U.S. patent application number 14/807775 was filed with the patent office on 2015-11-19 for simple method for producing superhydrophobic carbon nanotube array.
The applicant listed for this patent is CALIFORNIA INSTITUTE OF TECHNOLOGY. Invention is credited to Adrianus I. Aria, Masoud Beizai, Morteza Gharib.
Application Number | 20150329362 14/807775 |
Document ID | / |
Family ID | 44761121 |
Filed Date | 2015-11-19 |
United States Patent
Application |
20150329362 |
Kind Code |
A1 |
Aria; Adrianus I. ; et
al. |
November 19, 2015 |
SIMPLE METHOD FOR PRODUCING SUPERHYDROPHOBIC CARBON NANOTUBE
ARRAY
Abstract
Efficient methods for producing a superhydrophobic carbon
nanotube (CNT) array are set forth. The methods comprise providing
a vertically aligned CNT array and performing vacuum pyrolysis on
the CNT array to produce a superhydrophobic CNT array. These
methods have several advantages over the prior art, such as
operational simplicity and efficiency.
Inventors: |
Aria; Adrianus I.;
(Cambridge, GB) ; Beizai; Masoud; (Laguna Hills,
CA) ; Gharib; Morteza; (Altadena, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CALIFORNIA INSTITUTE OF TECHNOLOGY |
Pasadena |
CA |
US |
|
|
Family ID: |
44761121 |
Appl. No.: |
14/807775 |
Filed: |
July 23, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13081421 |
Apr 6, 2011 |
9115424 |
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14807775 |
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61321831 |
Apr 7, 2010 |
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Current U.S.
Class: |
428/195.1 |
Current CPC
Class: |
Y10T 428/23993 20150401;
C23C 14/5853 20130101; C01B 32/159 20170801; C01B 32/168 20170801;
C01B 32/17 20170801; B82Y 30/00 20130101; C23C 14/0605 20130101;
C23C 16/26 20130101; C01B 2202/06 20130101; C01B 2202/08 20130101;
Y10T 428/24802 20150115; C01B 2202/02 20130101; C01B 32/158
20170801; B82Y 40/00 20130101; C23C 16/56 20130101 |
International
Class: |
C01B 31/02 20060101
C01B031/02 |
Claims
1. A superhydrophobic carbon nanotube (CNT) array comprising: a
plurality of pyrolized vertically aligned carbon nanotubes (CNTs)
on a substrate surface, wherein the CNTs are without contamination
by either catalyst particles or amorphous carbon, and wherein the
CNTs are at least 85% free from oxygen-containing impurities.
2. The array of claim 1, wherein an outer surface of the CNT array
is at least 95% free from oxygen-containing impurities.
3. The array of claim 1, wherein the plurality of CNTs are anchored
to the surface.
4. The array of claim 1, wherein the plurality of CNTs are selected
from the group consisting of: single-wall CNTs, multiwall CNTs, and
a mixture of single-wall and multiwall CNTs.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 13/081,421, filed Apr. 6, 2011, which claims
priority to U.S. Provisional Application No. 61/321,831, filed Apr.
7, 2010. The contents of these priority documents and all other
references disclosed herein are incorporated in their entirety for
all purposes.
BACKGROUND OF THE INVENTION
[0002] Wetting properties of materials have interested researchers
for decades, due to their relevance to numerous applications. The
wetting properties of a material are dictated by its surface
chemistry (Emsley, J., Chemical Society reviews, 9(1):91-124
(1980); Wenzel, R. N., Industrial & Engineering Chemistry,
28(8):988-994 (1936)) and its topographic structure (Bhushan, B. et
al., Philosophical transactions-Royal Society. Mathematical,
Physical and engineering sciences, 367(1894):1631-1672 (2009); Gao,
L. and McCarthy, T Langmuir, 23(18):9125-9127 (2007); Gao, L. and
McCarthy, T., Journal of the American Chemical Society,
128(28):9052-9053 (2006); Krupenkin, T. et al., Langmuir,
20(10):3824-3827 (2004)).
[0003] Many investigations have been conducted to understand the
surface properties of superhydrophobic materials. A
superhydrophobic surface is extremely difficult to wet; it
typically has a static contact angle higher than 150.degree. and a
contact angle hysteresis less than 10.degree.. Wang, S. and Jiang,
L., Advanced materials, 19(21):3423-3424 (2007); Men, X. et al.,
Applied physics. A, Materials science & processing,
98(2):275-280 (2010); Bhushan, B. et al., Philosophical
transactions-Royal Society. Mathematical, Physical and engineering
sciences, 367(1894):1631-1672 (2009).
[0004] Superhydrophobic materials can be utilized as a protective
coating for creating a self-cleaning, nonstick surface (e.g., for
solar panels) and for preventing biofouling. Scardino, A. J. et
al., Biofouling: The Journal of Bioadhesion and Biofilm Research,
25(8):757-767 (2009). They can be used as electrodes to store
charge energy in a non-aqueous supercapacitor. They can also be
employed to reduce hydrodynamic skin friction drag in laminar and
turbulent flow. Rothstein, J., Annual Review of Fluid Mechanics,
42(1):89-109 (2010). Without intending to be bound by theory, the
existence of a thin layer of trapped air at the liquid-solid
interface is believed to allow a slip velocity at the wall of
superhydrophobic material, reducing shear stress or momentum
transfer from the flow to the wall. Ou, J. et al. Physics of
Fluids, 16:4635-4643 (2004); MM, T.; Kim, J. Physics of Fluids
16:L55-L58 (2004); Daniello, R. J. et al. Physics of Fluids 21,
online publ. no. 085103 (2009). This effect can produce advantages
at macro- or micro-scale. For example, superhydrophobic materials
could reduce fuel consumption of marine vessels and the efficiency
of liquid pipelines. They also could be used in drug delivery
devices to protect the device or drug from contact with blood, and
they could be used to alter the mechanical response of cells.
[0005] In recent years, production of synthetic materials that
exhibit superhydrophobic behavior has been reported. Among these
materials, vertically aligned, multi-walled carbon nanotube arrays
have gained enormous attention, due to their simple fabrication
process and inherent two-length scale topographic structure.
Efforts have been made to modify the surface chemistry of the
carbon nanotube arrays so that their wetting properties can be
tuned precisely. The carbon nanotube arrays can be made hydrophilic
by functionalizing their surfaces with oxygenated surface
functional groups that allow hydrogen bonds with water molecules to
form or hydrophobic by removing those oxygenated surface functional
groups from their surfaces.
[0006] Various oxidation processes can be used to functionalize the
surface of carbon nanotube arrays, such as high-temperature
annealing in air, UV/ozone treatment, oxygen plasma treatment, and
acid treatment. Processes like high-temperature annealing in air
and oxygen plasma treatment would be very costly to implement in
large scale, not to mention highly probable to over-oxidize the
carbon nanotube if an incorrect recipe were used. The acid
treatment is generally hazardous, making it inconvenient to work
with. On the other hand, the UV/ozone treatment is a simple, safe,
and cost-efficient method of producing more hydrophilic carbon
nanotubes.
[0007] However, no analogous simple, safe, cost-efficient process
has yet been identified for producing superhydrophobic carbon
nanotubes. Previously reported studies suggest that complicated
processes are always involved in producing superhydrophobic carbon
nanotube arrays. In order to make these arrays superhydrophobic,
they have to be coated with non-wetting chemicals such as
poly(tetrafluoroethylene) (PTFE), zinc (II) oxide, and
fluoroalkylsilane, (Huang, L. et al., The journal of physical
chemistry, B, 109(16):7746-7748 (2005); Lau, K. et al., Nano Lett.,
3(12):1701-1705 (2003); Feng, L. et al., Advanced materials,
14(24):1857-1860 (2002)) or be modified by plasma treatments, such
as CF4, CH4, and NF3. (Hong, Y. and Uhm, H., Applied physics
letters, 88(24):244101 (2006); Cho, S. et al., Journal of materials
chemistry, 17(3):232-237 (2007)); Balu, B. et al. Langmuir,
24:4785-4790 (2008). However, no prior art has reported a method
for producing a superhydrophobic CNT array surface from pure CNTs
grown by a simple self-assembly process.
[0008] In view of the foregoing, there is a need for a simple,
safe, cost-efficient process for producing superhydrophobic carbon
nanotubes. Such a process could help to speed the investigation and
the commercial application of superhydrophobic carbon nanotubes.
The present invention satisfies these and other needs.
BRIEF SUMMARY OF THE INVENTION
[0009] In one embodiment, the present invention presents a method
for producing a hydrophobic carbon nanotube (CNT) array, the method
comprising:
[0010] providing a vertically aligned CNT array; and
[0011] performing vacuum-pyrolysis on the CNT array to produce the
hydrophobic nanotube array. Preferably, the hydrophobic nanotube
CNT array is superhydrophobic (i.e., a superhydrophobic CNT
array).
[0012] Preferably, the vacuum-pyrolysis step is performed under
reduced pressure of about 0.5 torr to about 10 torr. More
preferably, the vacuum-pyrolysis step is performed under reduced
pressure of about 1 torr to about 5 torr.
[0013] Preferably, the vacuum-pyrolysis step is performed at a
reaction temperature of about 100.degree. C. to about 500.degree.
C. More preferably, the vacuum-pyrolysis step is performed at a
reaction temperature of about 125.degree. C. to about 300.degree.
C.
[0014] Preferably, the vacuum-pyrolysis step has a duration of
about one hour to about five hours.
[0015] Preferably, the vertically aligned CNT is anchored on a
surface. Preferably, the vertically aligned CNT array is a member
selected from a single-wall CNT array, a multiwall CNT array, and a
mixture of a single-wall CNT array and a multiwall CNT array.
[0016] Preferably, the vertically aligned CNT array is synthesized
using a synthesis technique that is selected from chemical vapor
deposition (CVD), laser ablation, and arc discharge. Preferably,
the vertically aligned CNT is provided by a CVD process. In one
aspect of the invention, the CVD process is continuous with the
vacuum-pyrolysis step.
[0017] Preferably, the method for producing a hydrophobic CNT array
further comprises an oxidation step before the vacuum pyrolysis
step to remove amorphous carbon.
[0018] Preferably, the method for producing a hydrophobic CNT array
further comprises removing contamination using the vacuum-pyrolysis
step.
[0019] Preferably, an outer surface of the superhydrophobic CNT
array is at least 85% free from oxygen-containing impurities. More
preferably, the outer surface is at least 95% free from
oxygen-containing impurities.
[0020] Preferably, the CNT array's static water droplet contact
angle increases between about 5% to 45% after the vacuum-pyrolysis
step. Preferably, the water droplet roll-off angle decreases by at
least twofold. Preferably, more than one method is used to assess
the array's superhydrophobicity (e.g., static water droplet contact
angle and water droplet roll-off angle). Preferably, the static
water droplet contact angle is between about 160.degree. to
180.degree.. Preferably, the water droplet roll-off angle is from
about 1.degree. to 5.degree., which means that a water droplet
would not maintain a stable position on the surface of the array
when the surface is tilted more than the roll-off angle.
[0021] Preferably, an outer surface of the superhydrophobic CNT
array is at least 85% free from oxygen-containing impurities. More
preferably, the outer surface is at least 95% free from
oxygen-containing impurities. Still more preferably, the outer
surface is at least 97% free from oxygen-containing impurities.
[0022] In another embodiment, the present invention presents a
hydrophobic CNT array, wherein the hydrophobic CNT array is
produced by any of the methods claimed herein. Preferably, the
hydrophobic CNT array is superhydrophobic.
[0023] These and other aspects, objects and embodiments will become
more apparent when read with the detailed description and drawings
that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1. (a) Low-magnification scanning electron mircroscope
(SEM) image of vertically aligned carbon nanotube array. (b)
High-magnification SEM image of the same array showing the presence
of some entanglements on the array's top surface.
[0025] FIG. 2. (a) Water droplet on a superhydrophobic carbon
nanotube array exhibiting an almost spherical shape with a
170.degree. (.+-.2.degree.) static contact angle. (b) Time-lapse
image of a water droplet bouncing off the surface of a
superhydrophobic carbon nanotube array that was tilted 2.5.degree..
Each frame was taken with a 17 ms interval.
[0026] FIG. 3. Dispersion of carbon nanotubes with various wetting
properties in industrial deionized (DI) water. The degree of CNT
hydrophobicity is decreasing from left to right. The four tubes
from left to right are: the dispersion of superhydrophobic CNTs
(contact angle about 170.degree.); hydrophobic CNTs (contact angle
about 143.degree.); hydrophilic CNTs (contact angle about
75.degree.); and strongly hydrophilic CNTs (contact angle about
30.degree.).
[0027] FIG. 4. A typical Fourier-transform infrared (FTIR) spectra
from superhydrophobic and hydrophilic carbon nanotube arrays
showing strong peaks at 810-1320 cm.sup.-1, 1340-1600 cm.sup.-1,
1650-1740 cm.sup.-1, and 2800-3000 cm.sup.-1, which indicate the
presence of C--O, C.dbd.C, C.dbd.O, and C-Hz stretching modes
respectively.
[0028] FIG. 5. Electrochemical impedance modulus and phase-angle
spectra of carbon nanotube arrays with various wetting properties
in 1 M NaCl aqueous solution. Superhydrophobic and hydrophilic
arrays are indicated by triangle and square markers
respectively.
[0029] FIG. 6. A process diagram for one embodiment of the present
method for making superhydrophobic carbon nanotubes.
DETAILED DESCRIPTION OF THE INVENTION
I. Definition of Terms
[0030] The terms "a," "an," or "the" as used herein not only
includes aspects with one member, but also includes aspects with
more than one member. For example, an embodiment including "a
vertically aligned CNT array" should be understood to present
certain aspects with at least a second vertically aligned CNT
array.
[0031] The term "about" as used herein to modify a numerical value
indicates a defined range around that value. If "X" were the value,
"about X" would generally indicate a value from 0.95X to 1.05X. Any
reference to "about X" specifically indicates at least the values
X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.01X, 1.02X, 1.03X, 1.04X,
and 1.05X. Thus, "about X" is intended to teach and provide written
description support for a claim limitation of, e.g., "0.98X." When
the quantity "X" only includes whole-integer values (e.g., "X
carbons"), "about X" indicates from (X-1) to (X+1). In this case,
"about X" as used herein specifically indicates at least the values
X, X-1, and X+1.
[0032] When "about" is applied to the beginning of a numerical
range, it applies to both ends of the range. Thus, "from about 5 to
45%" is equivalent to "from about 5% to about 45%." When "about" is
applied to the first value of a set of values, it applies to all
values in that set. Thus, "about 7, 9, or 11%" is equivalent to
"about 7%, about 9%, or about 11%."
[0033] A "hydrophobic" surface indicates a surface that is
difficult to wet because of its chemical composition or geometric
microstructure. A hydrophobic surface has a static contact angle
greater than 90.degree..
[0034] The term "or" as used herein should in general be construed
non-exclusively. For example, an embodiment of "a composition
comprising A or B" would typically present an aspect with a
composition comprising both A and B. "Or" should, however, be
construed to exclude those aspects presented that cannot be
combined without contradiction.
[0035] The term "outer surface of the carbon nanotube array" as
used herein includes a side or face of an array that is not
directly affixed to its support. Typically, the outer surface would
be more likely to contact the surrounding environment. For example,
typical tests for roll-off angles would place the drop of liquid in
contact with the outer surface of the array, not the inner surface,
which would be the side of the array affixed to the support.
[0036] A "superhydrophobic" surface indicates a surface that is
extremely difficult to wet because of its chemical composition or
geometric microstructure. A superhydrophobic surface has at least
one of the following characteristics: a static contact angle
greater than 150.degree., a contact angle hysteresis less than
10.degree., or a roll-off angle less than 5.degree.. Preferably, a
superhydrophobic surface has two of these characteristics; more
preferably, all three characteristics.
II. Embodiments
[0037] In one embodiment, the present invention presents a method
for producing a hydrophobic carbon nanotube (CNT) array, the method
comprising:
[0038] providing a vertically aligned CNT array; and
[0039] performing vacuum pyrolysis on the vertically aligned CNT
array to produce the hydrophobic nanotube array. Preferably, the
product CNT array is a superhydrophobic CNT array.
[0040] In one aspect, the present invention provides a vacuum
pyrolysis process to render carbon nanotube arrays
superhydrophobic. Without being bound by theory, such processes are
believed to reverse the effects of oxidation by removing the
oxygenated functional groups from the surface of the carbon
nanotube, while maintaining the macroscopic structures and packing
density of the arrays. Therefore, no deposition of any non-wetting
foreign material (e.g., polyfluorocarbons such as
poly(tetrafluoroethylene); metal salts, such as zinc (II) oxide) on
the array is needed to make them superhydrophobic.
[0041] The temperature, pressure, and duration of the vacuum
pyrolysis can affect the process's efficiency. Typically, a vacuum
pyrolysis process that is performed at a moderate vacuum of 2.5
Torr and a temperature of 250.degree. C. for three hours is
sufficient to completely deoxidize the array.
[0042] Preferably, the vacuum-pyrolysis step is performed under
reduced pressure of about 0.5 torr to about 10 torr, such as 0.5,
0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 torr. More
preferably, the vacuum-pyrolysis step is performed under reduced
pressure of about 1 torr to 5 torr or about 1 torr to 3 torr.
Alternatively, the vacuum-pyrolysis step is performed under reduced
pressure of about 1 torr to 3 torr. In general, lower pressure is
preferable. Without intending to be bound by theory, a lower
pressure during the reaction favors the oxygen-containing
impurities' dissociation from the surface. Higher pressures
disfavor the reaction, prolonging reaction times or even preventing
production of superhydrophobic CNT arrays.
[0043] At sufficiently low pressure, however, further decrease in
pressure produces only minor improvement in the reaction. For
example, reaction pressures of 1 torr and 0.5 torr produces similar
results in the vacuum pyrolysis (e.g., the process produced a
similar superhydrophilic surface after approximately the same total
reaction time).
[0044] When oxygen is present in the ambient gas, however, it can
oxidize the surface of the starting CNT array, especially during
pyrolysis at high temperatures and relatively high pressures (e.g.,
>10 torr). Preferably, the pyrolysis is free from oxygen.
Alternatively and more preferably, the pyrolysis is substantially
free of oxygen, thereby avoiding oxidation of the superhydrophobic
CNT surface.
[0045] Preferably, the vacuum-pyrolysis step is performed at a
reaction temperature of about 100.degree. C. to about 500.degree.
C. such as 100.degree. C., 150.degree. C., 200.degree. C.,
250.degree. C., 300.degree. C., 350.degree. C., 400.degree. C.,
450.degree. C., or 500.degree. C. More preferably, the
vacuum-pyrolysis step is performed at a reaction temperature of
about 125.degree. C. to 300.degree. C. (e.g., about 250.degree.
C.). Low temperatures (e.g., <100.degree. C., <75.degree. C.,
or <50.degree. C.) are disfavored because they may not provide
sufficient energy for the reaction to proceed efficiently. At high
temperatures (e.g., >500.degree. C., >575.degree. C.,
>625.degree. C., >700.degree. C., >800.degree. C., or
>900.degree. C.), the nanotubes or their support (especially if
the support is an organic polymer) may partially or completely
decompose. Generally, higher temperatures produce a higher chance
of decomposition and a faster rate of decomposition.
[0046] Preferably, the vacuum-pyrolysis step has a duration of
about one hour to about five hours. In general, higher temperature
and lower pressures during the pyrolysis step tend to decrease the
time required to produce a superhydrophobic CNT array. In some
aspects, the vacuum pyrolysis can be continuous. In some aspects,
the vacuum pyrolysis includes one or more periods of heating (e.g.,
two, three, or four heating cycles). In certain aspects, the
results of the procedure are dependent on the total heating time
rather than the number of heating cycles. In one preferred aspect,
the present invention provides an iterative process in which the
array is subjected to vacuum pyrolysis, assayed for
superhydrophobicity, and re-exposed to the vacuum-pyrolysis
conditions if the array were not found to be superhydrophobic.
[0047] CNT arrays are characterized by the orientation of the
individual nanotubes composing the array. In a vertically aligned
array, the axis running through the central point of a carbon
nanotube's inner diameter is perpendicular to the array's base
(i.e., if the nanotubes were pulled straight out from their bases,
they would be oriented like the teeth of a comb or the hair on a
head). This is in contrast to a horizontal array (e.g., like beads
on a string) or a disordered array. Preferably, the CNT arrays of
the present invention are vertically aligned arrays. Without
intending to be bound by theory, this vertical alignment minimizes
each CNT's contact area with water, reducing possible van der Waals
forces.
[0048] Preferably, the CNT array is anchored on a surface.
Non-anchored tubes can be scraped off, which makes it harder for
them to maintain their superhydrophobic properties. Preferably, the
CNT array is anchored to a silicon wafer base. Alternatively, the
CNT array is anchored to a polymeric base (e.g., silicone). Sansom,
E.; Rinderknect, D.; Gharib, M. Nanotech., 19, online publ. no.
035302 (2008). Procedures for making anchored, aligned nanotubes
and nanotube devices are known to the skilled artisan (e.g., U.S.
Patent Application 2009/0130370; U.S. Pat. No. 7,491,628; U.S.
Patent Application 2008/0145616; U.S. Patent Application
2010/0196446; Han, Z. J. et al. Appl. Phys. Lett. 94, online publ.
no. 223106 (2009); Men, X.-H. et al. Appl. Phys. A, DOI
10.1007/s00339-009-5425-6 (2009); Li, S. et al. J. Phys. Chem. B.
106, 9274-9276 (2002); and Zhang, L. et al. Langmuir 25:4792-4798
(2009), which are incorporated by reference in their entirety).
[0049] Individual carbon nanotubes within the array can be
single-wall or multiwall. Single-wall nanotubes include one layer
of carbon separating the inside and outside of the nanotube. The
layer may include different patterns of carbon-carbon bonds
depending on its two-dimensional bond geometry. Multiwall nanotubes
include more than one layer of carbon separating the inside and
outside. The multiple layers may be from a sheet wrapping over
itself or from separate, concentric nanotubes. Preferably, the
vertically aligned CNT array is a member selected from a
single-wall CNT array, a multiwall CNT array, and a mixture of a
single-wall CNT array and a multiwall CNT array.
[0050] A CNT array is also characterized by the packing density of
the individual nanotubes composing the array. The packing density
is the number of carbon nanotubes in an area; it is determined by
the average distance between the different nanotubes in the array.
In certain aspects of the present invention, a typical packing
density is about 10.sup.6 CNT/mm.sup.2. At this packing density,
the distance between nanotubes at this density is about three to
four times the diameter of the nanotube. A higher packing density
is generally preferred because more closely associated nanotubes
should make the array's surface more hydrophobic.
[0051] In certain preferred aspects, a major advantage of the
present invention is its ability to make even very short
superhydrophobic CNT arrays. Previous studies have suggested that
short CNT arrays cannot become superhydrophobic. Lau, K. K. S. et
al. Nano Lett. 3:1701-1705 (2009); Liu, H. et al. Soft Matter,
2:811-821 (2006). However, by using vacuum-pyrolysis methods, CNT
arrays can be made superhydrophobic regardless of length. For
example, a CNT array as short as 10 .mu.m can be converted into a
superhydrophobic array.
[0052] Preferably, the vertically aligned CNT array is synthesized
using a synthesis technique that is selected from chemical vapor
deposition (CVD), laser ablation, and arc discharge, using
procedures commonly known to the skilled artisan. Preferably, the
vertically aligned CNT is provided by a CVD process (e.g., Seo, J.
W. et al. New J. Physics, 5, 120.1-120.22 (2003)).
[0053] Carbon nanotube arrays can also be prepared using other
procedures known to the skilled artisan, such as those set forth in
U.S. Pat. No. 7,491,628; U.S. Patent Application No. 2008/0145616;
U.S. Patent Application No. 2003/0180472; and U.S. Patent
Application 2010/0247777.
[0054] In some aspects, the CVD process is continuous with (or at
least partially continuous with) the vacuum-pyrolysis step. For
example, if the CVD process is continuous with the vacuum-pyrolysis
step, the vacuum-pyrolysis process can be merged with the CNT
growth process to form a continuous process (e.g., if there is no
need to anchor the CNT array). During the cool-down from CVD
synthesis of nanotubes, a vacuum is applied rather than a flowing
inert gas. In some aspects, this modification eliminates a need for
inert gas purging.
[0055] Some CNT arrays can contain residual catalyst particles or
amorphous carbon, e.g., from the CNT synthesis. These impurities
may create defects in the array. In certain aspects, the process
set forth in the present invention further comprises an oxidation
step before the vacuum-pyrolysis step to remove amorphous carbon.
Preferably, if analytical techniques indicated a significant amount
of catalyst particle leftovers or amorphous carbon in the CNT
array, the array could be treated with ozone to oxidize the
impurities before the vacuum pyrolysis (e.g., by exposure to 185 nm
UV radiation in air for 1 hr).
[0056] Various other oxidation processes can be used to remove
catalyst particles leftovers or amorphous carbon other than the
ozone treatment. These other processes include hot air annealing,
oxygen plasma treatment, and acid (usually a mixture of nitric acid
and hydrochloric acid) treatment (e.g., Tohji, K. et al. Nature,
383:679 (1996)). While hot air annealing, oxygen plasma treatment,
and acid treatment are each more effective in removing the catalyst
particles leftovers and amorphous carbon than the ozone treatment,
these processes are harsher so that the chance to over-oxidize the
CNT array is high.
[0057] The easiest way to find catalyst particle leftovers and
amorphous carbon is by performing electron microscopy analysis on
the CNT samples; preferably, by using transmission electron
microscopy (TEM) on the CNT samples. If the catalyst particles are
only found inside the CNTs and if the thickness of amorphous carbon
is much less than the diameter of the CNTs, the preliminary
oxidation is unnecessary.
[0058] In one aspect, a preliminary oxidation is performed if (i)
there is any sign of more than one catalyst particle on the average
(e.g., preferably, the mean) found on the outer surface of each CNT
or (ii) the thickness of amorphous carbon is more than the diameter
of the CNT. For example, if TEM indicated 76 surface catalyst
particles in a sample comprising 75 nanotubes, the array would be
oxidized, but if TEM indicated only 75 or fewer particles in the
sample, the array would not be oxidized. Alternatively, if the
average number of outer surface catalyst particles is at least one,
the array is oxidized to remove them. In some preferred aspects,
about 25 to 250, about 50 to 200, or about 60 to 200 CNTs are
examined by TEM to make this determination.
[0059] Some CNT arrays can contain other impurities or contaminants
that may adversely affect the array's properties. These impurities
may be volatile or may decompose into volatile products under
vacuum-pyrolysis conditions. In certain aspects, the process set
forth in the present invention further comprises removing
contamination using the vacuum-pyrolysis step.
[0060] Preferably, the vacuum-pyrolysis step removes oxygen-bearing
impurities from an outer surface of the CNT array. More preferably,
the oxygen-bearing impurities are organic (i.e.,
carbon-containing). Oxygen-bearing, organic impurities can include
organic compounds containing hydroxyl, carbonyl (e.g., aldehyde or
ketone), or carboxyl (e.g., carboxylic acid) groups. Alternatively,
the impurities can be organic, oxygen-bearing groups chemically
bonded to the surface of the CNT array (e.g., a carboxy group with
a covalent, carbon-carbon bond attaching it to a carbon
nanotube).
[0061] Preferably, the water droplet roll-off angle decreases at
least two-fold; preferably, the angle decreases from two- to
twenty-fold. This is the general assay for superhydrophobicity, but
others can be used. Preferably, more than one method is used (e.g.,
static water droplet contact angle and water droplet roll-off
angle). Preferably, the static water droplet contact angle
increases between about 5% to about 45%, such as 5%, 10%, 15%, 20%,
25%, 30%, 35%, 40%, or 45% after the vacuum-pyrolysis step.
[0062] Preferably, the static water droplet contact angle is
between about 160.degree. to 180.degree. (alternatively, the static
water droplet contact angle is at least 150.degree.; preferably, at
least 160.degree.; and more preferably, at least 170.degree.).
Surfaces with static water droplet contact angles of at least
160.degree. are extremely hydrophobic, making them particularly
useful (i.e., they are not subject to the "petal effect" allowing
water to be pinned to the surface). Preferably, the water droplet
roll-off angle is from about 1.degree. to 5.degree., such as about
1.degree., 2.degree., 3.degree., 4.degree., or 5.degree.; more
preferably, the roll-off angle is from about 1.degree. to 3.degree.
(e.g., about 1.degree.). Preferably, the contact angle hysteresis
is at most 10.degree., such as between about 1.degree. to
10.degree. (e.g., about 1.degree., 2.degree., 3.degree., 4.degree.,
5.degree., 6.degree., 7.degree., 8.degree., 9.degree., or
10.degree.); more preferably, the contact angle hysteresis is at
most 5.degree..
[0063] The outer surface of the CNT array can also be monitored for
oxygen-bearing bonds as a way to identify the method's progress.
Such monitoring can be carried out with conventional methods (e.g.,
quantitative FTIR). Preferably, an outer surface of the
superhydrophobic CNT array is at least 85% free from
oxygen-containing impurities. More preferably, the outer surface is
at least 95% free from oxygen-containing impurities. Still more
preferably, the outer surface is at least 97% free from
oxygen-containing impurities. Alternatively, the outer surface can
be free from oxygen-containing impurities to the instrument's
effective limit of detection.
[0064] In another embodiment, the present invention presents a
superhydrophobic CNT array, wherein the hydrophobic CNT array is
produced by any of the methods claimed herein. Preferably, the
hydrophobic CNT array is superhydrophobic.
[0065] In certain preferred aspects, a major advantage of the
present invention is the use of a simple, high-yielding procedure
(vacuum pyrolysis) to produce superhydrophobic CNT arrays. Known
methods of generating superhydrophobic CNT arrays are generally
low-yielding, may involve corrosive reagents (e.g., the corrosive
gases used in plasma treatment), and may change other properties of
the CNT array's surface (e.g., treatment with metal oxide, which
makes a continuous metal oxide surface). The present invention
presents an alternative method for generating superhydrophobic
arrays that is simpler and more efficient. In addition, it better
preserves the microstructure of the CNT array.
[0066] In certain preferred aspects, another advantage of the
present invention is the effects of the removal of
oxygen-containing impurities from the CNT array's outer surface to
produce superhydrophobic CNT arrays. Known methods of generating
superhydrophobic CNT arrays are generally low-yielding, may involve
corrosive reagents (e.g., the corrosive gases used in plasma
treatment), and may change other properties of the CNT array's
surface (e.g., treatment with metal oxide, which makes a continuous
metal oxide surface). The present invention's removal of
oxygen-containing impurities is a simpler and more efficient method
of producing superhydrophobic arrays. In addition, it better
preserves the microstructure of the CNT array.
III. Examples
[0067] It is understood that the examples and embodiments described
herein are for illustrative purposes only. Various modifications or
changes thereof will be suggested to persons skilled in the art,
and they are to be included within the purview of this application
and the scope of the appended claims. In addition, each reference
provided herein is incorporated by reference in its entirety to the
same extent as if each reference was individually incorporated by
reference.
Example 1
Preparation of Superhydrophobic CNT Arrays
[0068] Carbon nanotube arrays used in this study were grown by the
standard chemical vapor deposition (CVD) technique on a silicon
substrate, using hydrogen and ethylene as the precursor gas.
Sansom, E. et al., Nanotechnology, 19(3):035302 (2008). The average
length of all the arrays was chosen to be about 14.+-.4 .mu.m (FIG.
1a), which was about the minimum length that can be made using CVD
techniques while preserving the overall vertical alignment and high
packing density of the arrays (FIG. 1b). The main reason this
length was chosen is for the difficulties in producing a
superhydrophobic surface out of short carbon nanotube arrays
reported in the previously reported studies. Lau, K. et al., Nano
letters, 3(12):1701-1705 (2003).
[0069] The CNT arrays were subjected to vacuum pyrolysis, typically
at a vacuum of 2.5 Torr and a temperature of 250.degree. C. for
three hours. After the pyrolysis, the array's static contact angle
was tested by conventional methods to determine its hydrophobicity.
If conventional analytical methods indicated that the array was not
superhydrophobic (e.g., if the static contact angle were less than
160.degree.), the array was re-subjected to vacuum pyrolysis for
another three hours (or longer if re-analysis after the second
pyrolysis indicated that the array was still not
superhydrophobic).
[0070] After being subjected to the vacuum-pyrolysis process, the
carbon nanotube arrays exhibited extreme water repellency. Their
superhydrophobicity was demonstrated by their ultra-high static
contact angle of 170.degree. (.+-.2.degree.) (FIG. 2a) and very low
contact angle hysteresis of 3.degree. (.+-.1.degree.). These arrays
also exhibit a very low roll-off angle of 1.degree. (cf. FIG. 2b,
though FIG. 2b shows a roll-off angle of 2.5.degree.). The static
contact angle, contact angle hysteresis, and roll-off angles were
measured using standard techniques known by the skilled artisan
(e.g., contact angles were measured with a contact angle
goniometer).
Example 2
Comparison of Post-Vacuum-Pyrolysis CNTs with Control CNTs
[0071] Comparison of water-based dispersions of the pre- and
post-vacuum pyrolysis carbon nanotubes provides further evidence of
the vacuum pyrolysis products' superhydrophobicity.
Superhydrophobic CNT arrays were prepared by the method of Example
1. These were compared with non-superhydrophobic control arrays
prepared by the same initial procedure, but not subjected to vacuum
pyrolysis (contact angle about 143.degree.) as well as hydrophilic
CNTs (contact angle about 75.degree.); and strongly hydrophilic
CNTs (contact angle about 30.degree.). The water-based dispersions
are obtained by scraping the nanotube arrays from their growth
substrates and ultrasonically dispersing them in standard
industrial deionized water for at least two hours.
[0072] The experiment demonstrated that nanotubes that have been
subjected to vacuum-pyrolysis were not dispersed in water even
after being sonicated for more than two hours (FIG. 3). In
contrast, the more hydrophilic nanotubes can be dispersed easily in
water. From this finding, one can conclude that the
vacuum-pyrolysis treatment is capable of completely deoxidizing
individual nanotubes within the array.
Example 3
FTIR and Electrochemical Characterization of Superhydrophobic CNT
Surface Chemistry
[0073] To study the effect of the vacuum-pyrolysis process on the
surface chemistry of the hydrophilic CNTs, FTIR spectrometry
analysis was conducted on array samples using standard methods for
the skilled artisan. The superhydrophobic samples were compared
with hydrophilic samples (contact angle 30.degree., as per Example
2's strongly hydrophilic CNTs). A small portion of the CNT array
(<1 mm.sup.2) was scraped from the growth substrate, dispersed
in 50 ml deuterated dichloromethane, drop-cast onto a KBr window,
and then dried overnight under mild vacuum (>5 torr) and without
heating to remove the solvent. The FTIR spectrometry analysis was
subsequently performed on the sample using an infrared laser with a
wavelength of 2500-12500 nm.
[0074] Four strong bands were detected on the hydrophilic arrays at
810-1320 cm.sup.-1, 1340-1600 cm.sup.-1, 1650-1740 cm.sup.-1, and
2800-3000 cm.sup.-1, which indicate the presence of C--O, C.dbd.C,
C.dbd.O and C--H.sub.x stretching modes respectively (FIG. 4). The
peaks at 970, 1028, 1154 and 1201 cm.sup.-1 correspond to C--O
stretching modes (Kuznetsova, A. et al., Chemical Physics Letters,
321(3-4):292-296 (2000)), and the broad shoulder band at 810-1320
cm.sup.-1 suggests the existence of C--O--C bonds from ester
functional groups. Sham, M. and Kim, J., Carbon, 44(4):768-777
(2006); Socrates, G., Infrared and Raman characteristic group
frequencies: tables and charts, 3rd ed. ed., Wiley: Chichester
(2001); Mawhinney, D. et al., Journal of the American Chemical
Society, 122(10):2383-2384 (2000); Kim, U. et al., Physical Review
Letters, 95(15):157402 (2005). The peaks at 1378, 1462, 1541 and
1574 cm.sup.-1 indicate the presence of C.dbd.C stretching
vibration modes of the carbon nanotube walls. Kuznetsova, A. et
al., Chemical Physics Letters, 321(3-4):292-296 (2000); Sham, M.
and Kim, J., Carbon, 44(4):768-777 (2006); Socrates, G., Infrared
and Raman characteristic group frequencies: tables and charts, 3rd
ed. ed., Wiley: Chichester (2001); Mawhinney, D. et al., Journal of
the American Chemical Society, 122(10):2383-2384 (2000). The narrow
band at a peak of 1703 cm.sup.-1 corresponds to C.dbd.O stretching
modes of either quinone or carboxylic acid ester groups.
Kuznetsova, A. et al., Chemical Physics Letters, 321(3-4):292-296
(2000); Sham, M. and Kim, J., Carbon, 44(4):768-777 (2006);
Mawhinney, D. et al., Journal of the American Chemical Society,
122(10):2383-2384 (2000); Kim, U. et al., Physical Review Letters,
95(15):157402 (2005).
[0075] These FTIR spectra show that the strength of all peaks
associated with the C--O and C.dbd.O stretching modes of the
superhydrophobic array is significantly lower than that of the
hydrophilic one, suggesting that the oxygen desorption process does
take place during vacuum-pyrolysis treatment. The strength of the
C.dbd.C stretching modes also seems to decrease slightly, implying
that the graphitic structures of the carbon nanotubes were still
intact after the vacuum-pyrolysis treatment. The triplet with peaks
at 2848, 2915 and 2956 cm.sup.-1 indicate C--H.sub.x bonds from the
hydrocarbon functional group. Kim, U. et al., Physical Review
Letters, 95(15):157402 (2005). This hydrocarbon triplet peaks seems
to be unaffected by vacuum-pyrolysis process, implying that these
peaks may be associated with contaminations in the FTIR instrument
(Kim, U. et al., Physical Review Letters, 95(15):157402 (2005)) and
have nothing to do with the wetting properties of the arrays.
[0076] Just like their wetting properties, the electrochemical
properties of carbon nanotube arrays are dictated by their surface
chemistry. As shown by the measured impedance modulus and phase
angle spectra, carbon nanotube arrays with different wetting
properties exhibit different electrochemical properties (FIG. 5).
For the superhydrophobic array, the frequency of constant impedance
spans for three decades from 1 kHz to 1 MHz. On the other hand, the
frequency of constant impedance for the hydrophilic arrays spans
for six decades from 1 Hz to 1 MHz. At a low frequency of 10 mHz,
the impedance modulus of the superhydrophobic array is about two
orders of magnitude higher than that of the hydrophilic one. The
impedance of the hydrophilic and the superhydrophilic CNT arrays
were found to be about 650.OMEGA. and 162 k.OMEGA. respectively at
frequency of 12 mHz in 1 M NaCl solution. This finding implies that
the specific capacitance for hydrophilic and the superhydrophilic
CNT array is about 3.3 F/g and 9.1 mF/g respectively.
[0077] Without being bound by theory, these findings are the result
of a thin film of air on the interface between the surface of the
superhydrophobic array and the aqueous electrolyte. This air film
inhibits electrons transfer from the arrays and obstructs protons
in the electrolyte to approach the surface of the array. On the
other hand, the hydrophilic array is completely wetted by the
aqueous electrolyte such that there is no air film that may inhibit
electron transfer from the arrays. Because of the air film's
presence film, the impedance of the superhydrophobic array was
measured to be two orders of magnitude higher than that of the
hydrophilic one.
Example 4
Flow-Diagram of One Embodiment of the Present Invention
[0078] This example illustrates a flow diagram of one embodiment of
the present invention (FIG. 6). The embodiment provides a vacuum
pyrolysis process (100) to render carbon nanotube arrays
superhydrophobic. In this instance, beginning with a vertically
aligned CNT array (110), the array is analyzed for any catalyst
particles or amorphous carbon contamination (117). If either or
both of these are present, an oxidation process is performed to
remove the contamination (121). Next, a vacuum-pyrolysis step is
performed at a reaction temperature and duration as indicated
herein (e.g., a temperature selected from about 100.degree. C. to
about 500.degree. C. and a duration selected from about one hour to
five hours) (125). After the vacuum-pyrolysis step is performed,
the static contact angle is determined. In certain embodiments, if
the static contact angle is within specification (136), the
roll-off angle is determined. In one aspect, if the roll-off angle
is within specification (147), the superhydrophobic CNT array is
produced (163). If either of the static angle or the roll-off angle
are not within specification, the vacuum-pyrolysis step (125) may
be performed iteratively to produce the superhydrophobic CNT array
(163).
CONCLUSIONS
[0079] In conclusion, the discoveries reported herein show that the
wetting properties of carbon nanotube arrays can be altered by
controlling the amount of oxygenated functional groups that are
bonded to their surface. The CNT arrays can be made hydrophilic by
oxidizing with, e.g., hot air, strong acids, UV/ozone, or oxygen
plasma. The CNT arrays can be made superhydrophobic by deoxidizing
with vacuum-pyrolysis treatment at moderate vacuum and temperature.
Such vacuum-pyrolysis treatment is capable of removing the
oxygenated functional groups that are attached to the CNTs'
surfaces.
[0080] All publications and patent applications cited in this
specification are herein incorporated by reference as if each
individual publication or patent application were specifically and
individually indicated to be incorporated by reference. Although
the foregoing invention has been described in some detail by way of
illustration and example for purposes of clarity of understanding,
it will be readily apparent to those of ordinary skill in the art
in light of the teachings of this invention that certain changes
and modifications may be made thereto without departing from the
spirit or scope of the appended claims.
* * * * *