U.S. patent application number 12/761157 was filed with the patent office on 2011-02-03 for mechanically stiff, electrically conductive composites of polymers and carbon nanotubes.
Invention is credited to Theodore F. Baumann, Alex V. Hamza, Sergei O. Kucheyev, Joshua D. Kuntz, Joe H. Satcher, JR., Marcus A. Worsley.
Application Number | 20110024698 12/761157 |
Document ID | / |
Family ID | 43526128 |
Filed Date | 2011-02-03 |
United States Patent
Application |
20110024698 |
Kind Code |
A1 |
Worsley; Marcus A. ; et
al. |
February 3, 2011 |
Mechanically Stiff, Electrically Conductive Composites of Polymers
and Carbon Nanotubes
Abstract
Using SWNT-CA as scaffolds to fabricate stiff, highly conductive
polymer (PDMS) composites. The SWNT-CA is immersing in a polymer
resin to produce a SWNT-CA infiltrated with a polymer resin. The
SWNT-CA infiltrated with a polymer resin is cured to produce the
stiff and electrically conductive composite of carbon nanotube
aerogel and polymer.
Inventors: |
Worsley; Marcus A.;
(Hayward, CA) ; Kucheyev; Sergei O.; (Oakland,
CA) ; Baumann; Theodore F.; (Discovery Bay, CA)
; Kuntz; Joshua D.; (Livermore, CA) ; Satcher,
JR.; Joe H.; (Patterson, CA) ; Hamza; Alex V.;
(Livermore, CA) |
Correspondence
Address: |
Lawrence Livermore National Security, LLC
LAWRENCE LIVERMORE NATIONAL LABORATORY, PO BOX 808, L-703
LIVERMORE
CA
94551-0808
US
|
Family ID: |
43526128 |
Appl. No.: |
12/761157 |
Filed: |
April 15, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61172363 |
Apr 24, 2009 |
|
|
|
Current U.S.
Class: |
252/511 ;
977/750 |
Current CPC
Class: |
C08J 5/24 20130101; H01B
1/24 20130101; B82Y 40/00 20130101; B82Y 30/00 20130101; Y10S
977/75 20130101; C08J 2383/04 20130101; Y10S 977/932 20130101; Y10S
977/783 20130101 |
Class at
Publication: |
252/511 ;
977/750 |
International
Class: |
H01B 1/04 20060101
H01B001/04; H01B 1/12 20060101 H01B001/12 |
Goverment Interests
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED
RESEARCH AND DEVELOPMENT
[0002] The United States Government has rights in this invention
pursuant to Contract No. DE-AC52-07NA27344 between the United
States Department of Energy and Lawrence Livermore National
Security, LLC for the operation of Lawrence Livermore National
Laboratory.
Claims
1. A method of making a stiff and electrically conductive composite
of carbon nano tube aerogel and polymer, comprising the steps of:
providing a single-walled carbon nanotubes carbon aerogel,
immersing said single-walled carbon nanotube carbon aerogel in a
polymer resin to produce a single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin, and curing said
single-walled carbon nanotubes carbon aerogel infiltrated with said
polymer resin to produce the stiff and electrically conductive
composite of carbon nanotube aerogel and polymer.
2. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of immersing said single-walled carbon nanotube carbon
aerogel in a polymer resin to produce a single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin
includes placing said single-walled carbon nanotube carbon aerogel
immersed in a polymer resin under vacuum.
2. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of curing said single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin to produce the stiff
and electrically conductive composite of carbon nanotube aerogel
and polymer comprises curing said single-walled carbon nanotubes
carbon aerogel infiltrated with said polymer resin at 60 or
150.degree. C.
3. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of providing a single-walled carbon nanotubes carbon
aerogel comprises providing SWNT-CA nanofoams with a SWNT loading
of 55 wt % (1 vol %) and a monolith density of 28 mg cm.sup.-3.
4. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of immersing said single-walled carbon nanotube carbon
aerogel in a polymer resin to produce a single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin
comprises immersing said single-walled carbon nanotube carbon
aerogel in polydimethylsiloxane resin.
5. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 4 wherein
said step of curing said single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin comprises curing said
single-walled carbon nanotubes carbon aerogel infiltrated with said
polydimethylsiloxane resin to produce the stiff and electrically
conductive composite of carbon nanotube aerogel and polymer.
6. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of immersing said single-walled carbon nanotube carbon
aerogel in a polymer resin to produce a single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin
comprises immersing said single-walled carbon nanotube carbon
aerogel in epoxy polymer resin.
7. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 4 wherein
said step of curing said single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin comprises curing said
single-walled carbon nanotubes carbon aerogel infiltrated with said
epoxy polymer resin to produce the stiff and electrically
conductive composite of carbon nanotube aerogel and polymer.
8. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 1 wherein
said step of immersing said single-walled carbon nanotube carbon
aerogel in a polymer resin to produce a single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin
comprises immersing said single-walled carbon nanotube carbon
aerogel in polydimethylsiloxane or epoxy resin.
9. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 4 wherein
said step of curing said single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin comprises curing said
single-walled carbon nanotubes carbon aerogel infiltrated with said
polydimethylsiloxane or epoxy resin to produce the stiff and
electrically conductive composite of carbon nanotube aerogel and
polymer.
10. A method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer, comprising the
steps of: dispersing nanotubes in an aqueous media or other media
to form a suspension, adding reactants and catalyst to said
suspension to create a reaction mixture, curing said reaction
mixture to form a wet gel, drying said wet gel to produce a dry
gel, pyrolyzing said dry gel to produce a single-walled carbon
nanotubes carbon aerogel, immersing said single-walled carbon
nanotube carbon aerogel in a polymer resin to produce a
single-walled carbon nanotubes carbon aerogel infiltrated with said
polymer resin, and curing said single-walled carbon nanotubes
carbon aerogel infiltrated with said polymer resin to produce the
stiff and electrically conductive composite of carbon nanotube
aerogel and polymer.
11. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 10
wherein said step of immersing said single-walled carbon nanotube
carbon aerogel in a polymer resin to produce a single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin
includes placing said single-walled carbon nanotube carbon aerogel
immersed in a polymer resin under vacuum.
12. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 10
wherein said step of curing said single-walled carbon nanotubes
carbon aerogel infiltrated with said polymer resin to produce the
stiff and electrically conductive composite of carbon nanotube
aerogel and polymer comprises curing said single-walled carbon
nanotubes carbon aerogel infiltrated with said polymer resin at 60
or 150.degree. C.
13. The method of making a stiff and electrically conductive
composite of carbon nanotube aerogel and polymer of claim 10
wherein said step of providing a single-walled carbon nanotubes
carbon aerogel comprises providing SWNT-CA nanofoams with a SWNT
loading of 55 wt % (1 vol %) and a monolith density of 28 mg
cm.sup.-3.
14. A mechanically stiff, electrically conductive composite of
polymer and carbon nanotubes comprising: a porous carbon material
having 5 to 95% by weight carbon nanotubes and 5 to 95% carbon
binder, and a polymer infiltrated within said porous carbon
material having 5 to 95% by weight carbon nanotubes and 5 to 95%
carbon binder.
15. The mechanically stiff, electrically conductive composite of
polymer and carbon nanotubes of claim 14 wherein said polymer
infiltrated within said porous carbon material having 5 to 95% by
weight carbon nanotubes and 5 to 95% carbon binder is
polydimethylsiloxane or epoxy.
16. A mechanically stiff, electrically conductive composite of
polymers and carbon nanotubes comprising: a mechanically stiff,
electrically conductive composite prepared by the method of
providing a single-walled carbon nanotubes carbon aerogel,
immersing said single-walled carbon nanotube carbon aerogel in a
polymer resin to produce a single-walled carbon nanotubes carbon
aerogel infiltrated with said polymer resin, and curing said
single-walled carbon nanotubes carbon aerogel infiltrated with said
polymer resin to produce the stiff and electrically conductive
composite of carbon nanotube aerogel and polymer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims benefit under 35 U.S.C.
.sctn.119(e) of U.S. Provisional Patent Application No. 61/172,363
filed Apr. 24, 2009 entitled "Route to mechanically stiff,
electrically conductive composites of polymers and carbon
nanotubes," the disclosure of which is hereby incorporated by
reference in its entirety for all purposes.
BACKGROUND
[0003] 1. Field of Endeavor
[0004] The present invention relates to and more particularly to a
composite of polymers and carbon nanotubes, and more particularly,
to a mechanically stiff, electrically conductive composites of
polymers and carbon nanotubes.
[0005] 2. State of Technology
[0006] The treatise, Introduction to Nanotechnology, by Charles P.
Poole, Jr., and Frank J. Owens, John Wiley &. Sons, 2003,
states: "Nanotechnology is based on the recognition that particles
less than the size of 100 nanometers (a nanometer is a billionth of
a meter) impart to nanostructures built from them new properties
and behavior. This happens because particles which are smaller than
the characteristic lengths associated with particular phenomena
often display new chemistry and physics, leading to new behavior
which depends on the size. So, for example, the electronic
structure, conductivity, reactivity, melting temperature, and
mechanical properties have all been observed to change when
particles become smaller than a critical size."
[0007] Carbon nanotubes (CNTs) possess a number of intrinsic
properties that make them promising candidates as filler material
in the design of new composite systems. CNTs can have electrical
conductivities as high as 1.times.10.sup.6 S m.sup.-1, thermal
conductivities as high as 3000 W m.sup.-1K.sup.-1, elastic moduli
of the order of 1 TPa, and are extremely flexible. Unfortunately,
the realization of these properties in macroscopic forms, such as
conductive polymer/CNT composites, has been limited. In these
composites, CNTs are typically dispersed throughout the polymeric
matrix by addition of the individual nanotubes or bundles to
precursor formulations. Since the loading levels and distribution
of the CNTs in the polymer determine the conductivity of the
composite, one of the challenges associated with the fabrication of
conductive polymer composites is attaining uniform dispersion of
the CNTs within the matrix. In addition, dispersion methods can
vary greatly depending on the characteristics of matrix material.
While measurable increases in electrical conductivity can be
achieved through addition of as little as 0.007 wt % CNTs to
polymer matrices, preparation of composites with conductivities
>1 S cm.sup.-1 requires either higher loadings of CNTs (>10
wt %) or specially-designed CNTs that facilitate dispersion in the
matrix. Thus, the fabrication of CNT-polymer composites with
conductivities on par with highly conductive semiconductors and
metals for applications such as electromagnetic interference
shielding can be an expensive endeavor. An attractive alternative
to the dispersion approach for the design of conductive polymer
composites would be the use of a low-density, electrically
conductive CNT foam as a scaffold that can be filled or infiltrated
with the polymer matrix. With this approach, the uniformity of the
dispersed phase, and hence the conductivity of the composite, is
established by the pre-formed CNT network of the scaffold. In
addition, this approach could be general and utilized with a wide
variety of polymer matrices.
SUMMARY
[0008] Features and advantages of the present invention will become
apparent from the following description. Applicants are providing
this description, which includes drawings and examples of specific
embodiments, to give a broad representation of the invention.
Various changes and modifications within the spirit and scope of
the invention will become apparent to those skilled in the art from
this description and by practice of the invention. The scope of the
invention is not intended to be limited to the particular forms
disclosed and the invention covers all modifications, equivalents,
and alternatives falling within the spirit and scope of the
invention as defined by the claims.
[0009] Many challenges remain in the effort to realize the
exceptional mechanical and electrical properties of carbon
nanotubes in composite materials. Applicants have developed highly
electrically conductive and mechanically stiff composites of
polymers and single-walled carbon nanotubes (SWNT). Conductive
SWNT-based nanofoams (aerogels) are used as scaffolds to create
polymer [poly(dimethylsiloxane)] composites. The resulting
composites possess electrical conductivities over 1 S cm.sup.-1 and
exhibit an .about.300% increase in the elastic modulus with as
little as 1 vol % nanotube content.
DEFINITION OF TERMS
[0010] Various terms used in this patent application are defined
below. [0011] CA=Carbon Aerogel [0012] CNT=Carbon Nanotubes [0013]
CA-CNT=Carbon Aerogel & Carbon Nanotube Composite [0014]
Nanofoam=Aerogel [0015] SWNT=Single-Walled Carbon Nanotubes [0016]
DWNT=Double-Walled Carbon Nanotubes [0017] SDBS=Sodium
Dodecylbenzene Sulfonate [0018] MESOPORPOUS=Pore Dia. 2 & 5 mm
[0019] PVA=Polyvinyl Alcohol [0020] CVD=Chemical Vapor Deposition
[0021] TEM=Transmission Electron Microscopy [0022] SEM=Scanning
Electron Microscopy [0023] R/C=Resorcinol to Catalyst Ratios [0024]
RF=Resorcinol and Formaldehyde Solids [0025]
BET=Brunauer-Emmett-Teller [0026] Mechanically Robust=Can withstand
strains greater than 10% before fracture [0027] Electrically
Conductive=Exhibits an electrical conductivity of 10 S/m or greater
[0028] Mechanically Stiff=Elastic modulus greater than 10 MPa
[0029] Ultralow-Density=Exhibits densities less than 50 mg/cc
[0030] Carbon Nanotube-Based Aerogel=Porous carbon material
consisting of 5 to 95% carbon nanotubes by weight [0031]
SWNT-CA=Single-Walled Carbon Nanotubes/Carbon Aerogel [0032]
PDMS/SWNT-CA=Polydimethylsiloxane (PDMS)/Single-Walled Carbon
Nanotubes/Carbon Aerogel
[0033] Applicants used SWNT-CAs as scaffolds to fabricate stiff,
highly conductive polymer (PDMS) composites via the infiltration
method with little to no degradation of the conductive network of
the CNT-based scaffold. Conductivities as high as 1 S cm.sup.-1
have been observed for SWNT loadings as low as 1 vol % (1.2 wt %)
in polymer/SWNT-CA composites. In addition to excellent electrical
conductivity, the polymer composite exhibited an .about.300%
increase in Young's modulus, producing not only a highly
conductive, but a stiffer composite as well. The exceptional
properties of this polymer composite and the general nature of the
fabrication method provide the potential for a whole new class of
composites based on the SWNT-CA scaffold.
[0034] The invention is susceptible to modifications and
alternative forms. Specific embodiments are shown by way of
example. It is to be understood that the invention is not limited
to the particular forms disclosed. The invention covers all
modifications, equivalents, and alternatives falling within the
spirit and scope of the invention as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The accompanying drawings, which are incorporated into and
constitute a part of the specification, illustrate specific
embodiments of the invention and, together with the general
description of the invention given above, and the detailed
description of the specific embodiments, serve to explain the
principles of the invention.
[0036] FIGS. 1A, 1B, 1C, and 1D are SEM images under different
magnifications of conductive PDMS/SWNT-CA composites.
[0037] FIGS. 2A and 2B show partial load-displacement curves for
PDMS and PDMS/CNT composite.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
[0038] Referring to the drawings, to the following detailed
description, and to incorporated materials, detailed information
about the invention is provided including the description of
specific embodiments. The detailed description serves to explain
the principles of the invention. The invention is susceptible to
modifications and alternative forms. The invention is not limited
to the particular forms disclosed. The invention covers all
modifications, equivalents, and alternatives falling within the
spirit and scope of the invention as defined by the claims.
[0039] Applicants synthesized ultralow-density SWNT-based foams
(SWNT-CA) with exceptional electrical and mechanical properties. In
these foams, carbon nanoparticles were used as a binder to
crosslink randomly oriented bundles of single-walled CNTs. These
SWNT-CAs simultaneously exhibited increased stiffness and high
electrical conductivity even at densities approaching 10 mg
cm.sup.-3. The foams are stable to temperatures approaching
1000.degree. C. and have been shown to be unaltered by exposure to
extremely low temperatures during immersion in cryogenic liquids
(such as liquid hydrogen). Therefore, in addition to use as
catalyst supports, sensors, and electrodes, these ultra-light and
robust foams can serve as scaffolds for the preparation of novel
CNT composites. As the conductive network is already established,
the CNT foam can simply be impregnated through the wicking process
with the matrix of choice, ranging from inorganic sols to polymer
melts to ceramic pastes, to prepare a variety of conductive CNT
composites. Applicants used SWNT-CA foam scaffolds for the
synthesis of a highly conductive poly(dimethylsiloxane) (PDMS)
composite. This polymer composite exhibits .about.300% increase in
the elastic modulus relative to the unloaded PDMS elastomer and
electrical conductivity over 1 S cm.sup.-1, the highest
conductivity reported for a polymer/SWNT composite at this CNT
loading level (1.2 wt % or 1 vol %).
[0040] Method of Preparation
[0041] SWNT-CA nanofoams, with a SWNT loading of 55 wt % (1 vol %)
and a monolith density of 28 mg cm.sup.-3, were prepared as
described in:
[0042] (1) Co-Pending patent application Ser. No. 12/652,616 titled
"Mechanically Robust, Electrically Conductive Ultralow-Density
Carbon Nanotube-Based Aerogels," filed Jan. 5, 2009 which is
incorporated herein in its entirety by this reference;
[0043] (2) the journal article, "Mechanically robust and
electrically conductive carbon nanotube foams," by Marcus A.
Worsley, Sergei O. Kucheyev, Joe H. Satcher, Jr., Alex V. Hamza,
and Theodore F. Baumann, in APPLIED PHYSICS LETTERS 94, 073115
(2009) which is incorporated herein in its entirety by this
reference; and
[0044] (3) "Properties of single-walled carbon nanotube-based
aerogels as a function of nanotube loading,) by Marcus A. Worsley,
Peter J. Pauzauskie, Sergei O. Kucheyev, Joseph M. Zaug, Alex V.
Hamza, Joe H. Satcher Jr., and Theodore F. Baumann, in Acta
Materialia 57 (2009) 5131-5136, which is incorporated herein in its
entirety by this reference.
[0045] Once the SWNTs are dispersed, organic sol-gel chemistry is
used crosslink the CNT bundles. Typically, organic sol-gel
chemistry involves the polymerization of organic precursors to
produce highly crosslinked organic gels that can be dried and
pyrolyzed to yield porous carbon structures. In this case, low
concentrations of the sol-gel precursors (resorcinol, formaldehyde)
and catalyst (sodium carbonate) are added to the CNT suspension to
induce polymerization primarily on the walls of the CNT bundles
and, more importantly, at the junctions between adjacent bundles to
form an organic binder.
[0046] The resulting gel is then dried and subsequently pyrolyzed
to convert the organic binder to carbon, yielding the SWNT-CA
nanofoam. The volume percent of SWNTs in each sample was calculated
from the initial mass of SWNTs added, a CNT density of 1.3 g
cm.sup.-3, and the final volume of the sample. The synthesis
process for the SWNT-CA allows for a range of possible shapes and
sizes. SWNT-CA right cylinders with diameters of .about.1 cm and
heights of .about.2 cm have been fabricated.
[0047] Composites were prepared by immersing the as-prepared
SWNT-CA in the polymer resin prior to cure. The immersed SWNT-CA is
placed under vacuum until no more air escaped from the scaffold,
suggesting full infiltration of the resin. The infiltrated SWNT-CA
is then cured at 60.degree. C. to produce the composite. The
dimensions of the composite are approximately equal to those of the
initial SWNT-CA.
[0048] Referring now to the drawings and in particular to FIGS. 1A,
1B, 1C, and 1D, scanning electron microscopy (SEM) images of
PDMS/SWNT-CA composites show that the SWNTs are homogenously
distributed throughout the polymer matrix, suggesting that there is
good wetting at the PDMS/SWNT-CA interface and that the CNT-based
scaffold is intact after infiltration and curing. FIG. 1A is a SEM
image under low magnification of the conductive PDMS/SWNT-CA
composite. FIG. 1B is a SEM image under high magnification of the
conductive PDMS/SWNT-CA composite.
TABLE-US-00001 TABLE 1 Physical properties of SWNT-CA scaffold,
polymers and conductive polymer composites CNT (vol %), Density/g
Material (wt %) cm.sup.-3 E/MPa /S cm.sup.-1 SWNT-CA 1, 55 0.028
1.0 1.12 PDMS 0, 0 1.04 4.2 <0.001 PDMS/SWNT-CA 1, 1.2 1.01 14
1.00
[0049] This observation is supported by the fact that the
electrical conductivity of the SWNT-CA scaffold is maintained even
in a fully dense insulating matrix as shown by Table 1. To
Applicant's knowledge, the conductivity of these polymer composites
(1 S cm.sup.-1) represents the highest conductivity reported for a
polymer/SWNT composite prepared at such a low CNT loading level
(1.2 wt % or 1 vol %). Interestingly, the electrical conductivity
of this composite is on par with the highest reported value for a
polymer/MWNT at a similar .about.1 wt % MWNT loading. As SWNTs
typically contain some fraction of semiconducting tubes, as
compared to MWNTs, which presumably are all metallic, one might
expect a higher conductivity in the MWNT composite with similar CNT
loadings. This observation highlights the need for further study in
this area and suggests that even larger improvements in the
conductivity of polymer composites are possible.
[0050] Referring now to FIGS. 2A and 2B, nanoindentation
measurements show that the PDMS/SWNT-CA experiences very elastic
behavior with an .about.300% increase in Young's modulus as
compared to the case of PDMS. The observed enhancement in modulus
is consistent with the increase expected based on the Halpin-Tsai
model for a nanotube bundle aspect ratio of .about.100. A similar
increase in modulus was observed by Dyke and Tour for a PDMS/SWNT
composite prepared with 1 wt % loading of surface-functionalized
SWNT. The improved modulus is also consistent with the observation
of a polymer shell that coats the CNT bundles in the SEM images as
shown in FIG. 1. The presence of the polymer shell suggests strong
bonding at the PDMS/SWNT-CA interface, a key element in successful
reinforcement. These results highlight the effectiveness of using a
pre-made CNT scaffold for structural reinforcement.
Example 1
[0051] SWNT-CA nanofoams, with a SWNT loading of 55 wt % (1 vol %)
and a monolith density of 28 mg cm.sup.-3, were prepared as
previously reported. Briefly, purified SWNTs were suspended in
deionized water and thoroughly dispersed via sonication.
[0052] Once the SWNTs were dispersed, organic sol-gel chemistry was
used crosslink the CNT bundles. Typically, organic sol-gel
chemistry involves the polymerization of organic precursors to
produce highly crosslinked organic gels that can be dried and
pyrolyzed to yield porous carbon structures. In this case, low
concentrations of the sol-gel precursors (resorcinol, formaldehyde)
and catalyst (sodium carbonate) were added to the CNT suspension to
induce polymerization primarily on the walls of the CNT bundles
and, more importantly, at the junctions between adjacent bundles to
form an organic binder.
[0053] The resulting gel was then dried and subsequently pyrolyzed
to convert the organic binder to carbon, yielding the SWNT-CA
nanofoam. The volume percent of SWNTs in each sample was calculated
from the initial mass of SWNTs added, a CNT density of 1.3 g
cm.sup.-3, and the final volume of the sample. The synthesis
process for the SWNT-CA allows for a range of possible shapes and
sizes. In this report, SWNT-CA right cylinders with diameters of
.about.1 cm and heights of .about.2 cm were fabricated.
[0054] Composites were prepared by immersing the as-prepared
SWNT-CA in the PDMS polymer resin prior to cure. The immersed
SWNT-CA was placed under vacuum until no more air escaped from the
scaffold, suggesting full infiltration of the resin. The
infiltrated SWNT-CA was then cured at 60.degree. C. to produce the
composite. The dimensions of the composite were approximately equal
to those of the initial SWNT-CA.
[0055] Materials and Methods
[0056] Materials. All reagents were used without further
purification. Resorcinol (99%) and formaldehyde (37% in water) were
purchased from Aldrich Chemical Co. Sodium carbonate (anhydrous)
was purchased from J. T. Baker Chemical Co. Highly purified SWNTs
were purchased from Carbon Solutions, Inc.
[0057] SWNT-CA preparation. The SWNT-CAs were prepared using
traditional organic sol-gel chemistry [1]. In a typical reaction,
purified SWNTs (Carbon Solutions, Inc.) were suspended in deionized
water and thoroughly dispersed using a VWR Scientific Model 75T
Aquasonic (sonic power .about.90 W, frequency .about.40 kHz). The
concentration of SWNTs in the reaction mixture was 1.3 wt %. Once
the SWNTs were dispersed, resorcinol (1.235 g, 11.2 mmol),
formaldehyde (1.791 g, 22.1 mmol) and sodium carbonate catalyst
(5.95 mg, 0.056 mmol) were added to the reaction solution. The
resorcinol-to-catalyst ratio (R/C) employed was 200. The amount of
resorcinol and formaldehyde (RF solids) used was 4 wt %. The
sol-gel mixture was then transferred to glass molds, sealed and
cured in an oven at 85.degree. C. for 72 h. The resulting gels were
then removed from the molds and washed with acetone for 72 h to
remove all the water from the pores of the gel network. The wet
gels were subsequently dried with supercritical CO2 and pyrolyzed
at 1050.degree. C. under a N2 atmosphere for 3 h. The SWNT-CAs
materials were isolated as black cylindrical monoliths. Foams with
a SWNT loading of 55 wt % (1 vol %) were prepared by this
method.
[0058] Characterization. Scanning electron microscopy (SEM)
characterization was performed on a JEOL 7401-F at 5-10 keV (20 mA)
in secondary electron imaging mode with a working distance of 2-8
mm. Electrical conductivity was measured using the four-probe
method with metal electrodes attached to the ends of cylindrical
samples. The amount of current transmitted through the sample
during measurement was 100 mA, and the voltage drop along the
sample was measured over distances of 3 to 6 mm. Seven or more
measurements were taken on each sample, and results were averaged.
Mechanical properties were studied by indentation in an MTS XP
Nanoindenter with a Berkovich diamond tip. A series of both
continuous and partial load-unload indents (with 5 cycles and an
unloading percentage of 100% for each cycle) was carried out in
laboratory air at room temperature. The loading rate was
continuously adjusted to keep a constant representative strain rate
of 10.sup.-3 s.sup.-1, defined as (dP/dt)cote/4P, where P is load,
t is time, and e=72.1.degree. is the equivalent cone angle of the
Berkovich tip used. For every cycle, the unloading rate was kept
constant and equal to the maximum loading rate of the cycle. The
Oliver-Pharr method [2] was used to analyze partial load-unload
data in order to calculate the indentation elastic modulus as a
function of the indenter penetration.
Example 2
[0059] SWNT-CA nanofoams, with a SWNT loading of 55 wt % (1 vol %)
and a monolith density of 28 mg cm.sup.-3, were prepared as
previously reported. Briefly, purified SWNTs were suspended in
deionized water and thoroughly dispersed via sonication.
[0060] Once the SWNTs were dispersed, organic sol-gel chemistry was
used crosslink the CNT bundles. Typically, organic sol-gel
chemistry involves the polymerization of organic precursors to
produce highly crosslinked organic gels that can be dried and
pyrolyzed to yield porous carbon structures. In this case, low
concentrations of the sol-gel precursors (resorcinol, formaldehyde)
and catalyst (sodium carbonate) were added to the CNT suspension to
induce polymerization primarily on the walls of the CNT bundles
and, more importantly, at the junctions between adjacent bundles to
form an organic binder.
[0061] The resulting gel was then dried and subsequently pyrolyzed
to convert the organic binder to carbon, yielding the SWNT-CA
nanofoam. The volume percent of SWNTs in each sample was calculated
from the initial mass of SWNTs added, a CNT density of 1.3 g
cm.sup.-3, and the final volume of the sample. The synthesis
process for the SWNT-CA allows for a range of possible shapes and
sizes. In this report, SWNT-CA right cylinders with diameters of
.about.1 cm and heights of .about.2 cm were fabricated.
[0062] Composites were prepared by immersing the SWNT-CA in the
epoxy polymer resin prior to cure. The immersed SWNT-CA was placed
under vacuum until no more air escaped from the scaffold,
suggesting full infiltration of the resin. The infiltrated SWNT-CA
was then cured at elevated temperature of 150.degree. C. to produce
the epoxy/SWNT-CA composite.
[0063] Materials and Methods
[0064] Materials. All reagents were used without further
purification. Resorcinol (99%) and formaldehyde (37% in water) were
purchased from Aldrich Chemical Co. Sodium carbonate (anhydrous)
was purchased from J. T. Baker Chemical Co. Highly purified SWNTs
were purchased from Carbon Solutions, Inc.
[0065] SWNT-CA preparation. The SWNT-CAs were prepared using
traditional organic sol-gel chemistry [1]. In a typical reaction,
purified SWNTs (Carbon Solutions, Inc.) were suspended in deionized
water and thoroughly dispersed using a VWR Scientific Model 75T
Aquasonic (sonic power .about.90 W, frequency .about.40 kHz). The
concentration of SWNTs in the reaction mixture was 1.3 wt %. Once
the SWNTs were dispersed, resorcinol (1.235 g, 11.2 mmol),
formaldehyde (1.791 g, 22.1 mmol) and sodium carbonate catalyst
(5.95 mg, 0.056 mmol) were added to the reaction solution. The
resorcinol-to-catalyst ratio (R/C) employed was 200. The amount of
resorcinol and formaldehyde (RF solids) used was 4 wt %. The
sol-gel mixture was then transferred to glass molds, sealed and
cured in an oven at 85.degree. C. for 72 h. The resulting gels were
then removed from the molds and washed with acetone for 72 h to
remove all the water from the pores of the gel network. The wet
gels were subsequently dried with supercritical CO2 and pyrolyzed
at 1050.degree. C. under a N2 atmosphere for 3 h. The SWNT-CAs
materials were isolated as black cylindrical monoliths. Foams with
a SWNT loading of 55 wt % (1 vol %) were prepared by this
method.
[0066] Characterization. Scanning electron microscopy (SEM)
characterization was performed on a JEOL 7401-F at 5-10 keV (20 mA)
in secondary electron imaging mode with a working distance of 2-8
mm. Electrical conductivity was measured using the four-probe
method with metal electrodes attached to the ends of cylindrical
samples. The amount of current transmitted through the sample
during measurement was 100 mA, and the voltage drop along the
sample was measured over distances of 3 to 6 mm. Seven or more
measurements were taken on each sample, and results were
averaged.
TABLE-US-00002 TABLE 2 Material CNT, vol % (wt %) .sigma.,
Scm.sup.-1 Epoxy 0 <0.001 Epoxy/SWNT-CA 1 (1.2) 1.01
[0067] Additional information about Applicants' invention is
disclosed in the journal article, "Stiff and electrically
conductive composites of carbon nanotube aerogels and polymers," by
Marcus A. Worsley, Sergei O. Kucheyev, Joshua D. Kuntz, Alex V.
Hamza, Joe H. Satcher, Jr., Theodore F. Baumann, in J. Mater.
Chem., 2009, 19, 3370-3372. The J. Mater. Chem., 2009, 19,
3370-3372, is incorporated herein in its entirety by this
reference.
[0068] While the invention may be susceptible to various
modifications and alternative forms, specific embodiments have been
shown by way of example in the drawings and have been described in
detail herein. However, it should be understood that the invention
is not intended to be limited to the particular forms disclosed.
Rather, the invention is to cover all modifications, equivalents,
and alternatives falling within the spirit and scope of the
invention as defined by the following appended claims.
* * * * *