U.S. patent application number 10/373638 was filed with the patent office on 2004-01-22 for molecular-level thermal management materials comprising single-wall carbon nanotubes.
Invention is credited to McElrath, Kenneth O., Smith, Kenneth A..
Application Number | 20040013598 10/373638 |
Document ID | / |
Family ID | 27766010 |
Filed Date | 2004-01-22 |
United States Patent
Application |
20040013598 |
Kind Code |
A1 |
McElrath, Kenneth O. ; et
al. |
January 22, 2004 |
Molecular-level thermal management materials comprising single-wall
carbon nanotubes
Abstract
The present invention relates to devices, processes and
materials comprising single-wall carbon nanotubes wherein the
single-wall carbon nanotubes serve to transport heat to or from a
nanometer scale region wherein that heat is generated or
dissipated. Because of their small physical size, excellent heat
conductivity, and relatively large surface area, single-wall carbon
nanotubes are novel in their function as nanometer-scale agents for
heat transport. Appropriately configured in association with a
source of heat such as the catalyst for an exothermic
polymerization reaction, single wall carbon nanotubes can
effectively conduct heat away from the reaction site. This thermal
management on a molecular level enables a new class of materials
and processes in all areas where heat transport is important.
Additionally, new materials such as improved polymer compositions
are produced by processes that are thermally-managed at the
molecular level by the objects of this invention.
Inventors: |
McElrath, Kenneth O.;
(Houston, TX) ; Smith, Kenneth A.; (Houston,
TX) |
Correspondence
Address: |
Kenneth D. Goodman
Williams, Morgan & Amerson, P.C.
Suite 1100
10333 Richmond
Houston
TX
77042
US
|
Family ID: |
27766010 |
Appl. No.: |
10/373638 |
Filed: |
February 24, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60358876 |
Feb 22, 2002 |
|
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Current U.S.
Class: |
423/447.2 |
Current CPC
Class: |
B82Y 30/00 20130101;
F28F 13/185 20130101; C09K 5/14 20130101 |
Class at
Publication: |
423/447.2 |
International
Class: |
D01F 009/12 |
Claims
What is claimed is:
1. A molecular level thermal management device comprising at least
one single wall carbon nanotube, wherein: at least some portion of
a single-wall carbon nanotube shares a nanometer-scale region with
a heat source, the single-wall carbon nanotube is in contact with
an environment to which it can transfer heat, and the single-wall
carbon nanotube transfers heat from the heat source to said
environment.
2. The device of claim 1, wherein the single-wall carbon nanotube
is in contact with the heat source.
3. The device of claim 1, wherein the heat source is a chemical
reaction.
4. The device of claim 1, wherein the heat source is an electronic
device.
5. The device of claim 1, wherein the device forms part of a
fixed-bed reactor, a micro-reactor, a catalyst support structure,
or a semiconductor electronic assembly.
6. A material comprising at least one device of claim 1.
7. A molecular level thermal management device comprising at least
one single wall carbon nanotube, wherein: at least some portion of
a single-wall carbon nanotube shares a nanometer-scale region with
a heat sink, the single-wall carbon nanotube is in contact with an
environment from which it can receive heat, and the single-wall
carbon nanotube transfers heat from said environment to the heat
sink.
8. The device of claim 7, wherein the single-wall carbon nanotube
is in contact with the heat sink.
9. The device of claim 7, wherein the heat sink is a chemical
reaction.
10. The device of claim 7, wherein the heat sink is an electronic
device.
11. The device of claim 7, wherein the device forms part of a
fixed-bed reactor, a micro-reactor, a catalyst support structure,
or a semiconductor electronic assembly.
12. A material comprising at least one device of claim 2.
13. A polymerization catalyst system comprising a polymerization
catalyst and a plurality of single-wall carbon nanotubes.
14. The polymerization catalyst system of claim 13, wherein the
polymerization catalyst is adapted to catalyze olefin
polymerization.
15. A polymerization process, wherein at least one monomer is
polymerized in the presence of a catalyst system that comprises a
polymerization catalyst and a plurality of single-wall carbon
nanotubes.
16. The process of claim 15, wherein the polymerization process
forms at least one polyolefin.
17. A polymer produced by polymerization of at least one monomer in
the presence of a polymerization catalyst system that comprises a
polymerization catalyst and a plurality of single-wall carbon
nanotubes.
18. The polymer of claim 17, wherein at least one monomer is an
olefin and the polymer is a polyolefin.
19. A high-energy material comprising at least one device according
to claim 1, and at least one explosive, rocket fuel, incendiary
chemical, or combination thereof.
20. A high-energy material comprising at least one device according
to claim 7, and at least one explosive, rocket fuel, incendiary
chemical, or combination thereof.
21. A fixed-bed polymerization reactor that comprises at least one
fixed-bed that comprises at least one polymerization catalyst
attached to single-wall carbon nanotubes which are formed into a
macroscopic porous structure which allows diffusion of at least one
monomer to an active polymerization site on the polymerization
catalyst and transport of at least one polymer and heat away from
the active site and out of the fixed-bed.
Description
[0001] This application claims priority from U.S. provisional
application 60/358,876, filed on Feb. 22, 2002, which is
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to devices, materials, and processes
comprising single-wall carbon nanotubes wherein the single-wall
carbon nanotubes serve to transport heat to or from a nanometer
scale region wherein that heat is generated or dissipated.
Single-wall carbon nanotubes (SWNT), commonly known as
"buckytubes," have been the subject of intense research since their
discovery due to their unique properties, including high strength,
stiffness, and thermal and electrical conductivity. SWNT are
fullerenes consisting essentially of sp.sup.2-hybridized carbon
atoms typically arranged in hexagons and pentagons. For background
information on single-wall carbon nanotubes, see B. I. Yakobson and
R. E. Smalley, American Scientist, Vol. 85, July-August, 1997, pp.
324-337. Multi-wall carbon nanotubes are nested single-wall carbon
cylinders and possess some properties similar to single-wall carbon
nanotubes. However, since single-wall carbon nanotubes have fewer
defects than multi-wall carbon nanotubes, the single-wall carbon
nanotubes are generally stronger and more conductive, both
thermally and electrically. Additionally, single-wall carbon
nanotubes have considerably higher available surface area per gram
of carbon than multi-wall carbon nanotubes.
[0003] In many electrical, chemical and physical processes, heat is
generated or required in nanometer-scale regions, often by
molecular-level interactions of a chemical or physical nature. In
circumstances where heat is generated, that heat often has
detrimental effects and must be removed from the process. In
processes where heat is required, it is most preferable that the
heat be delivered at a precise location on a molecular scale, but
that, heretofore, has generally been impossible. Even though heat
is generated or required by specific molecular-level interactions,
the transport of heat in most chemical and physical processes is
provided through its transport in bulk materials. Therefore, it is
anticipated that the art of chemical and physical processes will be
advanced by an invention that enables enhanced transport of heat
generated or required in molecular-level interactions, particularly
if those means operate at the nanometer scale.
SUMMARY OF THE INVENTION
[0004] This invention relates to devices, materials, and processes
that incorporate single-wall carbon nanotubes as heat transfer
agents to improve the efficacy of heat transport to and from
nanometer-scale regions. A nanometer-scale region, for the purposes
of this invention, is one contained within a sphere of 30
nanometers in diameter, more preferably 10 nanometers in diameter,
and most preferably 3 nanometers in diameter. Said nanometer-scale
region can contain either a heat source or a heat sink.
Molecular-level processes that act as heat sources or heat sinks
occur within such nanometer-scale regions. If a portion of one or
more single-wall carbon nanotubes lies within this nanometer-scale
region, it can dispense or absorb heat there and effectively
transport heat to or from that region. This invention enables a new
level of heat transfer engineering in many bulk-scale chemical and
physical processes, by providing for thermal management at the
molecular level.
[0005] One embodiment of the invention is a molecular level thermal
management device comprising at least one single wall carbon
nanotube. In this device, at least some portion of a single-wall
carbon nanotube shares a nanometer-scale region with a heat source,
the single-wall carbon nanotube is in contact with an environment
to which it can transfer heat, and the single-wall carbon nanotube
transfers heat from the heat source to said environment.
[0006] Another embodiment of the invention is a molecular level
thermal management device comprising at least one single wall
carbon nanotube. In this device, at least some portion of a
single-wall carbon nanotube shares a nanometer-scale region with a
heat sink, the single-wall carbon nanotube is in contact with an
environment from which it can receive heat, and the single-wall
carbon nanotube transfers heat from said environment to the heat
sink.
[0007] Another embodiment of the invention is a polymerization
catalyst system that comprises a polymerization catalyst and a
plurality of single-wall carbon nanotubes. Additional embodiments
are a polymerization process, wherein at least one monomer is
polymerized in the presence of the catalyst system, and the polymer
produced by that process.
[0008] Another embodiment of the invention is a fixed-bed
polymerization reactor. The reactor comprises at least one
fixed-bed that comprises at least one polymerization catalyst
attached to single-wall carbon nanotubes. The nanotubes are formed
into a macroscopic porous structure, which allows diffusion of at
least one monomer to an active polymerization site on the
polymerization catalyst and transport of at least one polymer and
heat away from the active site and out of the fixed-bed.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
[0009] Various embodiments of this invention use single-wall carbon
nanotubes to enable transport of heat to or from a nanometer scale
region. Implementation of this nanometer-scale heat transport
enables new devices, materials, and processes.
[0010] For clarity in the following description, however, this
invention will initially be discussed with respect to an embodiment
where single-wall carbon nanotubes serve to remove heat from a
nanometer-scale region where the heat is being produced. In this
embodiment, some portions of single-wall carbon nanotubes are
placed in close proximity to the region of heat generation, and
other portions of said nanotubes lie between that region and an
environment that enables removal of heat from the single-wall
carbon nanotube surface. In this embodiment, single-wall carbon
nanotubes are molecular-level heat transfer conduits that enable
heat removal from heat-generating molecular-level processes.
Single-wall carbon nanotubes are individual molecules that are
excellent conductors of heat. The small physical size of
single-wall carbon nanotubes permits portions of them to be located
in contact with or in very close proximity to the heat source. Heat
from the source can be transferred to the single-wall carbon
nanotubes through any of the known means of thermal energy
transfer, including, but not limited to, convection, radiation,
vibrational energy transfer, electronic energy- transfer, mass
transfer and accommodation, molecular heat conduction, and
combinations thereof. Upon receiving the heat energy within the
nanometer-scale region, the single-wall carbon nanotubes will then
efficiently conduct heat away from the nanometer-scale region and
distribute that heat over the single-wall carbon nanotube surface.
If that surface is in an environment where heat can be removed from
that surface, then the locally-generated heat will be effectively
dissipated, and the temperature at the heat-generation region will
be lowered. The environment for heat removal is one that allows
transfer of heat from the single-wall carbon nanotube surface by
any of the known means of thermal energy transfer, including, but
not limited to, convection, radiation, vibrational energy transfer,
electronic energy transfer, mass transfer and accommodation,
molecular heat conduction, and combinations thereof. The device of
this invention can comprise more than one single wall carbon
nanotube and heat can be transferred from one single-wall carbon
nanotube to another as it is transported. Single-wall carbon
nanotubes are particularly effective in redistribution of heat
because they are nanometer scale structures with excellent thermal
conductivity and relatively large surface areas.
[0011] One embodiment of the heat-removal device described above is
a catalyst system for an exothermic polymerization process. In this
embodiment, the catalyst system comprises single-wall carbon
nanotubes and a polymerization catalyst wherein the single-wall
carbon nanotubes are directly associated with the catalyst. This
association can, without limitation, include physisorption,
chemisorption, and/or chemical bonding of the single-wall carbon
nanotubes to the catalyst. The chemical bonding can be covalent,
ionic or a combination of both, and can occur on the single-wall
carbon nanotubes' open ends, closed ends, side walls, defects in
the side walls and combinations thereof. This catalyst system
composition enables formation of new high-molecular weight
polymers, improved polymerization processing methods, and new
composite compositions comprising single-wall carbon nanotubes and
polymers. During the polymerization process the catalyst
participates in an exothermic polymerization reaction forming a
polymer material, and the local heat produced in a nanometer-scale
region containing the catalyst is carried away by the nanotube
material.
[0012] Another embodiment of this invention is a material
comprising the devices described above. For instance, one can
create a bulk composition comprised of single-wall carbon nanotube
material combined with entities which serve as a heat sources or
sinks. Such a composition could, for instance, be a material
comprising single-wall carbon nanotubes with a catalyst that can
participate an exothermic chemical reaction.
[0013] Another embodiment of this invention is a process utilizing
one or more of the devices of this invention, and products of that
process. One example would be the polymerization process for
polyolefins discussed in Example 1, and products of that
process.
[0014] This invention admits many variations. In other embodiments,
the highly porous nature of single-wall carbon nanotube mats and
felts can enable new types of polymerization reactors, such as
fixed bed reactors, micro-reactors, catalyst support films, and
chemically-active materials comprising the present invention.
Suspended single-wall carbon nanotube catalysts with polymers
adsorbed on or wrapped around the nanotubes can be left in the
polymer material to provide new compositions of polymers reinforced
with highly dispersed nanotubes. Because of the intimate proximity
of the single-wall carbon nanotube structure to the polymerization
site, these materials have enhanced polymer alignment and comprise
polymers with molecular weights and mechanical properties enhanced
over those produced by other polymerization procedures. Such new
compositions will have improved properties such as strength,
electrical conductivity and processability into stronger films and
fibers. More generally, this invention admits the fabrication of a
wide range of materials and devices where thermal management is
important on a nanometer scale.
[0015] Other examples include providing heat to endothermic
reactions wherein the catalytic entity is placed near the end of a
single-wall carbon nanotube or bundle of such nanotubes. Yet other
examples include placing one or more single-wall carbon nanotubes
with one or more of their ends in proximity to one or more
electronic devices (e.g. transistors, diodes, multi-junction
devices, resistors, thermistors, sensors, reactive elements,
transducers, memory elements, and combinations thereof) in
semiconductor electronics assemblies wherein the single-wall carbon
nanotubes are added during an appropriate processing step. In this
embodiment, the single wall carbon nanotubes carry away heat
generated in junctions in the semiconductor assemblies. Another
example is in the creation of high-energy materials, such as
explosives, rocket fuel and incendiary chemicals where one seeks to
control the burning rate by molecular-level thermal management. In
other applications for energy-absorbing materials, molecular-level
thermal management can provide heat conduction that enables a
chemical reaction front to propagate through a material, enabling
dissipation of energy in the material. This application of the
invention is particularly useful in auto bodies and armor, and
other materials designed to absorb energy in a controlled-failure
scenario.
[0016] In one embodiment, single-wall carbon nanotubes are
incorporated in an olefin polymerization catalyst system to provide
a more effective catalytic process. Another embodiment of the
invention comprises improved polymer compositions generated by such
a catalyst system. In one particular embodiment, for example, a
device comprises single-wall carbon nanotubes that are configured
in proximity to nanometer-scale regions where heat is generated
during a process. Here, that configuration can be fabricated by
contacting an olefin polymerization catalyst with single-wall
carbon nanotubes ends, sides or combinations thereof. Another
embodiment of the invention is a material comprising such devices.
A further embodiment of the invention is a method that uses said
material in a chemical process, such as the production of a
polyolefin. Another embodiment of the invention comprises any
product of that production process. These products can include
polyolefin materials whose properties exceed those of known
polyolefin materials in the areas of molecular weight, molecular
orientation, strength, toughness, and thermal stability. This
method of polyolefin production also naturally produces a material
which is a composite of polyolefin polymer and single-wall carbon
nanotubes, and that material and the process for its production are
also embodiments of this invention.
[0017] Olefin polymerization catalysts are known to those skilled
in the art of manufacturing polyethylene, polypropylene,
polybutenes, polyisobutylenes, polystyrenes and various copolymers,
such as ethylene-butene copolymers, ethylene-propylene copolymers
and terpolymers, isobutylene-isoprene copolymers (butyl rubber) and
other polymers. Such polymerization catalysts include aluminum,
magnesium and titanium halides, conventional Ziegler-Natta, newer
metallocene and other "single-site" catalysts such as zirconium-
and titanium-based metallocenes with alumoxane or other
non-coordinating anionic co-catalysts, such as perfluorophenyl
borane compounds.
[0018] Association of chemical entities with single-wall carbon
nanotubes can be done by means known to those skilled in the art.
Examples of association include chemical bonding, van der Waals
interactive forces, polar interactions, and indirect contact
through other materials.
[0019] Incorporation of single-wall carbon nanotubes in olefin
polymerization catalyst systems provides an improved catalyst
composition that has functionality previously unknown in olefin
polymerization catalysts. This functionality derives from the
ability of the single-wall carbon nanotubes to receive and transfer
heat away from the point at which the polymerization reaction is
occurring. Additionally this invention includes a composition of
matter comprising association of a catalytic moiety (such as an
olefin polymerization catalyst) with one or more single-wall carbon
nanotubes that serve as a "molecular-level heat transfer
agent".
[0020] Olefin polymerization is a highly exothermic reaction. The
heat generated when the monomer reacts with the catalyst and is
inserted into the growing polymer chain must be transferred away
from the catalyst site. If this is not done, a runaway reaction can
result as the catalyst heats up and the reaction proceeds faster
releasing more heat. To control heat generation, catalysts and
reactor systems are designed to limit the rate of polymerization.
In addition, local heating at the catalyst site can cause
limitations in the molecular weight of the polymers made because,
at elevated temperatures, the rates of termination reactions
increase in comparison to the rates for propagation (chain growth)
reactions. Furthermore, local heating can cause catalyst
deactivation. By conducting heat away from the catalyst site, the
single-wall carbon nanotubes will allow higher molecular weight
polymers to be made at faster rates and with less catalyst
deactivation. Additionally, the enhanced molecular-level thermal
management provided by the catalyst composition described here
helps ensure a more uniform temperature throughout the
polymerization section of the reactor and mitigates against
formation of "runaway hot spots" in the reactor where polymer
growth termination and unwanted catalyst deactivation can
occur.
[0021] The preceding description of specific embodiments of the
present invention is not intended to be a complete list of every
possible embodiment of the invention. Persons skilled in this field
will recognize that modifications can be made to the specific
embodiments described here that would be within the scope of the
following claims.
* * * * *