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
APPLIED NANOTECH HOLDINGS, INC.; |
Austin |
TX |
US |
|
|
Assignee: |
APPLIED NANOTECH HOLDINGS,
INC.
Austin
TX
|
Family ID: |
41570534 |
Appl. No.: |
13/647017 |
Filed: |
October 8, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12180359 |
Jul 25, 2008 |
8283403 |
|
|
13647017 |
|
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Current U.S.
Class: |
523/468 ;
977/742 |
Current CPC
Class: |
C08K 3/041 20170501;
C08K 2201/004 20130101; B82Y 30/00 20130101; C08K 7/06 20130101;
C08J 2363/00 20130101; C08J 5/24 20130101; Y10T 428/2918 20150115;
C08K 3/04 20130101; C08J 5/005 20130101; C08K 7/24 20130101; C08K
3/04 20130101; C08L 63/00 20130101; C08K 7/24 20130101; C08L 63/00
20130101; C08K 3/041 20170501; C08L 63/00 20130101 |
Class at
Publication: |
523/468 ;
977/742 |
International
Class: |
C08L 63/02 20060101
C08L063/02; C08K 3/04 20060101 C08K003/04 |
Claims
1.-7. (canceled)
8. A method for making a composite material, comprising: shortening
carbon nanotubes to an average length of less than 2 .mu.m;
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 .mu.m.
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 .mu.m.
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 .mu.m.
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.
Description
[0001] 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.
[0002] BACKGROUND
[0003] 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/cm.sup.3) 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.
TABLE-US-00001 TABLE 1 SWNTs DWNTs MWNTs Surface area (m.sup.2/g)
300-600 300-400 40-300 Geometric aspect ratio ~10,000 ~5,000
100~1000 (length/diameter)
[0004] 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/cm.sup.3 and the epoxy matrix to has a density of 1.2
g/cm.sup.3). 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.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 illustrates a process for manufacturing
Nanocomposites in accordance with an embodiment of the present
invention;
[0006] FIG. 2 shows a SEM digital image of MWNTs;
[0007] FIGS. 3A-3C show SEM digital images of fracture surfaces of
a MWNT-reinforced epoxy, DWNT-reinforced epoxy, and SWNT-reinforced
epoxy, respectively;
[0008] FIG. 4A shows a SEM digital image of a fracture surface of a
DWNT-reinforced CFRP showing no DWNTs were penetrated inbetween
carbon fibers;
[0009] FIG. 4B shows a SEM digital image of a fracture surface of a
DWNT-reinforced CFRP showing DWNTs were filtered out to an end
layer of prepreg;
[0010] FIGS. 5A-5C show SEM digital images of shortened MWNTs,
DWNTs, and SWNTs, respectively; and
[0011] FIGS. 6A-6C show SEM digital images of fracture surfaces of
a MWNT-reinforced CFRP, DWNT-reinforced CFRP, and SWNT-reinforced
CFRP, respectively.
DETAILED DESCRIPTION
[0012] CNTs as short as or shorter than 2 .mu.m can be penetrated
inbetween the fibers and therefore significantly improve the
mechanical properties of the FRP.
[0013] 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 Hardener
[0014] Epoxy 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. FIG. 2 shows a digital image of an SEM of the
MWNTs. Except for the epoxy, other thermosets such as polyimide,
phenolics, cyanate esters, and bismaleimides or thermal plastics
such as nylon may also work.
[0015] FIG. 1 illustrates a schematic diagram of a process flow to
make epoxy/CNT Nanocomposites in accordance with an embodiment of
the present invention. All ingredients may be dried in a vacuum
oven at 70.degree. C. for 16 hours to eliminate moisture. The
loading of the CNTs may be 1.0 wt. % for each of the resins. CNTs
are placed in acetone 101 and dispersed by a micro-fluidic machine
in step 102 (commercially available from Microfluidics Co., model
no. Y110). The micro-fluidic machine uses high-pressure streams
that collide at ultra-high velocities in precisely defined
micron-sized channels. Its combined forces of shear and impact act
upon products to create uniform dispersions. The CNT/acetone then
forms as a gel 103 resulting in the CNTs well dispersed in the
acetone solvent, However, other methods, such as an
ultra-sonication process or a high shear mixing process may also be
used. A surfactant may be also used to disperse CNTs in solution.
Epoxy is then added in step 104 to the CNT/acetone gel to create an
epoxy/CNT/acetone solution 105, which is followed by an
ultra-sonication process in a bath at 70.degree. C. for 1 hour
(step 106) to create an epoxy/CNT/acetone suspension 107. The CNTs
may be further dispersed in epoxy in step 108 using a stirrer
mixing process at 70.degree. C. for half an hour at a speed of
1,400 rev/min. to create an epoxy/CNT/acetone gel 109. A hardener
is than added in step 110 to the epoxy/CNT/acetone gel 109 at a
ratio of 4.5 wt. % followed by stirring at 70.degree. C. for 1
hour. The resulting gel 111 may then be degassed in step 112 in a
vacuum oven at 70.degree. C. for 48 hours. The material 113 may
then be cured at 160.degree. C. for 2 hours. In order to test the
material 113, it may then be poured into a Teflon mold so that the
mechanical properties (flexural strength and flexural modulus) of
the specimens are characterized after a polishing process 115.
[0016] The above resin (epoxy/CNT/hardener) after being degassed at
70.degree. 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.
[0017] 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/m.sup.2.
Mechanical Properties of the Nanocomposites
[0018] Table 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.
TABLE-US-00002 TABLE 2 Mechanical properties Mechanical properties
of the resin of the CFRP Flexural Flexural Flexural Flexural
strength modulus strength modulus Sample (MPa) (GPa) (MPa) (GPa)
Neat epoxy 116 3.18 1394 62.3 Epoxy/MWNTs 149 3.54 1388 61.5 (1.0
wt. %) Epoxy/DWNTs 159 3.69 1354 61.7 (1.0 wt. %) Epoxy/SWNTs 164
3.78 1408 62.8 (1.0 wt. %)
[0019] 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 FIGS. 3A 3C). However, the CNTs were
filtered out to the end layer of the prepreg by the unidirectional
carbon fibers (see FIGS. 4A-4B for DWNT-reinforced epoxy CFRP).
That is because the CNTs are so long that they cannot be penetrated
inbetween the carbon fibers because the gap for the nearest carbon
fibers is only around 1 .mu.m. That is the reason why the
reinforcement of CNTs in resin did not transfer to the CFRP.
Shortening of the CNTs and Reinforcement of Epoxy Resin and
CFRP
[0020] 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.degree. 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.degree. C. for 12 hours. FIGS. 5A 5C show
SEM images of MWNTs, DWNTs, and SWNTs, respectively, shortened to
less than 2 .mu.m length.
[0021] 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.
TABLE-US-00003 TABLE 3 Mechanical properties Mechanical properties
of the resin of the CFRP Flexural Flexural Flexural Flexural
strength modulus strength modulus Sample (MPa) (GPa) (MPa) (GPa)
Neat epoxy 116 3.18 1394 62.3 Epoxy/MWNTs 150 3.60 1561 65.4 (1.0
wt. %) Epoxy/DWNTs 160 3.65 1603 67.3 (1.0 wt. %) Epoxy/SWNTs 162
3.70 1630 70.8 (1.0 wt. %)
[0022] Scanning electron microscopy (SEM) may then be used to check
the dispersion of the CNTs in the CFRP samples. As shown in FIGS.
6A-6C, shortened MWNTs, DWNTs, and SWNTs are penetrated and well
dispersed inbetween the carbon fibers.
* * * * *