U.S. patent application number 12/955843 was filed with the patent office on 2011-10-20 for membranes with functionalized carbon nanotube pores for selective transport.
This patent application is currently assigned to The Regents of the University of California. Invention is credited to Olgica Bakajin, Francesco Fornasiero, Sangil Kim, Aleksandr Noy, Hyung Gyu Park.
Application Number | 20110253630 12/955843 |
Document ID | / |
Family ID | 41398795 |
Filed Date | 2011-10-20 |
United States Patent
Application |
20110253630 |
Kind Code |
A1 |
Bakajin; Olgica ; et
al. |
October 20, 2011 |
MEMBRANES WITH FUNCTIONALIZED CARBON NANOTUBE PORES FOR SELECTIVE
TRANSPORT
Abstract
Provided herein composition and methods for nanoporous membranes
comprising single walled, double walled, or multi-walled carbon
nanotubes embedded in a matrix material. Average pore size of the
carbon nanotube can be 6 nm or less. These membranes are a robust
platform for the study of confined molecular transport, with
applications in liquid and gas separations and chemical sensing
including desalination, dialysis, and fabric formation.
Inventors: |
Bakajin; Olgica; (San
Leandro, CA) ; Noy; Aleksandr; (Belmont, CA) ;
Fornasiero; Francesco; (Oakland, CA) ; Park; Hyung
Gyu; (Zurich, CH) ; Kim; Sangil; (Livermore,
CA) |
Assignee: |
The Regents of the University of
California
Lawrence Livermore National Security, LLC
|
Family ID: |
41398795 |
Appl. No.: |
12/955843 |
Filed: |
November 29, 2010 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US2009/045675 |
May 29, 2009 |
|
|
|
12955843 |
|
|
|
|
61056940 |
May 29, 2008 |
|
|
|
Current U.S.
Class: |
210/651 ;
210/500.27; 427/244; 977/742; 977/750; 977/842; 977/962 |
Current CPC
Class: |
C02F 2103/08 20130101;
B01D 71/024 20130101; B01D 2257/504 20130101; B01D 2257/102
20130101; B01D 61/025 20130101; B01D 69/148 20130101; A61M 1/341
20140204; Y02A 20/131 20180101; Y02C 10/10 20130101; C02F 1/44
20130101; B01D 71/02 20130101; B01D 2256/10 20130101; A61M 1/34
20130101; A61M 2205/3306 20130101; B01D 67/0072 20130101; B01D
2323/36 20130101; C02F 2305/08 20130101; B01D 61/027 20130101; B01D
71/027 20130101; B82Y 30/00 20130101; B01D 71/021 20130101; C02F
1/442 20130101; B01D 67/0079 20130101; B01D 2325/18 20130101; Y02C
20/40 20200801; B01D 2256/24 20130101; B01D 2256/22 20130101; B01D
53/228 20130101 |
Class at
Publication: |
210/651 ;
427/244; 210/500.27; 977/742; 977/842; 977/962; 977/750 |
International
Class: |
B01D 71/02 20060101
B01D071/02; C02F 1/44 20060101 C02F001/44; B01D 67/00 20060101
B01D067/00; B01D 61/00 20060101 B01D061/00; B05D 5/00 20060101
B05D005/00; B01D 71/06 20060101 B01D071/06 |
Goverment Interests
STATEMENT OF GOVERNMENT SUPPORT
[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 process for the preparation of a membrane of selective
permeability, said process comprising: (a) wetting with a first
liquid phase a microporous support that is wettable by said first
liquid phase, said first liquid phase having dissolved therein a
first polymerizable species; (b) contacting said microporous
support thus wetted with a second liquid phase that is at least
partially immiscible with said first liquid phase and in which is
dissolved a second polymerizable species, one or both of said first
and second liquid phases having carbon nanotubes randomly dispersed
therein of an average length; (c) causing said first and second
polymerizable species to form a layer of a solid polymer over an
outer surface of said microporous support; (d) sealing said layer
to form a substantially continuous barrier around said nanotubes,
said barrier having a thickness that is less than said average
length of said nanotubes; and (e) recovering from said first and
second liquid phases said microporous support with said layer
adhering to said outer surface.
2. The process of claim 1, wherein said first and second
polymerizable species are mutually reactive by interfacial
polymerization to form said solid polymer that is insoluble in said
first and second liquid phases and that adheres to said microporous
support.
3. The process of claim 1, wherein steps (c) and (d) are performed
in sequence, said layer of step (c) is defined as an intermediate
layer and is a porous layer, and step (d) comprises forming an
outer layer over said intermediate layer, said outer layer forming
said barrier, and said outer layer having a thickness that is less
than said average length of said nanotubes.
4. The process of claim 1, wherein said carbon nanotubes are
single-walled carbon nanotubes.
5. The process of claim 1, wherein a ratio of said average length
of said carbon nanotubes to said thickness of said layer is from
about 1.3 to about 5.
6. The process of claim 1, wherein said average length of said
carbon nanotubes is from about 100 nm to about 2000 nm.
7. The process of claim 1, wherein said carbon nanotubes have an
inner diameter of about 0.4 nm to about 5 nm.
8. The process of claim 1, wherein said microporous support is a
member selected from the group consisting of polyethersulfone,
polysulfone, nylon, and polyester, and said first liquid phase is a
polar phase.
9. The process of claim 8, wherein the second and optionally the
third liquid phases are non-polar liquids.
10. The process of claim 1, wherein said first liquid phase is a
solution of said first polymerizable species in a polar solvent
selected from the group consisting of water, an alcohol, and a
glycol, and said second liquid phase is a solution of said second
polymerizable species in a non-polar solvent selected from the
group consisting of benzene, a halobenzene, an alkyl benzene, a
C.sub.5-C.sub.12 alkane, a halo-substituted C.sub.5-C.sub.12
alkane, and an alkyl-substituted C.sub.5-C.sub.12 alkane.
11. The process of claim 1, wherein said first polymerizable
species is an aromatic polyamine and said second polymerizable
species is an aromatic polycarboxylic acid halide.
12. The process of claim 1, wherein said first polymerizable
species is m-phenylenediamine and said second polymerizable species
is trimesoyl chloride.
13. A process for the preparation of a membrane of selective
permeability, said process comprising: (a) wetting with an aqueous
phase a microporous support selected from polysulfone or
polyethersulfone that is wettable by said aqueous phase, said
aqueous phase having dissolved therein m-phenylenediamine; (b)
contacting said microporous support thus wetted with a solvent
phase that is at least partially immiscible with said aqueous phase
and in which is dissolved trimesoyl chloride, one or both of said
aqueous and solvent phases having carbon nanotubes randomly
dispersed therein of an average length; (c) causing said
m-phenylenediamine and trimesoyl chloride to form a layer of a
solid polymer over an outer surface of said microporous support;
(d) sealing said layer to form a substantially continuous barrier
around said nanotubes, said barrier having a thickness that is less
than said average length of said nanotubes; and (e) recovering from
said aqueous and solvent phases said microporous support with said
layer adhering to said outer surface.
14. A membrane of carbon nanotubes formed by the process of claim
1.
15. A membrane with embedded carbon nanotubes, said membrane
comprising a plurality of carbon nanotubes open at both ends and
embedded in a solid, substantially continuous polymeric matrix,
said polymeric matrix having a thickness that is less than an
average of the lengths of said carbon nanotubes, said carbon
nanotubes having substantially random orientations relative to said
membrane and yet oriented such that at least a portion of said
plurality of carbon nanotubes have both open ends protruding from
said membrane to provide fluid communication through said
membrane.
16. The membrane of claim 14, further comprising a layer of
microporous material supporting said polymeric matrix.
17. The membrane of claim 14, wherein a ratio of said average of
the lengths of said carbon nanotubes to said thickness of said
polymeric matrix is from about 1.3 to about 5.
18. A method for desalination of water, said method comprising
passing said water through a membrane comprising a plurality of
nanotubes open at both ends and embedded in a solid, substantially
continuous polymeric matrix, said polymeric matrix having a
thickness that is less than an average of the lengths of said
nanotubes, said nanotubes having substantially random orientations
relative to said membrane and yet oriented such that at least a
portion of said plurality of nanotubes have both open ends
protruding from said membrane to provide fluid communication
through said membrane.
19. The method of claim 18, wherein said membrane further comprises
a layer of microporous material supporting said polymeric
matrix.
20. The method of claim 18, wherein the ratio of said average of
the lengths of said nanotubes to said thickness of said polymeric
matrix is from about 1.3 to about 5.
21. The method of claim 18, wherein said polymeric matrix has a
substantially planar exposed outer surface and contains from about
2.5.times.10.sup.8 to about 1.times.10.sup.12 nanotubes per square
centimeter of said exposed outer surface.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application of
and claims priority under 35 U.S.C. .sctn.120 to PCT/US2009/045675,
filed on May 29, 2009, which claims priority under 35 U.S.C.
.sctn.119(e) of U.S. Provisional Application No. 61/056,940, filed
on May 29, 2008, each of which is hereby incorporated by reference
in its entirety.
FIELD OF THE INVENTION
[0003] Provided herein are carbon nanotubes membranes and
nanofiltration membranes whose through-pores are made of sub-6 nm
carbon nanotubes with entrance modified by functional groups.
Charges at the pore entrance and the small diameter of the pores
ensures that these membranes are able to efficiently exclude ions
and small molecules while maintaining ultra-fast fluid
permeation.
BACKGROUND OF THE INVENTION
[0004] Ion transport across cellular membranes is essential to many
of life's processes, such as electrical signaling in nerves,
muscles, and synapses or cell's maintenance of homeostatic balance.
Biological systems achieve rapid, selective and ultra-efficient
trans-membrane mass transport by employing a large variety of
specialized protein channels of nanometer or subnanometer size
(Hille (2001) Ion Channel of Excitable Membranes (Sinauer
Associates, Inc., Sunderland)). High resolution x-ray structures,
protein sequencing, targeted mutations, and biophysical
characterizations have provided new insights on the link between
nanochannel protein architecture, transport rates, selectivity, and
gating properties.
[0005] Interestingly, these studies have shown that membrane
nanochannels share several common features. For example, aquaporins
(Sui et al. (2001) Nature 414:872-878; and Murata et al. (2000)
Nature 407:599-605), proton (Wikstrom (1998) Curr. Optin. Struct.
Biol. 8:480-488, Wikstrom et al. (2003) BBA-Bioenergetics
1604:61-65), and ion channels (Jiang et al. (2002) Nature
417:515-522; Jiang et al. (2002) Nature 417:523-526; Bass et al.
(2002) Science 298:1582-1587; Doyle et al. (1998) Science
280:69-77; Miyazawa et al. (2003) Nature 423:949-955; and Kuo et
al. (2003) Science 300:1922-1926) all have relatively narrow and
hydrophobic pore regions. By contrast, the selectivity filter
regions of membrane ion channels are enriched with charged
residues.
[0006] Despite progress made in recent decades, the complex
macromolecular nature of these biological machines still
complicates the understanding of the underlying mechanisms
responsible for fast mass transport, selectivity, gating, and the
functional role of hydrophobic pore lining and charged
functionalities. Thus, it is desirable to create simplified,
biomimetic nanochannels that could help to clarify the physics of
ion permeation at the nanoscale, as well as create the next
generation of membranes that employ efficient molecular transport
for applications ranging from water purification to separations of
biomolecules. Recent theoretical and experimental works have
proposed carbon nanotubes (CNTs) as candidates for such simplified
models of biological channels. The graphite walls of CNTs form
hydrophobic pores with diameters close to those of biological
channels.
[0007] Molecular dynamics (MD) and theoretical studies have shown
single-file transport for water along the nanotube axis
(Berezhkovskii & Hummer (2002) Phys. Rev. Lett. 89:4; Hummer et
al. (2001) Nature 414:188-190; Hummer (2007) Mol. Phys.
105:201-207; and Kalra et al. (2003) Proc. Natl. Acad. Sci. USA
100:10175-10180) that is reminiscent of the water wires observed in
aquaporins (Sui et al. (2001) Nature 414:872-878; and Murata et al.
(2000) Nature 407:599-605). Predicted (Hummer et al. (2001) Nature
414:188-190; Hummer (2007) Mol. Phys. 105:201-207; and Kalra et al.
(2003) Proc. Natl. Acad. Sci. USA 100:10175-10180) and
experimentally measured (Holt et al. (2006) Science 312:1034-1037;
and Majumder et al. (2005) Nature 438:44-44) water transport rates
through CNTs are extremely large and comparable to measured values
for aquaporins. MD simulations have revealed the water ordering
near the smooth hydrophobic walls to facilitate enhanced,
frictionless water transport.
[0008] In addition, chemical inertness of the carbon nanotube
sidewalls facilitate specific functionalization of the CNT pore
entrance with different functionalities. This specificity provides
an opportunity to create an artificial "selectivity filter" that
could impart gating properties to a CNT (Hinds et al. (2004)
Science 303:62-65; Majumder et al. (2005) J. Am. Chem. Soc.
127:9062-9070; Majumder et al. (2007) Langmuir 23:8624-8631;
Nednoor et al. (2005) Chem. Mater. 17:3595-3599; Nednoor et al.
(2007) J. Mater. Chem. 17:1755-1757; and Chopra et al. (2005) Adv.
Funct. Mater. 15:858-864).
[0009] Reverse osmosis (RO) is currently a method for desalination
of seawater. Seawater is an abundant reservoir of elemental water
on Earth and as such is one of the important potential sources of
fresh water that may be necessary for normal society functioning.
Seawater has high salinity, which makes it unsuitable for most of
human use, therefore seawater needs to be separated from its salt
content in the desalination process.
[0010] In a typical RO desalination process, an applied pressure in
excess of the osmotic pressure of the salt solution forces the
solution through a semipermeable membrane that allows permeation of
water while retaining the dissolved ions. This process requires
high pressure on the high concentration side of the membrane,
ranging from .about.15 bar for brackish water to .about.60 bar for
seawater. Fresh water then collects on the downstream side of the
membrane and the concentrated brine from the upstream side of the
membrane is then discarded.
[0011] Current membranes used for RO desalination are based on
cellulose acetate or aromatic polyamide polymers and present a thin
dense barrier layer in the polymer matrix where most separation
occurs. Since the barrier layer is effectively non-porous, the
transport of water through the membrane occurs at low rates through
a "solution-diffusion" mechanism: water absorbs on the upstream
side of the membrane, diffuses down the chemical potential gradient
(largely due to pressure gradient), and desorbs downstream. Salt
transport occurs in a similar fashion; however, the driving force
for transport is mainly the concentration gradient and the salt
flux is insensitive to the pressure gradient. Thus, to achieve good
water fluxes and high salt rejection, a very large applied pressure
is required. As a consequence, the energy cost associated to the
separation process is large. Also, these membranes may tend to foul
easily.
[0012] Biological pores regulate the cellular traffic of a large
variety of solutes, often with high selectivity and fast flow
rates. These pores share several common structural features: the
inner surface of the pore is frequently lined with hydrophobic
residues and the selectivity filter regions often contain charged
functional groups. Hydrophobic, narrow diameter carbon nanotubes
can provide a simplified model of membrane channels by reproducing
these critical features in a simpler and more robust platform.
Previous studies demonstrated that carbon nanotube pores can
support a water flux comparable to natural aquaporin channels.
SUMMARY OF THE INVENTION
[0013] Provided herein are sub-6-nm, aligned carbon nanotube
membrane nanofluidic platform for selective transport through the
pores of the nanotubes. In some embodiments, negatively charged
groups are introduced at the opening of the carbon nanotubes by
plasma treatment. In some embodiments, positively charged groups
are introduced at the opening of the carbon nanotubes by chemical
modification.
[0014] In one aspect, there is provided an array of carbon
nanotubes functionalized on at least one end of at least one of the
nanotubes, wherein the nanotubes have average pore size of less
than 6 nm or less.
[0015] In another aspect, there is provided a membrane for enhanced
fluid transport comprising, consisting essentially of, or
consisting of an array of carbon nanotubes functionalized on at
least one end of at least one of the nanotubes, wherein the
nanotubes have average pore size of less than 6 nm or less and a
matrix material disposed between the carbon nanotubes.
[0016] In another aspect, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of: a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm having at least one
functionalized nanotube and a matrix material disposed between the
carbon nanotubes.
[0017] In yet another aspect, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of: a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm with a charge density of
about 1-3 mM and have at least one functionalized nanotube; and a
matrix material disposed between the carbon nanotubes.
[0018] In yet another aspect, there is provided a chip comprising,
consisting essentially of, or consisting of a plurality of
membranes, as defined herein.
[0019] In yet another aspect, there is provided a method of
separating an analyte from a fluid by passing the fluid containing
the analyte through the carbon nanotubes or the membranes
comprising, consisting essentially of, or consisting of the carbon
nanotubes or the membranes, as defined herein.
[0020] In one aspect, there is provided a process for the
preparation of a membrane of selective permeability, the process
comprising, consisting essentially of, or consisting of:
[0021] (a) wetting with a first liquid phase a microporous support
that is wettable by the first liquid phase, the first liquid phase
having dissolved therein a first polymerizable species;
[0022] (b) contacting the microporous support thus wetted with a
second liquid phase that is at least partially immiscible with the
first liquid phase and in which is dissolved a second polymerizable
species, one or both of the first and second liquid phases having
carbon nanotubes randomly dispersed therein of an average
length;
[0023] (c) causing the first and second polymerizable species to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0024] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0025] (e) recovering from the first and second liquid phases the
microporous support with the layer adhering to the outer
surface.
[0026] In one aspect, there is provided a process for the
preparation of a membrane of selective permeability, the process
comprising, consisting essentially of, or consisting of:
[0027] (a) wetting with an aqueous phase a microporous support
selected from polysulfone or polyethersulfone that is wettable by
the aqueous phase, the aqueous phase having dissolved therein
m-phenylenediamine;
[0028] (b) contacting the microporous support thus wetted with a
solvent phase that is at least partially immiscible with the
aqueous phase and in which is dissolved trimesoyl chloride, one or
both of the aqueous and solvent phases having carbon nanotubes
randomly dispersed therein of an average length;
[0029] (c) causing the m-phenylenediamine and trimesoyl chloride to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0030] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0031] (e) recovering from the aqueous and solvent phases the
microporous support with the layer adhering to the outer
surface.
[0032] In one aspect, there is provided a membrane with embedded
carbon nanotubes, the membrane comprising, consisting essentially
of, or consisting of a plurality of carbon nanotubes open at both
ends and embedded in a solid, substantially continuous polymeric
matrix, the polymeric matrix having a thickness that is less than
an average of the lengths of the carbon nanotubes, the carbon
nanotubes having substantially random orientations relative to the
membrane and yet oriented such that at least a portion of the
plurality of carbon nanotubes have both open ends protruding from
the membrane to provide fluid communication through the
membrane.
[0033] In one aspect, there is provided a method for desalination
of water, the method comprising, consisting essentially of, or
consisting of passing the water through a membrane comprising a
plurality of nanotubes open at both ends and embedded in a solid,
substantially continuous polymeric matrix, the polymeric matrix
having a thickness that is less than an average of the lengths of
the nanotubes, the nanotubes having substantially random
orientations relative to the membrane and yet oriented such that at
least a portion of the plurality of nanotubes have both open ends
protruding from the membrane to provide fluid communication through
the membrane.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] This invention will be further described with reference
being made to the accompanying drawings.
[0035] FIG. 1 illustrates (a) Cross section schematic of a CNT
membrane representing the silicon support chip, the aligned DWNTs,
the filling silicon nitride matrix, and the CNT tips functionalized
with carboxylic groups. (b) Cross section SEM image of the
CNT/silicon nitride composite showing the gap-free coating of
silicon nitride. (c) Photographs of the membrane sides exposed to
the feed (top) and to the permeate (bottom). (d) Time variation of
permeate volume per unit area of freestanding membrane during the
filtration of 0.6 mM K.sub.3Fe(CN).sub.6 solution. The resulting
permeation flux, F, is .about.1000 larger than the calculated value
with the Hagen-Poiseuille equation, F.sub.HP. (e) Schematic of the
nanofiltration cell showing the column of feed solution (1)
pressurized at P=0.69 bar, the CNT membrane (2), the permeate
solution (3), feed (4) and permeate (5) chambers. (f) Capillary
electrophoresis chromatogram for feed (dotted line) and permeate
(solid line) showing a 91% exclusion of the ferricyanide anion
after nanofiltration of a 1.0 mM K.sub.3Fe(CN).sub.6 solution.
[0036] FIG. 2 illustrates an effect of pH on measured rejection for
a 0.5 mM pyrenetetrasulfonic acid tetrasodium (PTSNa.sub.4)
solution: (a) UV spectra for feed (dotted line) and permeate at
pH=3.8 (dashed line) and pH=7.2 (solid line); (b) anion and cation
rejection at pH=3.8 and pH=7.2.
[0037] FIG. 3 illustrates a dependence of K.sub.3Fe(CN).sub.6
(circles) and KCl (diamonds) rejections on (a) solution
concentration and (b) Debye length. Filled markers correspond to
anions, while empty markers correspond to cations. Dashed black
vertical line in (b) marks the average CNT diameter. Dotted line
and dashed line show the rejection coefficients calculated using
Donnan membrane equilibrium theory (Eq. 1) for a 1:3 and a 1:1
electrolyte. To illustrate the trends predicted by the Donnan
theory, the membrane charge density is set equal to 3.0 mM.
[0038] FIG. 4 illustrates rejection coefficients (bars) measured
for six salt solutions that have the same equivalent concentration
but different ion valence. Points (filled circles) indicate
rejections calculated with the Donnan theory, Eq. 1, with a
membrane charge density c.sub.x.sup.m=2.0 mM (this value was chosen
to fit K.sub.3Fe(CN).sub.6 rejection). This density corresponds to
about 7 charged groups per nanotube (see Supporting Information in
Example 1).
[0039] FIG. 5 illustrates comparison of anion and cation rejection
coefficients for: (a) two different membranes, M1 and M2, in
contact with a 0.3 mM K.sub.3Fe(CN).sub.6 solution, (b) with 1.0 mM
KCl solution, and (c) for the same membrane M1 in contact with a
1.0 mM K.sub.3Fe(CN).sub.6 solution.
[0040] FIG. 6 illustrates rejection coefficient for six salt
solutions having the same equivalent concentration but different in
valence. Bars represent experimental data for anions and cations:
points indicate rejections calculated with the hindered transport
(HT) theory, Eq. 2.
[0041] FIG. 7 shows nanofiltration of 1 mM KCl solution at 10 psi.
a) rejection coefficient and b) water fluxes measured for DWNT
membranes, and commercial nanofiltration membranes NF90 and
NF270.
[0042] FIG. 8 illustrates DNA based programmable gating of CNT
membranes.
[0043] FIG. 9 illustrates CNT embodiments with functionalization of
the end or the pore entrance of the CNT.
[0044] FIG. 10 illustrates various embodiments of the membrane
structure of the invention.
[0045] FIG. 11 illustrates various embodiments of the membrane
structure on a backing
[0046] FIG. 12 illustrates another embodiment of the membrane
structure of the invention.
[0047] FIG. 13 illustrates a membrane structure where the CNTs are
aligned by using an electric field.
[0048] FIG. 14 illustrates a comparison of water vapor fluxes
measured for a carbon nanotube membrane and for two commercial
PTFE-based membranes that are used in waterproof-breathable
fabrics.
[0049] FIG. 15 illustrates breathability of CNT membrane compared
with GoreTex.TM. and PTFE membrane at 40% relative humidity.
[0050] FIG. 16 illustrates comparison of silica membrane with CNT
membrane in terms selectivity and permeance.
[0051] FIG. 17 illustrates an anion rejection for binary
K.sub.2SO.sub.4/KCl salt solutions as a function of chloride anion
mole fraction X.sub.Cl.sub.- in the feed solution.
[0052] FIG. 18 illustrates a membrane structure where a carbon
nanotube array is filled with a parylene polymer by vapor phase
infiltration.
DETAILED DESCRIPTION OF THE INVENTION
1. Definitions
[0053] Before the present compositions, and methods are described,
it is to be understood that the invention is not limited to the
particular methodologies, protocols, and reagents described, as
these may vary. It is also to be understood that the terminology
used herein is intended to describe particular embodiments of the
present invention, and is in no way intended to limit the scope of
the present invention as set forth in the appended claims.
[0054] Unless defined otherwise, all technical and scientific terms
used herein have the same meanings as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the present
invention, the preferred methods and materials are now described.
All technical and patent publications cited herein are incorporated
herein by reference in their entirety. Nothing herein is to be
construed as an admission that the invention is not entitled to
antedate such disclosure by virtue of prior invention.
[0055] In accordance with the present invention and as used herein,
the following terms are defined with the following meanings, unless
explicitly stated otherwise.
[0056] As used in the specification and claims, the singular form
"a", "an" and "the" include plural references unless the context
clearly dictates otherwise.
[0057] All numerical designations, e.g., pH, temperature, time,
concentration, and molecular weight, including ranges, are
approximations which are varied (+) or (-) by increments of 0.1 or
1.0, where appropriate. It is to be understood, although not always
explicitly stated that all numerical designations are preceded by
the term "about". It also is to be understood, although not always
explicitly stated, that the reagents described herein are merely
exemplary and that equivalents of such are known in the art.
[0058] As used herein, the term "acidic group" refers to the group
which donates a hydrogen ion to the base or which when dissolved in
water gives a solution with hydrogen ion activity greater than pure
water, i.e., a pH less than 7.0. The acidic groups are negatively
charged groups at pH higher than 7.0.
[0059] As used herein, the term "amide" refers to --CONH.sub.2
group.
[0060] As used herein, the term "amine" refers to --NH.sub.2
group.
[0061] As used herein, the term "array" refers to a group of carbon
nanotubes with same attributes as the individual carbon
nanotube.
[0062] As used herein, the term "basic group" refers to the group
which accepts a hydrogen ion or which when dissolved in water gives
a solution with pH greater than 7.0. The basic groups are
positively charged groups at pH lower than 7.0.
[0063] As used herein, the term "carboxylic acid" refers to --COOH
group.
[0064] As used herein, the term "comprising" or "comprises" is
intended to mean that the devices and methods include the recited
elements, but not excluding others. "Consisting essentially of"
when used to define devices, methods, or kit of parts, shall mean
excluding other elements of any essential significance to the
combination for the stated purpose. Thus, a composition consisting
essentially of the elements as defined herein would not exclude
other materials or steps that do not materially affect the basic
and novel characteristic(s) of the claimed invention. "Consisting
of" shall mean excluding more than trace amount of elements of
other ingredients and substantial method steps. Embodiments defined
by each of these transition terms are within the scope of this
invention.
[0065] As used herein, the term "dendrimer" refers to repeatedly
branched molecules. Dendritic molecules are repeatedly branched
species that are characterized by their structure perfection. The
latter is based on the evaluation of both symmetry and
polydispersity. The area of dendritic molecules can roughly be
divided into the low-molecular weight and the high-molecular weight
species. The first category includes dendrimers and dendrons
whereas the second encompasses dendronized polymers, hyperbranched
polymers, and brush-polymers (also called bottle-brushes).
Dendrimers and dendrons are repeatedly branched, monodisperse, and
usually highly symmetric compounds. There is no apparent difference
in defining dendrimer and dendron. A dendron usually contains a
single chemically addressable group that is called the focal point.
Because of the lack of the molar mass distribution high-molar-mass
dendrimers and dendrons are macromolecules but not polymers. The
properties of dendrimers are dominated by the functional groups on
the molecular surface. Dendritic encapsulation of functional
molecules allows for the isolation of the active site, a structure
that mimics the structure of active sites in biomaterials because
dendritic scaffolds separate internal and external functions. For
example, a dendrimer can be water-soluble when its end-group is a
hydrophilic group, like a carboxyl group.
[0066] As used herein, the term "desalted water" refers to water
from which salt has been substantially removed.
[0067] As used herein, the term "fluid" refers to both gas as well
as liquid.
[0068] As used herein, the terms "functional," or "functionalized,"
or "functionalization," refer to any group that imparts selectivity
to the carbon nanotubes in transporting fluids. The functional
groups include, without limitation, charged groups, non-charged
groups, or permanent charged groups.
[0069] As used herein, the term "liquid" refers to any liquid that
has the particles loose and can freely form a distinct surface at
the boundaries of its bulk material. Examples of liquid include,
but are not limited to, water, industrial streams, chemicals, or
bodily liquids. Examples of water include, without limitation,
salted water, sea water, well water, underground water, and waste
water. Examples of industrial stream include, without limitation,
pharmaceutical industry process stream, or food industry process
stream. Examples of chemicals include, without limitation,
chemicals used in pharmaceutical industry, laboratories, or
research organizations. Examples of bodily liquids include, without
limitation, diluted, untreated, or treated body fluids such as
milk, blood, plasma, urine, amniotic liquid, sweat, saliva,
etc.
[0070] As used herein, the term "membrane" intends a porous
material whose lateral dimension is significantly larger than the
dimensions across it.
[0071] As used herein the term "nanotube" intends a substantially
cylindrical tubular structure of which the most inner diameter size
is an average of less than about 6 nm. Nanotubes are typically, but
not exclusively, carbon molecules and have novel properties that
make them potentially useful in a wide variety of applications in
nanotechnology, electronics, optics, and other fields of materials
science. They exhibit extraordinary strength and unique electrical
properties, and are efficient conductors of heat. The nanotube is a
member of the fullerene structural family, which also includes
buckyballs. Where buckyballs are spherical in shape, a nanotube is
cylindrical, with at least one end typically capped with a
hemisphere of the buckyball structure. The name is derived from
their size, since the diameter of a nanotube can be on the order of
a few nanometers (approximately 50,000 times smaller than the width
of a human hair), while they can be up to several millimeters in
length. The nanotubes can be single-walled nanotubes (SWNTs),
double-walled nanotubes (DWNTs) and multi-walled nanotubes (MWNTs).
Nanotubes may be composed primarily or entirely of sp.sup.2 bonds,
similar to those of graphite. This bonding structure, stronger than
the sp.sup.3 bonds found in diamond, provides the molecules with
their unique strength. Nanotubes naturally align themselves into
"ropes" held together by Van der Waals forces. Under high pressure,
nanotubes can merge together, trading some sp.sup.2 bonds for
sp.sup.3 bonds, giving great possibility for producing strong,
unlimited-length wires through high-pressure nanotube linking
[0072] Nanotubes are comprised of various materials, which include
but are not limited to carbon, silicon, silica and selenium.
Inorganic nanotubes such as boron nitride have also been
synthesized. Carbon nanotubes include single wall, double wall, and
multiwall types. A "single-wall" is one tubular layer, straight or
tortuous, of carbon atoms with or without a cap at the ends, while
a "double-wall" is two concentric tubular layers, straight or
tortuous, of carbon atoms with or without a cap at the ends and a
"multi-wall" intends more than two concentric tubular layers,
straight or tortuous, of carbon atoms with or without a cap at the
ends.
[0073] The nanotubes can be arranged in an array wherein a
plurality of nanotubes are organized in spatial arrangement with
each other. For example, they can be aligned substantially parallel
to each other as "substantially vertically aligned" and be
generally or substantially perpendicular to a substrate. Nanotubes
can be grown off of surfaces that have catalyst particles disposed
on the surface in an ordered or disordered array.
[0074] As used herein, the term "non-charged group" refers to the
group that has no positive or negative charge on it.
[0075] As used herein, the term "permanent charged group" refers to
the group which has the charge not dependent on the surrounding pH.
For example, quartenary ammonium ion has a positive charge.
[0076] As used herein, the term "polymer" is a large molecule
(macromolecule) composed of repeating structural units typically
connected by covalent chemical bonds. Examples of polymer include,
but are not limited to, linear and branched polyethylene glycol
(PEG), polyamides, polyesters, polyimides and polyurethanes.
Examples of polyamides include, but are not limited to, nylon 6;
nylon 6,6; and nylon 6,12. Examples of polyesters include, but are
not limited to, poly(ethylene terephthalate), poly(trimethylene
terephthalate), and poly(trimethylene naphthalate).
[0077] As used herein, the term "polyelectrolyte" refers to
polymers whose repeating units bear an electrolyte group. These
groups will dissociate in aqueous solutions (water), making the
polymers charged. Polyelectrolyte properties are thus similar to
both electrolytes (salts) and polymers (high molecular weight
compounds), and are sometimes called polysalts. Like salts, their
solutions are electrically conductive. Like polymers, their
solutions are often viscous. Charged molecular chains, commonly
present in soft matter systems, play a role in determining
structure, stability and the interactions of various molecular
assemblies. One of the role of polyelectrolytes is in biology and
biochemistry. Many biological molecules are polyelectrolytes. For
instance, polypeptides (thus all proteins), and polynucleotides
such as DNA, and RNA are polyelectrolytes including both natural
and synthetic polyelectrolytes. Other examples of polyelectrolytes
include, without limitation, polysterenesulfonate (PSS).
[0078] As used herein, the term "salted water" refers to water with
salt (Na.sup.+Cl.sup.-) in it. The salted water can be sea water.
Along with Na.sup.+ and Cl.sup.- ions, the salted water can contain
one or more of additional ions. Examples of ions include, but are
not limited to, magnesium, sulfur, calcium, potassium, strontium,
barium, radium, bromine, etc.
[0079] As used herein, the term "substantially" refers to more than
about 50%.
[0080] As used herein, the term "transport" refers to separation as
well as filtration of the fluid.
2. Carbon Nanotubes
[0081] The various embodiments described herein include carbon
nanotubes, membranes, fabric, articles and devices comprising,
consisting essentially of, or consisting of membranes, and methods
of making these membranes, fabric, articles, and devices. In one
aspect, the membranes surprisingly provide faster than expected and
thus efficient liquid and gaseous fluid transport despite nanoscale
pore size. Moreover, they are mechanically robust, and they provide
a versatile system to commercialize fluid transport for particular
applications.
[0082] In one aspect, there is provided an array of carbon
nanotubes functionalized on at least one end of at least one of the
nanotubes, wherein the nanotubes have average pore size less than
about 6 nm or less as described herein.
[0083] Also provided herein are carbon nanotubes and nanofiltration
membranes whose through-pores are made of sub-6 nm carbon nanotubes
with at least one end or the pore entrance of at least one of the
nanotube modified by functional groups. The functional groups can
be charged groups or uncharged groups. These carbon nanotube
membranes exhibit high permeability since water and gas flow
through carbon nanotubes is orders of magnitude faster than through
other pores with the same or smaller diameter.
[0084] The charged groups at the pore entrance and/or the small
diameter of the pores causes these membranes to be able to
efficiently exclude ions while maintaining ultra fast water
permeation. Negatively charged groups provide rejection for anions
and can be introduced at the opening of the carbon nanotubes by
plasma treatment. Positively charged groups provide rejection for
cations and can be introduced by chemical modification. Rejection
depends on electrostatic action between the membrane and ions in
solution.
[0085] The carbon nanotubes are aligned or not aligned and are
embedded in a ceramic or in a polymeric matrix that fills the
spaces between carbon nanotubes. In some embodiments, the carbon
nanotubes are single wall, double-wall nanotubes, or multi-wall
nanotubes. In some embodiments, substantially all of the nanotubes
of the array are substantially vertically-aligned. In some
embodiments, more than about 50% of the nanotubes are
vertically-aligned. In some embodiments, more than about 60%; more
than about 70%; more than about 80%; more than about 90%; more than
about 95%; or about 100% of the carbon nanotubes are vertically
aligned.
[0086] The carbon nanotubes are opened at both ends and at least
one end or the pore entrance of at least one of the nanotube is
modified with functional groups.
[0087] The nanotube pore entrance can contain functional groups
that change conformation or charge upon change in pH or change in
temperature. The pH or temperature change can then trigger changes
in membrane selectivity. An example of pH sensitive rejection is
carboxylic group functionalization because carboxylic croup changes
charge with the change of pH. An example for temperature-sensitive
membrane-selectivity change is the use of hydrogen-bonded hairpin
that can be broken up and reformed (for example a RNA hairpin).
These embodiments will be provided in detail below.
[0088] In one embodiment of this invention, carboxylic groups are
created on the carbon nanotube rim by the etching processes used
for opening the carbon nanotubes and for removing the excess
filling matrix eventually covering the tips. These etching
processes include argon ion milling, reactive ion etching, oxygen
plasma, water plasma, and air plasma. When in contact with an
aqueous salt solution at a pH larger than the pKa of an acid, for
example, carboxylic acid, these functional groups are ionized and
form a rim of charges at the carbon nanotube entrance.
[0089] In some embodiments, the nanotube is functionalized with the
same or different group. In some embodiments, the nanotube is
functionalized with the same group. In some embodiments, the at
least one end or the pore entrance of at least one of the nanotube
is functionalized with a charged group. Examples of charged groups
attached to the end or the pore entrance of the nanotube, include,
but are not limited to, sulfonate, phosphonate, ammonium,
carboxylate, etc. In some embodiments, the at least one end or the
pore entrance of at least one of the nanotube is functionalized
with a non-charged group. Example of non-charged group includes,
but is not limited to, non-charged dendrimer.
[0090] In some embodiments, the nanotube is functionalized with an
acidic group or a basic group. In some embodiments, the nanotube is
functionalized with a permanent charged group. In some embodiments,
the nanotube is functionalized with a group selected from
carboxylic acid, sulfonic acid, phosphonic acid, amine, amide,
polymer, dendrimer, and a polyelectrolyte. In some embodiments, the
nanotube is functionalized with an amide or polyamide. In some
embodiments, the nanotube is functionalized with a short oligomer
or a long oligomer of, for example, polyethylene glycol (PEG)
polymer. In some embodiments, the nanotube is functionalized with
polyelectrolytes. In some embodiments, the nanotube is
functionalized with a dendrimer. Example of dendrimer includes,
without limitation, poly(amidoamine) (PAMAM).
[0091] The functionalization of the nanotubes enhances rejection of
the ions in the fluid, enhances selectivity of the membranes,
and/or reduces fouling of the membranes.
[0092] For carbon nanotube pores with sub-6 nm diameter, steric
hindrance and/or electrostatic interactions between the charged
functionalities on the membrane and ionic species in solution
enable effective rejection of ions during salt solution
filtration.
[0093] In some embodiments, the nanotube is functionalized with
polymers, branched polymers, dendrimers, or poly(m-aminobenzene
sulfonic acid). In some embodiments, the nanotube end or pore
entrance is modified by attaching a short chain or long chain
primary amine through an amide bond as shown below:
##STR00001##
[0094] The multiwall nanotube in the above reaction is for
illustration purposes only. It is to be understood that the
reaction can be carried out with single-wall as well as double-wall
nanotubes too.
[0095] In some embodiments, the nanotube is functionalized with a
polyelectrolyte, such as a single stranded or double stranded DNA
(deoxyribonucleic acid). DNA-based gating of nanotube membranes is
based on attaching a short single-stranded DNA hairpin to the mouth
of the CNT membrane pore. The ssDNA (single strand DNA) can
(according to the MD simulations, Gao et al. (2003) Nano Lett.
3:471) spontaneously insert into the CNT pore channel. This
invention can be realized in several configurations. An embodiment
is as shown in FIG. 8. In the normally-closed configuration the
mouth of the nanotube is blocked by a partially-inserted DNA
hairpin attached to the nanotube mouth. Addition of a complementary
DNA strand extracts the DNA strand from the channel and opens up
the pore. In the normally-open configuration, the DNA hairpin is
complexed with the slightly longer complementary DNA; addition of
the reverse complementary sequence strips the complement off the
hairpin and causes the hairpin to block the nanotube opening. The
benefits of this approach include the ability to regulate the
permeability of CNT membrane using very specific sequences of DNA.
Possible uses of this embodiment range from timed delivery of
reagents or drugs, to creation of "smart surfaces" that would
release antibiotics, antidotes or other chemicals when triggered by
presence of a specific pathogenic DNA sequence outside of the
membrane.
[0096] In some embodiments, a short section of the carbon nanotube,
embedded in a matrix, is removed at the entrance. That region of
the matrix is modified to create a gate region. The walls of the
pore formed in the matrix are used to anchor chemical groups
allowing for control of the length of the gate region.
[0097] The at least one end or the pore entrance of at least one of
the nanotubes can be functionalized in various ways, as depicted in
FIG. 9. In some embodiments, the functional groups are attached to
the end or tips of the CNTs (FIG. 9A). In some embodiments, CNTs
are preferentially etched, leaving a pore of the matrix above it
and the functional groups are attached to the sidewalls of the pore
created in the polymer matrix (FIG. 9B). In some embodiments, the
inner side walls of the CNTs are functionalized by breaking the
carbon-carbon bonds and attaching functional groups, such as for
example, amide groups or charged groups such as tertiary amine,
etc. (FIG. 9C). In some embodiments, both the matrix surface and
the CNT mouth are functionalized with the ion-rejecting compound or
the charged group. In some embodiments, the nanotube mouth is
functionalized with a charged group and the matrix surface is
functionalized with the foulant-rejecting moiety (such as PEG) to
create a dual-functionalized membrane.
[0098] In some embodiments, the functionalization of at least one
end or pore entrance of at least one nanotube in the membrane
provides selectivity to the membrane in terms of the nature of the
ions that can be removed from the water. For example, the nanotube
end functionalized with carboxylate anion will selectively reject
anions from water and the nanotube end functionalized with an amino
cation will selectively reject cations from the water.
[0099] In some embodiments, the membranes possess temporarily
protected pores. For example, a group that closes CNT and is
released by external stimulus is useful as a way to protect the
inside of the CNT from being filled or damaged during membrane
fabrication, storage and transportation. This kind of group
protection can be realized using photo-cleavable ligands.
[0100] Example of photo-cleavable ligand includes, but is not
limited to, 4-t-butyl-.alpha. nitrobenzyl cleavable with UV
light.
[0101] In each of the above embodiments, it should be understood,
although not explicitly stated that the nanotubes are
functionalized with from about 5%-100% of the site available for
functionalization; from about 10%-90%; from about 25%-75%; from
about 50%-75%; or from about 50%-100%. In some embodiments,
functionalization of the nanotubes with just one functional group
is sufficient to impart properties to the membrane. In some
embodiments, all the available sites on the nanotubes are
functionalized to impart properties to the nanotubes. In some
embodiment, the functionalization of the nanotube in a membrane
provides an enhanced selectivity in the transport of the fluid than
a non-functionalized nanotube. In some embodiment, the
functionalization of the nanotube in a membrane provides an
enhanced rejection of the salt from a salted water than a
non-functionalized nanotube.
[0102] In each of the above embodiments, it should be understood,
although not explicitly stated that the average pore sizes of the
carbon nanotube membranes can be for example about 0.5 nm to about
6 nm, or about 1 nm to about 2 nm. In one embodiment, they are on
average less than about 6 nm, but still of sufficient internal
diameter to allow gas and liquid molecules to pass through them.
Thus, alternative embodiments include nanotubes having average
pores sizes of less than about 6 nm, or alternatively, less than
about 5 nm, or alternatively, less than about 4 nm, or
alternatively, less than about 3 nm, or alternatively, less than
about 2 nm, or alternatively, less than about 1 nm, or
alternatively between about 0.5 nm and about 6 nm, or alternatively
between about 1 nm and about 4 nm and yet further, between about 1
nm and about 3 nm or yet further, between about 0.5 nm and about 2
nm.
[0103] In each of the above embodiments, it should be understood,
although not explicitly stated that the number of pores having the
aforementioned pore sizes in the membrane can be from greater than
about 40%, or alternatively greater than about 45%, or
alternatively more than about 50%, or alternatively, more than
about 55%, or alternatively, more than about 60%, or alternatively
more than about 65%, or alternatively more than about 70%, or
alternatively more than about 75%, or alternatively more than about
80%, or alternatively more than about 85%, or alternatively more
than about 90% or alternatively, more than about 95%, each of the
total number of pores in the membrane. Typically, pore size is
determined by TEM (Transmission Electron Microscope) or Raman
spectroscopy method, although other methods are known in the
art.
[0104] The carbon nanotubes in the membrane can be substantially
single walled nanotubes or alternatively double walled nanotubes or
alternatively multiwalled nanotubes or yet further comprise a
combination of any of single-, double- or multiwalled. An array of
substantially any one type of carbon nanotube (e.g., single, double
or multi) intends greater than about 70%, or 80%, or 90% of the
nanotubes in the array are of that type.
[0105] In one embodiment, the nanotubes can have open ends on one
side, or on each side of the membrane. Opening can be determined by
for example fluid transport through the carbon nanotube as well as
analytical methods such as nanoscale electron microscopy. Nanotubes
can be used in applications such as composites or cold emitters
wherein the nanotube is open on but one side or is open on neither
side.
[0106] In some cases, carbon nanotubes can also comprise catalyst
nanoparticles at one end. For the purpose of illustration only,
catalyst nanoparticles include, but are not limited to pure or
alloyed iron, cobalt, nickel, molybdenum and platinum. In one
embodiment, more than 10%; more than 20%; more than 30%; more than
40%; more than 50%; more than 60%; or more than 70% of the
nanotubes are free of catalyst nanoparticles used for carbon
nanotube formation. In a further embodiment, more that 80%, or yet
further, more than 90%, or even further more than 95% of the
nanotubes are free of catalyst nanoparticles used for carbon
nanotube formation.
[0107] The carbon nanotubes in a membrane also can be characterized
by an areal density. For example, areal density can be for example
at least 1.times.10.sup.10/square centimeter, or alternatively at
least 1.5.times.10.sup.10/square centimeter, or alternatively at
least 2.times.10.sup.10/square centimeter, or alternatively at
least 2.5.times.10.sup.10/square centimeter, or alternatively, at
least 3.times.10.sup.10/square centimeter, or alternatively at
least 3.5.times.10.sup.10/square centimeter, or alternatively at
least 4.times.10.sup.10/square centimeter.
[0108] The carbon nanotubes in a membrane also can also be
characterized by a charge density. For example, charge density can
be for example at least about 0.5-4 mM, or alternatively at least
1-3 mM, or alternatively at least 2-3 mM, or alternatively at least
1-2 mM, or alternatively, at least 1.5-3 mM, or alternatively at
least 0.5-2 mM, or alternatively at least 1.5-2.5 mM.
[0109] The carbon nanotubes can be characterized by an average
length. The upper end on length is not particularly limited and
CNTs hundreds of microns long, such as 500 microns long, can be
made. For example, average length can be about 0.1 microns to about
500 microns, or about 5 microns to about 250 microns, or about 0.1
microns to about 5 microns, or about 0.2 microns to about 20
microns, or about 0.2 microns to about 10 microns, or about 0.2
microns to about 5 microns. Average length can be greater than
about 0.5 micron, or alternatively greater than about 1 microns, or
alternatively, greater than about 3 microns, or alternatively,
greater than about 4 microns, or alternatively, about 5 microns to
about 100 microns, or alternatively, about 5 microns to about 150
microns, or alternatively, about 5 microns to about 50 microns, or
yet further about 1 micron to about 50 microns. The carbon
nanotubes arranged in an array can be characterized by high aspect
ratio gaps between the individual carbon nanotubes, wherein the
length is much greater than the width. For example, aspect ratio of
these gaps can be at least 1,000 length/width.
[0110] For the pore sizes described herein, efficient ion rejection
is largely due to the electrostatic repulsion between the charges
strategically placed on the through-pore entrance and the co-ions
in solutions. Efficient ion rejection is achieved for millimolar or
sub-millimolar salt concentration. Increasing the number of charges
at the nanopore entrance by targeted functionalization improves ion
rejection performances. For larger pore diameters, rejection
performances may degrade quickly with increasing nanotube size. In
another embodiment of this invention, the charged carbon nanotube
pores have a sub-nanometer diameter. For these carbon nanotube
sizes, efficient ion exclusion is obtained for much larger salt
solution concentrations due to the simultaneous contribution of
steric hindrance, size exclusion, and electrostatic repulsion
mechanisms.
[0111] Pressure-driven filtration experiments, coupled with
capillary electrophoresis analysis of the permeate and feed, are
used to quantify ion exclusion in these membranes as a function of
solution ionic strength, pH, and ion valence. In some embodiments,
the carbon nanotube membranes exhibit ion exclusion as high as 98%
under certain conditions. In some embodiments, the ion exclusion
results may support a Donnan-type rejection mechanism, dominated by
electrostatic interactions between fixed membrane charges and
mobile ions, while steric and hydrodynamic effects may be minor or
negligible.
[0112] A model of nanofluidic platform consisting of sub-2 nm
carbon nanotube membranes fabricated by conformal deposition of
silicon nitride on densely-packed, vertically-aligned carbon
nanotube forests has been demonstrated (FIG. 1a-c) (Holt et al.
(2006) Science 312:1034-1037). The etching process is used to
expose and to selectively uncap the carbon nanotubes to introduce
hydroxyl (OH), carbonyl (C.dbd.O), and carboxylic (COOH) functional
groups at the nanotube entrance (Yang (2005) Langmuir 21:8539-8545;
and Li et al. (2007) J. Phys. Chem. B 111:1672-1678). In
particular, ionization of these carboxylic groups provides a ring
of negative charges at the pore entrance that could affect the ion
transport through the nanotube pore.
3. Membranes
[0113] In one aspect, there is provided a membrane for an enhanced
fluid transport comprising, consisting essentially of, or
consisting of a substantially vertically-aligned array of carbon
nanotubes as provided herein and a matrix material disposed between
the carbon nanotubes. In a particular embodiment, there is provided
a membrane for an enhanced fluid transport comprising, consisting
essentially of, or consisting of a substantially vertically-aligned
array of carbon nanotubes functionalized at least one end of at
least one of the nanotubes, wherein the nanotubes have average pore
size of about 6 nm or less and a matrix material disposed between
the carbon nanotubes.
[0114] In another embodiment, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of: a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm having at least one
functionalized nanotube; and a matrix material disposed between the
carbon nanotubes.
[0115] In another embodiment, it is contemplated that the membranes
may be used to selectively transport certain ions, but reject other
ions across the membrane. This may be achieved by selecting a
functional group at the end of the nanotube that rejects certain
ions while allowing other ions to transport across the
membrane.
[0116] In yet another embodiment, there is provided a membrane for
an enhanced transport of desalted water from salted water
comprising, consisting essentially of, or consisting of: a
substantially vertically-aligned array of carbon nanotubes, wherein
the nanotubes have average pore size of about 1-2 nm with a charge
density of about 1-3 mM and have at least one functionalized
nanotube; and a matrix material disposed between the carbon
nanotubes.
[0117] In some embodiments, the membrane described herein provides
an enhanced selectivity in the transport of the fluid larger than a
non-functionalized nanotube. In some embodiments, the membrane
described herein provides an enhanced rejection of the salt from a
salted water than a non-functionalized nanotube.
[0118] These membranes can have pore sizes on the molecular scale
(ranging from approximately 1 nm to approximately 2 nm). They are
robust, mechanically and chemically stable. Enhanced gas transport
through the membranes compared to other materials of similar pore
size is demonstrated. Molecular dynamics simulations predict high
water flows through these materials too. Due to high molecular flux
and possibility of size exclusion, the possible applications of
these materials include but are not limited to: 1) Gas separations
such as (but not limited to) removal of hydrocarbons, CO.sub.2
sequestration; 2) water desalination/demineralization (described
below); 3) dialysis; and 4) breathable material for protection from
chemical and biological agents.
[0119] The nanoporous membranes can be fabricated from a variety of
a substantially vertically aligned array of single wall,
double-walled, or multi-wall CNTs, grown via an atmospheric
pressure chemical vapor deposition process, as known in the art.
For example, ethylene, hydrogen, and argon can be used as process
gases, and a thin metal multilayer deposited on silicon can serve
as the substrate to catalyze the growth. It is the uniqueness of
the metal catalyst layer that enables one to grow carbon nanotubes,
including SWCNTs, in a substantially vertically aligned array, as
opposed to growth in the plane of the substrate. This vertically
aligned array of nanotubes typically has internal diameters ranging
from, for example, 0.8-2 nm, a tube-tube spacing of less than 50
nm, preferably 1.0 to 5.0 nm, and a height (thickness) of 5-10
.mu.m. MWCNT arrays may have internal diameters on the order of
5-20 nm.
[0120] Once grown, the nanotube array can be coated by a matrix
material to immobilize the tubes and enable processing into a
membrane. Matrix fill can be continuous or form a closed cell
structure. A factor here is the use of a conformal material that
can fill the high aspect ratio (approximately 1000 length/diameter)
gaps between these tubes, such that the carbon nanotubes serve as
the only pores in the material. A variety of matrix materials,
ranging from inorganic material to polymeric material (e.g.
parylene, polydimethylsiloxane, polyimide) may be used. Polymeric
material includes, but is not limited to, linear polymers such as
polyethylene, polyacrylates, or polystyrene and cross linked
polymers such as epoxy resins. It can also be semi-permeable such
as polyamide or non-permeable such as epoxy resin.
[0121] Examples of inorganic material include, but are not limited
to, ceramics (e.g. silicon nitride, silicon dioxide). The matrix
material can also be for example an oxide material such as for
example silicon or aluminum oxide. Silicon oxide materials can be
made from, for example, (TEOS) tetraethyloxysilane. The matrix
material could also include silicon from, for example, a silicon
source. Polysilicon can be used.
[0122] Any number of additional matrix materials can be used which
can have the functional characteristics of having negligible, low
or high molecular permeability. In some embodiments, the matrix
material has a selective molecular permeability where it allows
certain molecules to penetrate while preventing others. Other
functional characteristics can include optical impermeability, or
opaqueness, indicating transmitting negligible light intensity over
a certain range of wavelengths, compared to the internal space of
the carbon nanotubes. Matrix can also be transparent. The membrane
can have a thickness of for example about 100 nm to about 2
microns, or about 400 nm to about 800 nm.
[0123] Low-stress silicon nitride and TEOS oxide (tetraethoxysilane
oxide) have been successfully used to achieve conformal, void-free
coatings on multiwall nanotube arrays (outer diameters of 20-50
nm), resulting in a high strength composite membrane. In addition
to using CVD (Chemical Vapor Deposition) coatings, filling can be
achieved using Atomic Layer Deposition. In some embodiments, the
matrix material comprises a ceramic. In some embodiments, the
matrix material comprises silicon nitride. In some embodiments, the
matrix material comprises low stress silicon nitride. In some
embodiments, the matrix material comprises a polymer. In some
embodiments, the matrix material comprises TEOS oxide.
[0124] It is to be noted that ceramics like silicon nitride are
particularly advantageous for desalting/demineralization
applications, due both to their high temperature stability (films
deposited at 800.degree. C.) and solvent resistance (to strong
acids/bases), which would facilitate removal of the organic and
inorganic foulants on the membrane. Parylene has also exhibited
conformal properties on multiwall CNT arrays, with both high
temperature stability (melting point up to 420.degree. C.) and
solvent resistance.
[0125] Provided herein is a method for producing a CNT-based
membrane using low-stress silicon nitride as a conformal matrix
material. This method provides a graphitic CNT membrane using a
ceramic matrix material. In contrast to polymer matrices, silicon
nitride has a negligible molecular permeability, leaving the cores
of embedded CNTs as the only pores in the membrane. In addition,
the nanotubes can also serve as a template for the production of
nanoporous silicon nitride since they can be selectively removed by
oxidation. Another advantage of silicon nitride is its vapor phase
deposition. Materials deposited in the liquid phase such as spun-on
polymers may involve elaborate curing processes to reduce CNT
agglomeration and ensure retention of alignment.
[0126] In some embodiments, the matrix material has negligible
molecular permeability. In some embodiments, the matrix material is
a rigid material. In some embodiments, the membrane has a thickness
of about 0.1 microns to about 2 microns. In some embodiments, the
matrix material has a thickness of about 400 nm to about 800
nm.
[0127] It may be desirable to ensure adhesion between the carbon
nanotube and the matrix such that the composite material as a whole
is mechanically robust. In some embodiments, the matrix material
encapsulates the carbon nanotubes. In some embodiments, the matrix
material conformally coats the carbon nanotubes. In some
embodiments, the matrix material is free of gaps between the outer
surface of the nanotubes and the matrix material. To this end,
tensile strain tests on the material, as well as nanoindentation
tests to examine closely the nanotube/matrix interface can be
carried out. In some embodiments, the membrane does not fracture
when tested with a one atmosphere pressure drop.
[0128] In one aspect, the membranes are characterized functionally
in that they should not pass particles or nanoparticules such as
for example 100 nm or 25 nm fluorescently labeled polystyrene beads
or metallic nanoparticles of for example size of 2, 5, or 10 nm. In
additional, microscopic and spectroscopic techniques using AFM
(atomic force microscopy) and UV-VIS spectroscopy can functionally
characterize the exclusion of 2 nm gold colloidal nanoparticles in
membrane permeation.
[0129] In some embodiments, the membrane does not pass 100 nm
fluorescently-labeled polystyrene beads. In some embodiments, the
membrane does not pass 25 nm fluorescently-labeled polystyrene
beads. In some embodiments, the membrane does not pass 2 nm, 5 nm,
or nm gold nanoparticles.
[0130] In some embodiments, the gaps in the nanotubes are high
aspect ratio gaps of about 1,000 length/diameter or less. In some
embodiments, the gaps are high aspect ratio gaps of at least about
100 length/diameter.
[0131] In some embodiments, the membrane provides enhanced gas
transport compared to the Knudsen transport prediction for same
sized pores. In some embodiments, the membrane provides enhanced
gas transport compared to the Knudsen transport prediction for same
sized pores, wherein the enhancement is at least three orders of
magnitude for an air flow rate. In some embodiments, the membrane
provides enhanced gas transport compared to the Knudsen transport
prediction for same sized pores, wherein the enhancement is at
least 16 times that for an air flow rate. In some embodiments, the
membrane provides enhanced gas transport compared to the Knudsen
transport prediction for same sized pores, wherein the enhancement
is at least 50 times that for an air flow rate.
[0132] In some embodiments, the membrane provides enhancement of
water flow over no-slip, hydrodynamic flow prediction. In some
embodiments, the membrane provides enhancement of water flow over
no-slip, hydrodynamic flow by at least 10 times. In some
embodiments, the membrane provides enhancement of water flow over
no-slip, hydrodynamic flow by at least 500 times.
[0133] In some embodiments, the membrane provides an air
permeability of at least one cc/s-cm.sup.2-atm and a water
permeability of at least one mm.sup.3/s-cm.sup.2-atm. In some
embodiments, the membrane provides an air permeability of at least
two cc/s-cm.sup.2-atm and a water permeability of at least two
mm.sup.3/s-cm.sup.2-atm. In some embodiments, the membrane provides
a gas selectivity relative to helium which is higher than that from
a Knudsen model.
[0134] In each of the embodiments described herein, it should be
understood, although not explicitly stated that the nanotubes have
a height of about 0.2 microns to about 5 microns, and the matrix
material comprises a ceramic or polymer. In some embodiments, the
nanotubes have a height of about 0.2 microns to about 5 microns,
and the matrix material comprises a polymer. In some embodiments,
the nanotubes have a height of about 0.2 microns to about 5
microns, and the matrix material comprises a ceramic. In some
embodiments, the membrane provides enhanced gas transport compared
to Knudsen transport prediction for same sized pores.
[0135] In some embodiments, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm having at least one
functionalized nanotube; and a matrix material disposed between the
carbon nanotubes, wherein the membrane provides an enhanced
selectivity in the transport of desalted water from salted water
than a nanotube without a functionalized tip.
[0136] In some embodiments, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of: a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm having at least one
functionalized nanotube; and a matrix material disposed between the
carbon nanotubes, wherein the membrane provides an enhanced
rejection of the salt from a salted water than a nanotube without a
functionalized tip.
[0137] In some embodiments, there is provided a membrane for an
enhanced transport of desalted water from salted water comprising,
consisting essentially of, or consisting of: a substantially
vertically-aligned array of carbon nanotubes, wherein the nanotubes
have average pore size of about 1-2 nm with a charge density of
about 1-3 mM and have at least one functionalized nanotube; and a
matrix material disposed between the carbon nanotubes, wherein the
membrane provides an enhanced rejection of the salt from a salted
water than a nanotube without a functionalized tip.
[0138] After coating, the excess matrix material can be removed
from the membrane, and the carbon nanotubes can be opened, as they
are initially capped at the top and blocked at the bottom with
catalyst particles. This can be easily achieved by use of a plasma
etching process.
[0139] In some embodiments, there is provided a nanoporous membrane
prepared by the methods described herein. In some embodiments, the
substantially vertically aligned carbon nanotube array in the
nanoporous membrane is a single wall array, and the nanotubes have
diameters on the order of 0.8 nm to 2 nm, a tube-tube spacing of
less than 50 nm, and a height of 5 microns to 10 microns. In some
embodiments, the vertically aligned carbon nanotube array in the
nanoporous membrane is a multi wall array, and the nanotubes have
diameters on the order of 5 nm to 10 nm, a tube-tube spacing of
less than 5 nm, and a height of 5 microns to 10 microns.
[0140] Another embodiment is a fabric comprising, consisting
essentially of, or consisting of the membrane having the array of
nanotubes as provided herein and a porous polymer or fiber fabric
supporting material. Articles can include articles that comprise a
plurality of membranes including for example chips comprising,
consisting essentially of, or consisting of a plurality of
membranes, as well as systems and devices wherein membranes are
placed on top of each other in multilayer formats.
[0141] In some embodiments, there is provided a membrane of carbon
nanotubes of selective permeability formed by the process
comprising:
[0142] (a) wetting with a first liquid phase a microporous support
that is wettable by the first liquid phase, the first liquid phase
having dissolved therein a first polymerizable species;
[0143] (b) contacting the microporous support thus wetted with a
second liquid phase that is at least partially immiscible with the
first liquid phase and in which is dissolved a second polymerizable
species, one or both of the first and second liquid phases having
carbon nanotubes randomly dispersed therein of an average
length;
[0144] (c) causing the first and second polymerizable species to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0145] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0146] (e) recovering from the first and second liquid phases the
microporous support with the layer adhering to the outer
surface,
[0147] thereby forming a membrane of carbon nanotubes of selective
permeability.
[0148] In some embodiments, there is provided a membrane of carbon
nanotubes of selective permeability formed by the process
comprising:
[0149] (a) wetting with an aqueous phase a microporous support
selected from polysulfone or polyethersulfone that is wettable by
the aqueous phase, the aqueous phase having dissolved therein
m-phenylenediamine;
[0150] (b) contacting the microporous support thus wetted with a
solvent phase that is at least partially immiscible with the
aqueous phase and in which is dissolved trimesoyl chloride, one or
both of the aqueous and solvent phases having carbon nanotubes
randomly dispersed therein of an average length;
[0151] (c) causing the m-phenylenediamine and trimesoyl chloride to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0152] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0153] (e) recovering from the aqueous and solvent phases the
microporous support with the layer adhering to the outer surface,
thereby forming a membrane of carbon nanotubes of selective
permeability.
[0154] In some embodiments, there is provided a membrane with
embedded carbon nanotubes, the membrane comprising a plurality of
carbon nanotubes open at both ends and embedded in a solid,
substantially continuous polymeric matrix, the polymeric matrix
having a thickness that is less than an average of the lengths of
the carbon nanotubes, the carbon nanotubes having substantially
random orientations relative to the membrane and yet oriented such
that at least a portion of the plurality of carbon nanotubes have
both open ends protruding from the membrane to provide fluid
communication through the membrane.
[0155] Some embodiments of the process by which the above noted
membranes are formed are described in detail in the section below
on the method of making membranes.
[0156] Some embodiments of the membranes in the above noted three
embodiments are as follows:
[0157] In some embodiments, the above noted membrane further
comprises a layer of microporous material supporting the polymeric
matrix.
[0158] In some embodiments, a ratio of the average of the lengths
of the carbon nanotubes to the thickness of the polymeric matrix is
from about 1.3 to about 5.
[0159] In some embodiments, a ratio of the average of the lengths
of the carbon nanotubes to the thickness of the polymeric matrix is
from about 2 to about 4.
[0160] In some embodiments, the polymeric matrix has a thickness of
from about 50 nm to about 300 nm.
[0161] In some embodiments, the average length of the nanotubes is
from about 100 nm to about 2000 nm.
[0162] In some embodiments, the average length of the nanotubes is
from about 200 nm to about 1000 nm.
[0163] In some embodiments, the nanotubes are carbon nanotubes with
inner diameters of about 0.4 nm to about 5 nm.
[0164] In some embodiments, the nanotubes are carbon nanotubes with
inner diameters of about 0.4 nm to about 1.2 nm.
[0165] In some embodiments, the polymeric matrix has a
substantially planar surface and contains from about
2.5.times.10.sup.8 to about 1.times.10.sup.12 nanotubes per square
centimeter of the surface.
[0166] In some embodiments, the polymeric matrix has a
substantially planar surface and contains from about
2.5.times.10.sup.9 to about 2.5.times.10.sup.11 nanotubes per
square centimeter of the surface.
[0167] In some embodiments, the polymeric matrix is a polyamide. In
some embodiments, the polymeric matrix is an aromatic
polyamide.
4. Method of Making Membranes
[0168] Fabrications methods for the membranes provided herein, can
comprise at least two general steps. In a first step, the array of
substantially vertically aligned carbon nanotubes can be
fabricated. In a second step, the gaps between the nanotubes can be
filled with matrix material. Vapor deposition can be used for
either or both steps. The carbon nanotubes can be processed so that
they are sufficiently open and provide for fluid flow. In some
cases, the filling step can be carried out when the carbon
nanotubes are closed, but then the carbon nanotubes can be
subsequently opened by for example etching.
[0169] If desired, carbon nanotubes can be removed by for example
oxidation to leave open channels free of or substantially free of
carbon nanotubes. Vapor deposition can be used by methods known in
the art and described in the working examples below. The carbon
nanotubes can be grown on a substrate comprising metallic
nanoparticles or metallic layers. For filling the gaps between the
carbon nanotubes, vapor deposition can be used including chemical
vapor deposition.
[0170] Some embodiments of the membrane structure are as defined in
FIG. 10.
[0171] In some embodiments, CNTs are substantially aligned and span
the whole membrane thickness. An embodiment of such membrane
structure is as shown in FIG. 10A. These membranes could be made
using CNTs that get aligned on a substrate during CVD synthesis.
CNTs are functionalized after being embedded in a matrix.
[0172] In some embodiments, CNTs are randomly dispersed in a matrix
and the molecular flow partially happens through CNTs and partially
through the matrix. An embodiment of such membrane structure is as
shown in FIG. 10B. These membranes can be made using unaligned bulk
CNTs that are dispersed into a matrix. The functionalization of
CNTs is performed before they are embedded into the matrix. The
matrix in this case is semi-permeable for molecules, retaining some
and letting others go through. The permeability of the matrix alone
for the molecules of interest is low. The addition of dispersed
CNTs provide high flux channels for molecular transport that
enhance the permeability of the membrane at least 2.times. and up
to 100.times. compared to membranes without CNTs. Functional groups
on CNTs serve two purposes for these membranes: 1) they improve
membrane selectivity and 2) they enable better dispersion of CNTs
in a matrix, allowing for higher CNT density and enhanced
permeability.
[0173] In some embodiments, the membrane structure is similar to
the membrane structure depicted in FIG. 10B except that the CNTs
are aligned or partially aligned using an external field such as
electric field (as shown in FIG. 10C). The alignment of the CNTs
using an electric field is provided in detail below. Alignment
further improves permeability by reducing the path length a
permeable molecule has to follow to cross the entire membrane
thickness.
[0174] In some embodiments, the membrane structure is similar to
the membrane structure depicted in FIG. 10A except that CNTs are
not aligned and the CNTs that span the membrane thickness only
contribute to the permeability (as shown in FIG. 10D).
[0175] In some embodiments, the membrane structure is similar to
the membrane structure depicted in FIG. 10A and further where the
matrix acts as a semi-permeable material and the functionalized
aligned CNTs contribute also to the permeability and selectivity of
the membrane.
[0176] In some embodiments, the membrane structure is similar to
the membrane structure depicted in FIG. 10D and further where the
matrix acts as a semi-permeable material and the randomly
dispersed, functionalized CNTs (both embedded and spanning the
whole membrane thickness) contribute also to the permeability and
selectivity of the membrane.
[0177] The membrane structures, as described herein, can be
supported on a backing material. As shown in FIG. 11, the membrane
structure can be directly on a backing (FIG. 11A), on a backing
with a cushion layer (such as hydrogel, FIG. 11B) or free standing,
supported on a mesh. For example, the membranes on a backing could
be synthesized using interfacial polymerization with CNTs added
into either organic or aqueous phase.
[0178] In yet another embodiment, the CNTs are dispersed in such a
way that the CNTs are longer than the thickness of the film. An
example of such embodiment is as shown in FIG. 12. In this
embodiment, bulk CNTs are added to the polymer before membrane
fabrication. As the result of the process, CNTs are randomly
oriented in the membrane, which causes a significant portion of the
nanotubes to span the whole membrane thickness. Membrane etching on
both sides then produces a permeable membrane. In some embodiments,
the top surface of the CNT array is coated with a protective layer
(skin layer), such as fast depositing parylene (PA) that prevents
the CNTs from collapsing into each other during matrix
infiltration. This selective skin layer is shown as 1 in FIG. 12.
In some embodiments, the membrane structure comprises a porous
bottom support structure, shown as 2 in FIG. 12, which acts as a
boundary confining surface. Examples of bottom support structure
include, but are not limited to, polysulfone (PSF),
polyethersulfone (PES), etc. The membrane may be opened by either
etching the whole protective parylene layer or just opening the CNT
pores on top of the parylene layer. In some embodiments, the
transport of the fluid can also go through the fill.
[0179] In one aspect, the fabrication sequence of the membrane
structure of FIG. 12 comprises, consists essentially of or consists
of the following steps:
a) Functionalized CNTs are dispersed in an aqueous phase (for
example, water, m-phenylenediamine etc.) or solvent phase (for
example, hexane, trimesoyl chloride, etc.); b) PSF membrane support
is dipped into the aqueous phase; c) excess aqueous solution is
removed from the surface of the membrane support; d) the membrane
support is dipped into the solvent phase; e) the membrane support
is cured at the oven; and f) stored in water.
[0180] In one aspect, there is provided a process for a preparation
of a membrane of selective permeability, the process
comprising:
[0181] (a) wetting with a first liquid phase a microporous support
that is wettable by the first liquid phase, the first liquid phase
having dissolved therein a first polymerizable species;
[0182] (b) contacting the microporous support thus wetted with a
second liquid phase that is at least partially immiscible with the
first liquid phase and in which is dissolved a second polymerizable
species, one or both of the first and second liquid phases having
carbon nanotubes randomly dispersed therein of an average
length;
[0183] (c) causing the first and second polymerizable species to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0184] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0185] (e) recovering from the first and second liquid phases the
microporous support with the layer adhering to the outer
surface.
[0186] In one aspect, there is provided a process for the
preparation of a membrane of selective permeability, the process
comprising:
[0187] (a) wetting with an aqueous phase a microporous support
selected from polysulfone or polyethersulfone that is wettable by
the aqueous phase, the aqueous phase having dissolved therein
m-phenylenediamine;
[0188] (b) contacting the microporous support thus wetted with a
solvent phase that is at least partially immiscible with the
aqueous phase and in which is dissolved trimesoyl chloride, one or
both of the aqueous and solvent phases having carbon nanotubes
randomly dispersed therein of an average length;
[0189] (c) causing the m-phenylenediamine and trimesoyl chloride to
form a layer of a solid polymer over an outer surface of the
microporous support;
[0190] (d) sealing the layer to form a substantially continuous
barrier around the nanotubes, the barrier having a thickness that
is less than the average length of the nanotubes; and
[0191] (e) recovering from the aqueous and solvent phases the
microporous support with the layer adhering to the outer
surface.
[0192] Some embodiments of the above noted aspects are as
follows:
[0193] In some embodiments, the carbon nanotubes are open at both
ends.
[0194] In some embodiments, the first and second polymerizable
species are mutually reactive by interfacial polymerization to form
the solid polymer that is insoluble in the first and second liquid
phases and that adheres to the microporous support.
[0195] In some embodiments, the steps (c) and (d) are performed
simultaneously and the layer is the barrier.
[0196] In some embodiments, the steps (c) and (d) are performed in
sequence, the layer of step (c) is defined as an intermediate layer
and is a porous layer, and step (d) comprises forming an outer
layer over the intermediate layer, the outer layer forming the
barrier, and the outer layer having a thickness that is less than
the average length of the nanotubes.
[0197] In some embodiments, the step (d) is formed by interfacial
polymerization by contacting the intermediate layer with a third
liquid phase that is at least partially immiscible with the first
liquid phase and in which is dissolved a third polymerizable
species that is reactive with one or both of the first and second
polymerizable species to form a solid polymer that is insoluble in
the first, second, and third liquid phases.
[0198] In a further aspect, the first liquid phase is a polar phase
and second (and third) liquid phase(s) are non-polar liquids. In
one further aspect, the non-polar liquid is a solution in a solvent
that is a mixture of hexane and chloroform with weight ration 1:1
to 10:1. In a further aspect, the non-polar liquid is a solution in
a solvent that is a mixture of hexane and chloroform at a
hexane:chloroform weight ration of from about 2:1 to about 5:1. In
a yet further aspect, the microporous support is wettable by a
polar liquid, the first liquid phase is a polar liquid and the
second and third liquid phases are non-polar liquids.
[0199] In some embodiments, the carbon nanotubes are single-walled
carbon nanotubes.
[0200] In some embodiments, the first liquid phase is a polar
liquid. Examples of polar liquid include, but are not limited to,
water, an alcohol such as ethanol, methanol, isopropanol, etc., and
a glycol.
[0201] In some embodiments, the polar liquid is an aqueous
solution.
[0202] In some embodiments, the microporous support is wettable by
a polar liquid, the first liquid phase is a polar liquid, and the
second and third liquid phases are non-polar liquids.
[0203] In some embodiments, a ratio of the average length of the
carbon nanotubes to the thickness of the layer is from about 1.3 to
about 5.
[0204] In some embodiments, a ratio of the average length of the
carbon nanotubes to the thickness of the intermediate and outer
layers combined is from about 1.3 to about 5.
[0205] In some embodiments, a ratio of the average length of the
carbon nanotubes to the thickness of the intermediate and outer
layers combined is from about 2 to about 4.
[0206] In some embodiments, the layer has a thickness of from about
50 nm to about 300 nm.
[0207] In some embodiments, the intermediate and outer layers have
a combined thickness of from about 100 nm to about 300 nm.
[0208] In some embodiments, the microporous support has first and
second opposing outer surfaces, and step (b) is performed with the
first outer surface blocked to limit formation of the polymer layer
to the second outer surface.
[0209] In some embodiments, the average length of the carbon
nanotubes is from about 100 nm to about 2000 nm.
[0210] In some embodiments, the average length of the carbon
nanotubes is from about 200 nm to about 1000 nm.
[0211] In some embodiments, the carbon nanotubes have an inner
diameter of about 0.4 nm to about 5 nm.
[0212] In some embodiments, the carbon nanotubes have an inner
diameter of about 0.4 nm to about 1.2 nm.
[0213] In some embodiments, the carbon nanotubes have an inner
diameter of about 1 nm to about 10 nm.
[0214] In some embodiments, the carbon nanotubes have an inner
diameter of about 5 nm to about 200 nm.
[0215] In some embodiments, the microporous support has a molecular
weight cutoff of from about 1 kDa to about 10 MDa.
[0216] In some embodiments, the microporous support has a molecular
weight cutoff of from about 5 kDa to about 300 kDa.
[0217] In some embodiments, the layer so formed has a flat surface
on a side of the layer opposite the microporous support, and the
nanotubes are dispersed in the second liquid phase at a
concentration such that the layer so formed contains from about
2.5.times.10.sup.8 to about 1.times.10.sup.12 nanotubes per square
centimeter of the flat surface.
[0218] In some embodiments, the layer so formed has a flat surface
on the side of the layer opposite the microporous support, and the
nanotubes are dispersed in the second liquid phase at a
concentration such that the layer so formed contains from about
2.5.times.10.sup.9 to about 2.5.times.10.sup.11 nanotubes per
square centimeter of the flat surface.
[0219] In some embodiments, the one of the first and second liquid
phases comprises a non-polar solution in a non-polar solvent, and
the polymerizable species dissolved in the non-polar solution
constitutes from about 0.05 g/100 mL to about 3 g/100 mL of the
non-polar solution, and the other of the first and second liquid
media comprises a polar solution in a polar solvent, and the
polymerizable species dissolved in the polar solution constitutes
from about 0.2 g/100 mL to about 5 g/100 mL of the polar
solution.
[0220] In some embodiments, the one of the first and second liquid
phases comprises a non-polar solution in a non-polar solvent, and
the polymerizable species dissolved in the non-polar solution
constitutes from about 0.05 g/100 mL to about 1 g/100 mL of the
non-polar solution, and the other of the first and second liquid
media comprises a polar solution in a polar solvent, and the
polymerizable species dissolved in the polar solution constitutes
from about 0.2 g/100 mL to about 2 g/100 mL of the polar
solution.
[0221] In some embodiments, the microporous support is a member
selected from the group consisting of polyethersulfone,
polysulfone, nylon, and polyester, and the first liquid phase is a
polar phase.
[0222] In some embodiments, the first liquid phase is a solution of
the first polymerizable species in a polar solvent selected from
the group consisting of water, an alcohol, and a glycol, and the
second liquid phase is a solution of the second polymerizable
species in a non-polar solvent selected from the group consisting
of benzene, a halobenzene, an alkyl benzene, a C.sub.5-C.sub.12
alkane, a halo-substituted C.sub.5-C.sub.12 alkane, and an
alkyl-substituted C.sub.5-C.sub.12 alkane.
[0223] In some embodiments, the first liquid phase is a solution in
a polar solvent selected from the group consisting of water, an
alcohol, and a glycol, and the second and third liquid phases are
solutions in a non-polar solvent selected from the group consisting
of benzene, a halobenzene, an alkyl benzene, a C.sub.5-C.sub.12
alkane, a halo-substituted C.sub.5-C.sub.12 alkane, and an
alkyl-substituted C.sub.5-C.sub.12 alkane.
[0224] In some embodiments, the first polymerizable species is an
aromatic polyamine and the second polymerizable species is an
aromatic polycarboxylic acid halide.
[0225] In some embodiments, the first polymerizable species is
m-phenylenediamine and the second polymerizable species is
trimesoyl chloride.
[0226] In some embodiments, the first polymerizable species is an
aromatic polyamine and the second and third polymerizable species
are aromatic polycarboxylic acid halides.
[0227] In some embodiments, the first polymerizable species is
m-phenylenediamine and the second and third polymerizable species
is trimesoyl chloride.
[0228] In some aspects, an electric field is used to align the CNTs
for membrane fabrication. An example of such embodiment, is as
shown in FIG. 13. This procedure uses the conducting nature of CNTs
or a fraction of CNTs. The application of electric field (either a
DC or AC field) results in the induced torque on the CNTs that
orients them parallel to the E-field lines. Thus at least a large
portion of the CNTs in the matrix becomes oriented. Then the matrix
is cured to permanently immobilize the CNTs in the aligned
orientation. The curing methods include, but are not limited to,
heat, radical polymerization, UV cure or the like.
[0229] In some embodiments, the fabrication sequence of the
membrane structure using an electric field comprises, consists
essentially of or consists of the following steps:
a) chemically-modified SWNTs (for example, amine) are dispersed in
a solvent (for example, THF); b) the dispersed SWNT solution is
mixed with a polymer (for example, epoxy); c) the mixture is
magnetically stirred; d) Indium Tin Oxide (ITO) glass coated with
thin polyvinyl acetate (PVA) layer is prepared (that allows for
release of the structure in water); e) the SWNT/polymer solution is
dropped between ITO glasses; f) AC electric field is applied; and
g) after curing or evaporation of the solvent, the assembly is put
into water bath to remove PVA layer and separate SWNT/polymer film
from ITO glass.
[0230] In yet another embodiment, there is provided a membrane
structure and a fabrication sequence of the membrane structure
using a vapor phase infiltration of carbon nanotube array with
parylene polymer fill. An example of such embodiment is illustrated
in FIG. 18. In this embodiment, the nanotube array is coated by
polymeric material deposited from vapor phase (for example,
parylene) to fill the space between the nanotubes to create a
matrix that holds the nanotubes together and precludes mass
transport through that filled layer through any other channels
except the inner pores of carbon nanotubes. The filled CNT layer
can then be released from the substrate to form a free-standing
membrane that can then be etched from both sides to form a
permeable membrane.
[0231] Other embodiments for making the membranes are described
below. Without limited by any theory, it is to be understood that
the order of one or more steps may be altered in the methods of
making the membrane described herein.
[0232] In one aspect, there is provided a method of making a
membrane comprising, consisting essentially of, or consisting
of:
[0233] a) fabricating a substantially vertically-aligned array of
carbon nanotubes wherein the nanotubes have average pore size of
about 2 nm or less, and wherein the array comprises gaps between
the carbon nanotubes;
[0234] b) filling the gaps between the nanotubes with a ceramic
matrix material;
[0235] c) opening the nanotubes providing flow through the
membrane; and
[0236] d) functionalizing a tip of the nanotube with a functional
group.
[0237] In another aspect, there is provided a method of making a
membrane for enhanced fluid transport comprising, consisting
essentially of, or consisting of:
[0238] a) providing a substantially vertically-aligned array of
carbon nanotubes wherein the nanotubes have average pore size of
about 2 nm or less;
[0239] b) disposing a matrix material between the carbon
nanotubes;
[0240] c) opening the nanotubes providing flow through the
membrane; and
[0241] d) functionalizing a tip of the nanotube with a functional
group.
[0242] In another aspect, there is provided a method for
fabricating nanoporous membranes comprising, consisting essentially
of, or consisting of:
[0243] a) growing a substantially vertically aligned carbon
nanotube array on a substrate with high aspect ratio gaps between
the nanotubes wherein the nanotubes have average pore size of about
2 nm or less;
[0244] b) coating the array with a conformal matrix material
capable of conformably filling the high aspect ratio gaps between
the nanotubes to immobilize the nanotubes upon hardening of the
conformal matrix material;
[0245] c) opening the ends of the nanotubes; and
[0246] d) functionalizing a tip of the nanotube with a functional
group.
[0247] In yet another aspect, there is provided a method of making
a membrane comprising, consisting essentially of, or consisting
of:
[0248] a) fabricating a substantially vertically-aligned array of
carbon nanotubes, wherein the nanotubes have average pore size of
about 2 nm or less and wherein the array comprises gaps between the
carbon nanotubes;
[0249] b) filling the gaps between the nanotubes with polymeric
matrix material;
[0250] c) opening the nanotubes providing flow through the
membrane; and
[0251] d) functionalizing a tip of the nanotube with a functional
group.
[0252] In some embodiments, the fabrication step comprises vapor
deposition. In some embodiments, the filling step comprises vapor
deposition. In some embodiments, the fabrication step comprises
vapor deposition, and the filling step comprises vapor
deposition.
[0253] In some embodiments, the fabrication step comprises
providing a substrate surface comprising, consisting essentially
of, or consisting of metal nanoparticle catalyst for vapor
deposition. In some embodiments, a thin metal multilayer deposited
on silicon is used as the substrate to catalyze the growth. In some
embodiments, the thin metal multilayer is Fe. In some embodiments,
the thin metal multilayer has a thickness of about 5 nm to about 10
nm.
[0254] In some embodiments, the filling step comprises chemical
vapor deposition. In some embodiments, the filling step comprises
vapor deposition when the carbon nanotubes are capped.
[0255] In some embodiments, the methods further comprise etching on
both sides of the membrane to open the carbon nanotubes. In some
embodiments, the methods further comprise removing the carbon
nanotubes.
[0256] In some embodiments, the methods further comprise removing
the nanotubes after hardening of the matrix material. In some
embodiments, the nanotubes are removed by oxidation.
[0257] In some embodiments, acetylene, ethylene, hydrogen, and
argon are used as process gases for growing the nanotube array.
Without limited by any theory, it is to be understood that any
carbon containing gas may be used in this process.
[0258] In some embodiments, the conformal material is silicon
nitride. In some embodiments, the conformal material is TEOS
oxide.
[0259] In some embodiments, the CVD is used for the coating
process. In some embodiments, the ALD is used for the coating
process.
[0260] In some embodiments, the nanotubes are opened by removing
excess matrix material from the membrane. In some embodiments, the
excess matrix material is removed from the membrane using a plasma
etching process.
[0261] In some embodiments, the polymeric matrix material comprises
parylene.
4. Method of Using Membranes
[0262] A further embodiment is a method for separating analytes
from a fluid and therefore purifying a fluid by passing the liquid
or gas to be purified through at least one carbon nanotube as
described herein. In one aspect, the nanotubes are contained within
a membrane and the fluid to be purified is water for example from
fresh water sources or sea water containing salt. In some
embodiments, the liquid is blood or plasma. The method may also
comprise collecting the liquid or gas after passing through the one
or more nanotubes.
Water Desalination
[0263] Further described herein are water flow measurements through
microfabricated membranes with sub-6 nanometer (inner diameter)
aligned functionalized carbon nanotubes as pores. The measured
water flow exceeds values calculated from continuum hydrodynamics
models by more than two orders of magnitude and is comparable to
flow rates extrapolated from molecular dynamics simulations. The
gas and water permeabilities of these nanotube-based membranes are
several orders of magnitude higher than those of commercial
polycarbonate membranes, despite having order of magnitude smaller
pore sizes.
[0264] The membranes can be used in a wide variety of applications
including for example water desalination, water demineralization,
gas separation including removal of hydrocarbons, carbon dioxide
sequestration, dialysis, and breathable material for protection
from chemical and biological agents.
[0265] Both charge and size effects can impact exclusion. The
nanotubes are charged at the end with positive or negative charges
so that charged particles can be repulsed or attracted to the
nanotubes. Charge prevents ions from entering the nanotube which
might otherwise enter the nanotube if not for the charge.
[0266] Membranes can be used on substrates including for example
silicon or glass substrates, as well as porous substrates. Another
application is for use as a high capacity adsorbent material.
[0267] The membranes provided herein can be used in various fluid
or liquid separation methods, e.g., water purification,
demineralization, and desalination. For a general review of
desalination procedures see "Review of the Desalination and Water
Purification Technology Roadmap" available from the United States
Bureau of Reclamation, United States Department of the Interior.
See also for example U.S. Pat. Nos. 4,302,336; 4,434,057;
5,102,550, 5,051,178, and 5,376,253.
[0268] The CNT membranes can operate on the basis of both size and
charge screening (Donnan exclusion and Coulombic repulsion)
effects. Although many conventional membranes rely on both effects,
a novelty point for this CNT membrane lies in the higher water flux
achievable under conventional operating pressures. While the
present embodiments are not limited by theory, some principles are
noted. The nanometer size of CNTs (for example, 0.5-6 nm), which
approaches that of many solvated ions of interest to desalination
process, suggests that many species would be unable to enter the
nanotube and make it across the membrane. Indeed, recent molecular
dynamics simulations of osmotic water transport through carbon
nanotube membranes (Karla et al. (2004) PNAS 100(18):10175) suggest
that 0.8 nm diameter carbon nanotubes are sufficient to block
species as small as hydrated Na.sup.+ and Cl.sup.-. Yet another
screening effect is caused by charge layer overlap at the "mouth"
of the nanotube pore where charges are present (Miller et al.
(2001) JACS 13(49):12335).
[0269] In electrolyte solutions, counterions present (those of
opposite charge to the functional groups on the membrane surface)
to balance these tip charges. Under the appropriate ionic strength
and pore size, an overlap of these counterion charge layers occurs.
The net effect of this is the creation of an "ion gate" that will
exclude co-ions of like charge with the functional groups and only
permit counterions to pass through the channel. As a result, the
CNT membrane is designed for cation (for acid functionality) or
anion (for base functionality) transmission. A characteristic of
this type of exclusion is a dependency on the co-ion valency. For
example, for a base-functionalized membrane (carrying positive
charge), species such as Ca.sup.2+ and Mg.sup.2+ would be rejected
to a greater extent than monovalent species like Na.sup.+ and
K.sup.+ (Yaroshchuk (2001) Sep. and Purification Tech.
143:22-23).
[0270] High water permeability for the proposed membrane can be
carried out and the results interpreted in view of several studies
(for example, Kahn et al. (2004) PNAS 100(18):10175; Hummer (2001)
Nature 414:188; Koga et al. (2001) Nature 412:802) that have
predicted high water flux through SWCNTs. The high flux predictions
are partly a consequence of inherent atomic nanotube interior,
which leads to nearly frictionless transport. Another factor, which
appears to be unique to the non-polar CNT/polar molecule system,
relates to molecular ordering that can occur on this nanometer
scale. These molecular dynamic simulations (Kahn et al. (2004) PNAS
100(18):10175; Hummer (2001) Nature 414:188; Koga et al. (2001)
Nature 412:802) have suggested one-dimensional ordering of water
molecules confined within carbon nanotubes, leading to single
hydrogen bonds between them. These so-called "water wires", which
are of relevance in biological systems (Rouseau et al. (2004) Phys.
Chem. Chem. Phys. 6:1848), are able to shuttle in and out of the
carbon nanotube channels rapidly as a consequence of their ordering
and non-interaction with the pore walls. Recent experiments using
neutron diffraction have indeed confirmed the existence of these
"water wires" within carbon nanotube pores (Kolesnikov (2004) Phys.
Rev. Lett. 93: 035503-1), suggesting that the predicted rapid
transport rates should be experimentally observable.
[0271] Water desalination can be carried out by passing the water
through multiple membranes to produce purification which removes
for example at least 50 mole percent, or at least 60 mole percent,
or at least 70 mole percent, or at least 80 mole percent, or at
least 90 mole percent of the target molecule or ion such as for
example chloride or sodium.
[0272] In some embodiments, there is provide a method for
desalination of water, the method comprising passing the water
through a membrane comprising a plurality of nanotubes open at both
ends and embedded in a solid, substantially continuous polymeric
matrix, the polymeric matrix having a thickness that is less than
an average of the lengths of the nanotubes, the nanotubes having
substantially random orientations relative to the membrane and yet
oriented such that at least a portion of the plurality of nanotubes
have both open ends protruding from the membrane to provide fluid
communication through the membrane.
[0273] In some embodiments, the membrane further comprises a layer
of microporous material supporting the polymeric matrix.
[0274] In some embodiments, the ratio of the average of the lengths
of the nanotubes to the thickness of the polymeric matrix is from
about 1.3 to about 5.
[0275] In some embodiments, the ratio of the average of the lengths
of the nanotubes to the thickness of the polymeric matrix is from
about 2 to about 4.
[0276] In some embodiments, the polymeric matrix has a thickness of
from about 50 nm to about 300 nm.
[0277] In some embodiments, the average length of the nanotubes is
from about 100 nm to about 2000 nm.
[0278] In some embodiments, the average length of the nanotubes is
from about 200 nm to about 1000 nm.
[0279] In some embodiments, the nanotubes are carbon nanotubes with
inner diameters of about 0.4 nm to about 5 nm.
[0280] In some embodiments, the nanotubes are carbon nanotubes with
inner diameters of about 0.4 nm to about 1.2 nm.
[0281] In some embodiments, the polymeric matrix has a
substantially planar exposed outer surface and contains from about
2.5.times.10.sup.8 to about 1.times.10.sup.12 nanotubes per square
centimeter of the exposed outer surface.
[0282] In some embodiments, the polymeric matrix has a
substantially planar exposed outer surface and contains from about
2.5.times.10.sup.9 to about 2.5.times.10.sup.11 nanotubes per
square centimeter of the exposed outer surface.
[0283] In some embodiments, the polymeric matrix is a polyamide. In
some embodiments, the polymeric matrix is an aromatic
polyamide.
Fabric
[0284] This section describes the development of a
chemical/biological (CB) agent-resistant membrane based upon carbon
nanotube including single wall carbon nanotube membranes, as
described herein. This membrane can act as a molecular sieve,
exhibiting size selectivity against large molecules, a category
into which many CB agents may fall (e.g., VX, Sarin, Mustard). The
size selectivity of the nanotubes enables air and moisture to be
exchanged, while acting as a barrier against CB agents. This
combination creates a "breathable material" that can be eventually
incorporated into a CB garment, suitable for use, by a
warfighter.
[0285] A robust membrane comprising substantially
vertically-aligned CNTs, or randomly oriented nanotubes, embedded
in a biocompatible, gas- and liquid-impermeable polymer matrix
material can be fabricated. The nanotubes can span the membrane and
will be open on both sides, serving as the only channel for air and
water permeation. As a consequence of the uniqueness of the carbon
nanotube surface, high air and water permeability can be achieved,
making this membrane a choice for incorporation into a garment. The
CNT membrane can satisfy the needs of the warfighter, while
offering superior performance to conventional materials used.
Without being bound by theory, the size exclusion basis of
operation of this CNT membrane is believed to provide its greatest
advantage over conventional activated carbon, adsorption-based
materials, as well as over membrane-based fabric that feature
larger pore sizes. Significantly, comparable or better air
permeability can be achieved, despite the much smaller pore size.
This membrane is also flexible, durable, and resistant to
fouling.
[0286] One of the issues with the current protective fabrics is
their inability to provide high breathability and high degree of
protection at the same time. Some of the current robust protective
fabrics (e.g. solid membrane chemical protective suits) have
substandard breathability and some of the more breathable fabrics
(LANX) provide substandard or temporary protection. Fabrics
incorporating CNT membranes of the invention combine high
protective capability (enabled by chemical modification of CNT
pores to provide selectivity) with high breathability provided by
unique transport efficiency of CNT pores. This combination
distinguishes CNT membrane-based fabrics from other types of
protective fabrics.
[0287] Protective fabrics are typically incorporated in a
"layering" system that comprises an inner layer, a mid layer
(optional), and shell layer. Each layer performs a different
function: the inner layer, which is closest to the skin absorb
sweat and deliver the moisture to the outer layers typically
through capillary action, or wicking. The mid-layer provides
thermal insulation; therefore it is omitted in warm or moderate
climates. The outermost layer, called a shell layer, functions as a
protecting layer. It can also provide a good moisture outlet (hence
such fabrics are called "breathable" fabrics). Solid polymer
garments (such as commonly used chemically-protective butyl rubber
gloves) provide good protection to the wearer; yet they cannot
transport moisture out, which blocks the main evaporative cooling
pathways and creates a humid environment inside the garment. Such
environment compromises the individual's health and safety by
increasing the risk of heat stress, especially in a moderately warm
climate.
[0288] An example of the current state-of-the-art shell fabric that
provides some level of protection as well as some degree of
moisture management is Gore-Tex.TM., which has become a virtual
standard in technical outdoor fabrics. In outdoor use, Gore-Tex.TM.
blocks liquid water and wind, but lets through water vapor
(evaporated sweat). A Gore-Tex.TM. fabric is mainly composed of
five layers: (1) abrasion resistant outermost shell, (2) protective
mesh, (3) Gore-Tex membrane, (4) protective mesh, and (5) soft
inner layer. The Gore-Tex membrane itself is made of
thermo-mechanically expanded PTFE (polytetrafluoroethylene) and
other fluoropolymers. The typical membrane pore density is ca.
1.4.times.10.sup.9 cm.sup.-2. Estimations bracket the pore size of
the membrane between 50 and 150 nm, which is still roughly 700
times larger than the size of a water molecule. The tough exterior
layers of the Gore-Tex fabric give the material resistance to
mechanical stresses such as abrasion, as well as bear additional
water repellant coatings. Liquid water drops may or may not pass
through this exterior layer, but if they do, they are stopped by
the sub-micron scale hydrophobic fluoropolymer membrane pores. Yet,
moisture vapor generated by the skin and passed through the inner
layers can still move out through the pores.
[0289] Gore-Tex membrane provides a leap in moisture management in
comparison with the solid plastic garments, yet its pore size is
too large to provide sufficient protection from most CB agents and
it fails to satisfy the moisture management requirements in warm
climates. In particular, its vapor permeability is still too low to
sustain efficient moisture transport driven by a small partial
vapor pressure gradients typical for military use in warm
climates.
[0290] Functionalized carbon nanotube membrane of the invention
provides two advantages over the existing articles of breathable
protective membrane fabrics. First, the CNT pore size are at least
2 orders of magnitude smaller, enabling the membrane to reject
large agents based on size exclusion, which could be further
enhanced by chemical modification of the pore narrowing it down
even more. Second, CNT membrane structure and unique pore
characteristics provide enhanced air permeability. CNT membrane has
smaller pores but the pore density of those pores is relatively
high, typically about 10.sup.10 cm.sup.-2. Each of those pores has
enhanced transport characteristics unique to CNTs. The resulting
high air and water vapor permeability of the CNT membrane makes it
more breathable than the existing articles of breathable
membrane-based fabrics (FIG. 14). FIG. 14 illustrates a comparison
of water vapor fluxes measured for a carbon nanotube membrane and
for two commercial PTFE-based membranes that are used in
waterproof-breathable fabrics. CNT membrane data were collected
using a home-built pressure-driven flow test.
[0291] In particular, at 40% relative humidity, the water vapor
permeability of the CNT membrane was found to exceed the
permeability of GoreTex by about an order of magnitude (FIG.
15).
[0292] WO 2007/025104, filed Aug. 23, 2006, that describes the
nanoporous membranes used for desalination, dialysis and fabric
formation, is incorporated herein by reference in its entirety in
the present disclosure.
Dialysis
[0293] The membranes as described herein also find use in
biological applications, e.g., for nanofiltration similar to that
performed by the kidney. For example, the nanotubes and membrane
containing the nanotubes can be used for separation of analytes in
blood or serum and therefore provides methods and materials for
dialysis ex vivo and in vivo.
[0294] Some of the recent advances in dialysis have been in the
area of porosity-controlled, high-flux synthetic membranes.
Porosity control is important to achieve the desired
separation/sieving profile, with maximal permeability for solutes
of <40 kD molecular weight and minimal or no permeation of
albumin (48 kD molecular weight, approximately 6-7 nm effective
diameter). High-flux membranes offer the important advantage of
reducing the treatment time. Multiwall carbon nanotube membranes
offer both the requisite porosity control (filtering out albumin on
the basis of size exclusion), as well as a much higher flux than
that offered by current nanoengineered dialysis membranes. The
presence of negatively charged functional groups on the membrane
also help reduce the permeation of the similarly charged
albumin.
Gas Separation
[0295] Gas permeability of MWCNT/SiNx membranes is characterized
and membranes show measured rates of up to three orders of
magnitude greater than predicted by conventional models. For gas
diffusion within the molecular flow regime, wherein the local gas
mean free path is more than one order of magnitude greater than the
pore diameter, the Knudsen diffusion model is typically applied.
This model assumes no interaction between gas molecules and diffuse
scattering of gas molecules from the surface dominating. The gas
permeability measured for this membrane is up to three orders of
magnitude greater than predicted by Knudsen diffusion (shown in WO
2007/025104), assuming the nitrogen porosimetry-observed average
pore size of 7 nm and an upper limit of pore density equal to that
of the MWCNTs (as observed by scanning electron microscopy). FIG. 5
of WO 2007/025104 presents this data for variety of gases in the
form of molecular weight-normalized flow rate versus pressure drop,
along with the Knudsen prediction. These results constitute the
first experimental demonstration of enhanced gas flux through a
carbon nanotube membrane.
[0296] Gas permeability of DWCNT/SiNx membranes is characterized
and membranes show measured rates of up to two orders of magnitude
greater than predicted by conventional models i.e. Knudsen model
(Holt et al. (2006) Science 312:1034-1037).
[0297] This enhancement in gas flux through carbon nanotubes has
previously been predicted by molecular dynamics simulations for
SWCNTs, related to their inherent atomic smoothness, leading to
spectacular rather than diffuse reflection of gas molecules from
the pore surface. In particular, single wall carbon nanotubes are
predicted by these simulations to exhibit a three order of
magnitude higher gas flux than comparably-sized nanomaterials such
as zeolites (nanoporous alumina or silica materials); this flux is
also three orders of magnitude lighter than predicted by assuming
Knudsen diffusion. More recently, simulations on SWCNTs of up to
8.1 nm in diameter (Bhatia et al. "Comparisons of Diffusive and
Viscous Contributions to Transport Coefficients of Light Gases In
Single-Walled Carbon Nanotubes", submitted to Molecular Simulation,
2005) have similarly predicted an almost two order of magnitude
enhancement as compared with the diffuse reflection limit.
[0298] As will be apparent to those of skill in the art, the
membranes as described herein can also be for filtration and
separation of large airborne particles from gases using the
techniques described. Different gases in gas mixtures can also be
separated from each other using these membranes. For example, one
of the important gas pairs for separation is CO.sub.2/N.sub.2. It
has been demonstrated that the unfunctionalized membranes do not
exhibit high selectivity of CO.sub.2/N.sub.2 but that
functionalization with groups, such as but not limited to, amine
increases the gas selectivity of the membranes. Functionalization
often also decreases the permeability of the membrane. Due to the
extremely high permeability of sub 6-nm CNT membranes, even with
the expected permeability loss of two orders of magnitude due to
functionalization, the membranes are still superior to conventional
materials (such as mesoporous silica).
[0299] FIG. 16 illustrates trade-off between the increased
selectivity and permeance. For example, functionalized silica
membrane showed higher selectivity but the permeance decreased by
one or two orders of magnitude (Sakamoto et al. (2007) Microporous
and Mesoporous Materials 101:303-311, Kumar et al. (2008) Ind. Eng.
Chem. Res. 47:201-208). With the expected permeance decrease by, at
most, two orders of magnitude and high gas selectivities due to
functionalization, CNT membrane permeance range is comparable to
current mesoporous membrane systems with low gas selectivities. In
FIG. 16, MCM48 is mesoporous mobil crystalline materials (MCM)-48
silica membrane; PC is polycarbonate membrane; PI is polyimide
membrane; and FDA-PI is 4,4-(hexafluoroisopropylidene)diphthalic
anhydride-polyimide or fluorine polyimide membrane.
EXAMPLES
[0300] The invention is further understood by reference to the
following examples, which are intended to be purely exemplary of
the invention. The present invention is not limited in scope by the
exemplified embodiments, which are intended as illustrations of
single aspects of the invention only. Any methods that are
functionally equivalent are within the scope of the invention.
Various modifications of the invention in addition to those
described herein will become apparent to those skilled in the art
from the foregoing description and accompanying figures. Such
modifications fall within the scope of the appended claims.
[0301] Unless otherwise stated all temperatures are in degrees
Celsius. Also, in these examples and elsewhere, abbreviations have
the following meanings
TABLE-US-00001 AFM = atomic force microscopy CNT = carbon nanotube
CVD = chemical vapor deposition DWNT = double-wall nanotube ITO =
indium tin oxide MD = molecular dynamics MWNT = multi-wall nanotube
PVA = polyvinyl acetate RO = reverse osmosis SWNT = single-wall
nanotube TEM = transmission electron microscopy TEOS =
tetraethyloxy silane UV-VIS = ultraviolet-visible
Example 1
[0302] In this study, nanofiltration experiments are used to
quantify ion exclusion in the sub-2-nm carbon nanotube pores and to
investigate the fundamental mechanisms governing ion transport and
ion exclusion in this system. Charged nanochannels can utilize both
steric hindrance and electrostatic repulsion to achieve ion
rejection (Schaep et al. (1998) Sep. Purif. Technol. 14:155-162;
Schaep et al. (2001) Sep. Purif. Technol. 22-3:169-179; and
Childress & Elimelech (2000) Environ. Sci. Technol.
34:3710-3716). To understand the relative importance of these
rejection mechanisms, ion exclusion and selectivity as a function
of solution concentration, pH, ion valence, and ion size is
investigated. The measurements obtained in this experiment provide
an indication that ion rejection in nanopores of this size is
predominantly governed by the electrostatic effects and demonstrate
that Donnan's membrane equilibrium model (Donnan (1924) Chem. Rev.
1:73-90; and Donnan (1995) (reprinted from Zeitshrift fur
Elektrochemie and Angewandte Physikalische Chemie, vol 17, pg
572,1911). J Membrane Sci. 100:45-55) accounts for most of the
experimentally observed transport selectivities.
Materials and Methods
Materials
[0303] The salts used in this study are: potassium ferricyanide
(K.sub.3Fe(CN).sub.6, 99+% purity, Aldrich, St. Louis, Mo.),
potassium chloride (KCl, 99.999%, Aldrich), potassium sulfate
(K.sub.2SO.sub.4, 99%, Sigma, St. Louis, Mo.), calcium sulfate
dehydrate (CaSO.sub.4, 98%, Sigma), calcium chloride (CaCl.sub.2,
99.5%, EM Science; Darmstadt, Germany),
tris(2,2'-bipyridyl)dichlororuthenium hexahydrate
(Ru(bipy).sub.3Cl.sub.2, Fluka, Buchs, Switzerland),
1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (PTSNa.sub.4,
Invitrogen, Carlsbad, Calif.). 4-methylbenzylamine (97% purity) and
.alpha.-hydroxyisobutyric acid (.alpha.-HIBA) are purchased from
Sigma-Aldrich. All salt solutions and buffers are prepared using 18
M.OMEGA. water generated by a Milli-Q laboratory water purification
system (Millipore, Bedford, Mass.), and subsequently filtered
through a 0.1 .mu.m PVDF filter (Millipore).
Membrane Fabrication
[0304] Silicon nitride/CNT composite membranes were fabricated
according to the previously reported method (Holt (2006) Science
312:1034-1037). Briefly, a dense, vertically-aligned array of
double-walled carbon nanotubes (DWNT) with sub-2 nm diameters is
grown by catalytic chemical vapor deposition (CVD) on the surface
of a silicon chip using ethylene as carbon source and Fe/Mo as
catalyst. Conformal encapsulation of the nanotubes by low-pressure
silicon nitride deposition produces a gap-free matrix that fills
the volume between DWNTs. Excess silicon nitride on both sides of
the membrane and the catalyst particles are removed by argon ion
milling. Reactive ion etching in an oxygen containing plasma
further exposes and opens the carbon nanotubes. The final result is
a silicon nitride membrane with DWNT pores that span the entire
membrane thickness and have carboxylic functional groups at their
tips (Yang et al. (2005) Langmuir 21:8539-8545; and Li et al.
(2007) J. Phys. Chem. B 111:1672-1678). The free-standing membrane
area is about 0.175 mm.sup.2 with a DWNT density of about
2.5-10.sup.11 cm.sup.2 (Holt et al. (2006) Science
312:1034-1037).
Nanofiltration Experiments
[0305] A schematic of the filtration cell is shown in FIG. 1e. A
2.times.2-cm CNT membrane sandwiched between two O-rings divides
the cell in two chambers. The top chamber (feed) is filled with
about 2 ml of salt solution, while the bottom chamber (permeate) is
sealed with a small vial containing 1 ml of distilled water, whose
function is to minimize errors in the measured rejection by
limiting permeate evaporation before the analysis of ion
concentration. The feed solution is pressurized at 0.69 bar with a
controlled nitrogen gas line, while the permeate is at atmospheric
pressure. Permeate flow rate is measured as height variation of the
column of salt solution in the top chamber with respect to time.
When 100-150 .mu.l of solution has permeated through the CNT
membrane, the nanofiltration experiment is stopped, and solution
samples from both feed and permeate are collected for subsequent
analysis by either capillary electrophoresis or UV-vis
spectroscopy. Samples that are not immediately analyzed are stored
at 4.degree. C. in sealed vials to prevent evaporation. For testing
Donnan prediction about the rejection dependence on ion valence,
salt solutions with the same equivalent concentration are used:
salt content is 0.5 mM for all solutions except KCl (1.0 mM) and
K.sub.3Fe(CN).sub.6 (0.3 mM).
Capillary Electrophoresis Analysis
[0306] A Hewlett Packard 3D CE capillary electrophoresis system
(Agilent Technologies, Santa Clara, Calif.) is used to determine
both anion and cation concentration. Fused silica capillaries with
50 .mu.m internal diameter and 40 cm length from injection point to
detection window were purchased from Agilent Technologies. Samples
are introduced into the capillary by a 5-s hydrodynamic injection
at 50 mbar. Non-absorbing ions are detected by indirect UV method.
For anion analysis, the running buffer is Agilent inorganic anion
buffer (pH=7.7) containing 1,2,4,5-benzenetetracarboxylic acid as
background electrolyte; the applied voltage is -25 kV; and the
detection wavelength is 210 nm. For cation analysis, either lonPhor
cation DDP buffer (pH=4.5) (Dionex, Sunnyvale, Calif.) or UV Cat-1
buffer (Weston et al. (1992) J. Chromatogr. 602:249-256; and Weston
et al. (1992) J. Chromatogr. 593:289-295) are used as prepared in
the laboratory (5 mM 4-methylbenzylamine, 6.5 mM
.alpha.-hydroxyisobutyric acid; pH=4.3). The detection wavelengths
are 225 and 214 nm for IonPhor and UV Cat-1 buffers, respectively,
and the applied voltage is 30 kV. A direct detection method is used
to measure Ru(bipy).sub.3.sup.2+ concentration, since the cation
strongly absorbs at 286 and 452 nm. Measurements for feed and
permeate concentration (from peak area) are repeated at least three
times, and typically agree within 2-3%. Average values are used for
rejection calculations.
Experiments Testing Rejection Sensitivity to Solution pH
[0307] PTSNa.sub.4 rejection is measured at two different pHs, 7.2
(no pH adjustment) and 3.8. A few drops of 0.1N HCl are used to
reduce the pH of a 0.5 mM PTSNa.sub.4 solution at the desired level
while maintaining nearly constant ionic strength and osmotic
pressure. The ionic strength, Debye length, and osmotic pressure
are 5.0 mM, 4.34 nm, 0.062 bar for the experiment at neutral pH,
and 5.16 mM, 4.28 nm, 0.070 bar, respectively, for the experiment
at acidic pH. Thus, the added hydrochloric acid for pH adjustment
has minor impact on ionic strength, osmotic pressure, and Debye
length.
[0308] Full PTS.sup.4- UV-spectrum is obtained with a Lambda 25
UV-vis spectrometer (PerkinElmer, Waltham, Mass.) after a 1:20
dilution with 18 M.OMEGA. water. PTS.sup.4- concentration is
measured at 244, 283, and 375 nm. Measured anion rejection
coefficients are independent of the chosen wavelength. Na.sup.+
concentration is obtained by capillary electrophoresis as explained
above.
Results
[0309] To quantify ion rejection in CNT membranes, pressure driven
filtration is used for electrolyte solutions (FIG. 1e) followed by
capillary electrophoresis (CE) analysis of the ion concentration in
the permeate and feed solutions (FIG. 1f). Several observations
emerge from these experiments. First, carbon nanotube membranes
maintain the extraordinarily high rates of water flow reported in
the previous study (FIG. 1d) (Holt et al. (2006) Science
312:1034-1037). Filtering the ionic solutions through the membrane
for extended periods of time does not result in the membrane
clogging. Second, CE measurements indicate that CNT membranes
reproducibly (see Supporting Information below) exclude a large
portion of the ionic species present in the feed solution. For
example, passing of 1.0 mM potassium ferricyanide
(K.sub.3FeCN.sub.6) solution under a 0.69 bar pressure differential
across the membrane results in the exclusion of .about.91% of the
anions and 79% of the cations. For 1.0 mM Potassium chloride (KCl)
solution under 0.69 bar, CNT membranes exhibit smaller, yet still
significant rejection of Cl.sup.- (45%) and K.sup.+ (37%). These
rejection ratios are comparable to the rejection ratios exhibited
by a tight nanofiltration membrane (Filmtec NF90) tested under the
same conditions. Note that the DWNT membranes provide an order of
magnitude higher flux than the commercial nanofiltration membrane
Filmtec NF90.
Modulation of the Electrostatic Field at the CNT Mouth by Solution
pH
[0310] The size of the CNT membrane pores is 1.3-2.5 times larger
than the solvated radii of the ions used in the studies (Table 1).
Reported hydrated radii in Table 1 are from reference (Nightingale
(1959) J. Phys. Chem-US 63:1381-1387), except for
Fe(CN).sub.6.sup.3- (crystallographic radius (Carter et al. (2003)
Austr. J. Chem. 56:675-678)) and Ru(bipy).sub.3.sup.2+ (Majumder et
al. (2005) J. Am. Chem. Soc. 127:9062-9070)). Ionic diffusivities
are from reference (Newman & Thomas-Alyea (2004)
Electrochemical Systems (John Wiley & Sons, Inc., Hoboken)),
except for Ru(bipy).sub.3.sup.2+ (Majumder M et al. as above).
TABLE-US-00002 TABLE 1 Studied ionic species: valence z, hydrated
radius .gamma..sub.h, Stokes radius .gamma..sub.s, and bulk
diffusivity D.sub..infin.. Ion z .gamma..sub.h [nm] .gamma..sub.s
[nm] D.sub..infin. [10.sup.-5 cm.sup.2/s] Fe(CN).sub.6.sup.3- -3
0.475 0.273 0.896 SO.sub.4.sup.2- -2 0.379 0.230 1.065 Cl.sup.- -1
0.332 0.121 2.032 K.sup.+ 1 0.331 0.125 1.957 Ca.sup.2+ 2 0.412
0.310 0.791 Ru(bipy).sub.3.sup.2+ 2 0.590 0.475 0.516
[0311] For these solute-to-pore size ratios, a sieving effect due
to steric hindrance or hydrodynamic interactions with the pore wall
may contribute to the observed ion rejection (Dechadilok & Deen
(2006) Ind. Eng. Chem. Res. 45:6953-6959; and Deen (1987) AlChE
3:1409-1425). It is also likely that the rejection mechanism
involves charge repulsion due to the interaction of the ions with
the ionized carboxylic groups at the CNT mouth (Yang et al. (2005)
Langmuir 21:8539-8545; and Li et al. (2007) J. Phys. Chem. B
111:1672-1678). To test the importance of the electrostatic
interaction, the exclusion characteristics of the CNT membrane at
two different solution pH values was measured, one above the
pK.sub..alpha. of the COOH group on the surface (pK.sub.a=5.5)
(Vezenov et al. (1997) J. Am. Chem. Soc. 119:2006-2015) (and, also,
on a carbon nanotube tip, pK.sub.a=4.5 (Wong et al. (1998) Nature
394:52-55; and Wong et al. (1998) J. Am. Chem. Soc.
120:8557-8558)), and one below it.
[0312] For these experiments, a 0.5 mM pyrenetetrasulfonic acid
tetrasodium salt solution (PTSNa.sub.4) is used because the large
PTS.sup.4- ion remains ionized over a wide range of solution pH
values (Nagai et al. (2006) J. Control Release 115:18-25). Also,
the selected low solution concentration minimizes possible
screening of electrostatic interactions (see next section). As the
solution pH changes from a high to a low value, the COO.sup.-
groups become protonated and neutral, which should result in a
sharp drop in the membrane rejection ratio. Indeed, at a pH=7.2,
PTS.sup.4- absorption in the permeated solution is nearly
undetectable (FIG. 2a), indicating an almost complete exclusion
(96% of anions, FIG. 2b). However, at pH=3.8, the rejection ratio
drops sharply to only 60% (FIG. 2b). These results support a major
role of electrostatic interactions in ion rejection.
Ion Rejection and Electrostatic Screening at the CNT Mouth
[0313] If electrostatic interactions at the nanotube mouth play a
role in ion rejection, then the rejection properties of the
membrane should be highly sensitive to the degree of electrostatic
screening and, thus, to solution ionic strength. Indeed, Applicants
observe that variations in the electrolyte concentration of the
solution produce large modulations of the membrane rejection ratio
(FIG. 3a-b). For K.sub.3Fe(CN).sub.6 filtration, anion rejection is
almost complete and independent of the solution ionic strength as
long as the Debye length .lamda..sub.D is larger than the carbon
nanotube diameter d.sub.CNT (FIG. 3). The Debye length is defined
as
o r k B T 2 N A e 2 I ' , ##EQU00001##
where .epsilon..sub.o and .epsilon..sub.r are the vacuum and
relative permittivity, respectively, k.sub.B is the Boltzmann
constant, T the absolute temperature, e the elementary charge,
N.sub.A the Avogadro number, and I the ionic strength of the
solution. Because Applicants' feeds are single salt solutions, I is
proportional to the feed concentration, c.sub.o, and
.lamda..sub.D.alpha.C.sub.o.sup.-1/2.
[0314] However, when .lamda..sub.D drops down close to d.sub.CNT,
Fe(CN).sub.6.sup.3- exclusion rapidly decays to a value as low as a
few percent. K.sup.+ rejection shows an identical trend although it
is somewhat (.about.10%) lower than Fe(CN).sub.6.sup.3- rejection
at low ionic strength, a difference that disappears with increasing
salt concentration. Anion and cation rejections for KCl mirror the
trends observed for K.sub.3Fe(CN).sub.6 with the exception that the
maximum measured rejection was .about.54% for Cl.sup.- and 41% for
K.sup.+. Notably, KCl rejection decays less sharply with decreasing
.lamda..sub.D. Similar to the trend observed in the
K.sub.3Fe(CN).sub.6 rejection experiments, percent anion exclusion
is slightly higher than percent cation exclusion (see Supporting
Information for a possible explanation of this small
difference).
[0315] These trends can be rationalized if an exclusion mechanism
is considered that accounts for the effect of the Donnan membrane
equilibrium. The Donnan model provides a well-known classical
description of the electrochemical equilibrium that is established
when an ionic solution contacts a charged membrane. Because
electrostatic forces with the fixed charges on the membrane
counteract the tendency of the co-ions (ions having the same charge
sign of the pore charges) to move in the direction of Applicants'
concentration gradient, charged species distribute unequally
between membrane and solution phase. This results in the membrane
being enriched with counter-ions and depleted of co-ions. As a
consequence, a potential difference is established at the
solution/membrane interphase (Donnan potential). When a pressure
gradient is applied in a filtration experiment, the Donnan
potential tends to exclude co-ions from the membrane. Because of
the electroneutrality requirement, which arises from the energetic
cost of charge separation, counter-ions have to be rejected as
well. Donnan theory provides the following expression for the
rejection coefficient, R, of ideal point-charge ions permeating
through a charged membrane (Schaep et al. (1998) Sep. Purif.
Technol. 14:155-162):
R = 1 - c i m c i = 1 - ( z i c i z i c i m + c x m ) z i / z j ,
Eq . 1 ##EQU00002##
where c.sub.i and c.sub.i.sup.m, are the concentrations of co-ions
in the solution and in the membrane phase respectively,
c.sub.x.sup.m is the membrane charge concentration, and subscripts
i and j indicate co-ions and counter-ions, respectively. Eq. 1
indeed provides an ion-exclusion dependence on the Debye length
that closely approximates the measured trend. The explicit
expression of the rejection coefficient dependence on .lamda..sub.D
can be easily obtained by substituting c.sub.i with
.alpha./.lamda..sub.D.sup.2 in Eq. (1), where .alpha. is defined
as
o r k B T N A e 2 ( z i 2 + z i z j ) . ##EQU00003##
[0316] Eq. 1 also predicts that the rejection coefficient decreases
faster by decreasing .lamda..sub.D for a 1:3 salt (such as
K.sub.3FeCN.sub.6) than for a 1:1 salt (such as KCl), which is
exactly what the experimental data show (FIG. 3b). The decay of
rejection with increasing salt concentration can be explained by
the simple reasoning that follows. For a charged pore with diameter
greater than the permeating ion, Applicants expect significant
exclusion of co-ions when the range of ion electrostatic
interaction (.lamda..sub.D) with the pore charges is much larger
than the pore size, d.sub.CNT. With increasing salt concentration,
as .lamda..sub.D becomes comparable to d.sub.CNT, a rejection
coefficient based on electrostatic interaction quickly decreases
because the electrostatic potential decays rapidly with
1/.lamda..sub.D away from a charged wall (Newman & Thomas-Alyea
(2004) Electrochemical Systems (John Wiley & Sons, Inc.,
Hoboken)). The observed concentration dependence of rejection
coefficients alone does not provide a definitive proof that the
charges on the CNT entrance are responsible for the reduced ion
rejection at larger concentrations since the reduction of ion
rejection may simply be a result of the variation of the driving
forces for transport rather than a consequence of the reduced range
of electrostatic interaction. Indeed, for both neutral and charged
solutes at constant applied pressure, an increase in feed
concentration reduces water permeation and increases the ion
permeation rate. The effective driving force for water permeation
is reduced due to the raising osmotic pressure, while the effective
driving force for ion permeation is increased due to increased
concentration gradient. However, a combination of the concentration
dependence and the observed sensitivity of the rejection properties
to the change of solution pH does provide a strong indication that
electrostatic forces are one of dominant contributors to the ion
rejection.
Ion Valence and Ion Exclusion
[0317] One of the important consequences of the Dorman exclusion
mechanism is the extreme sensitivity of the rejection ratio to the
valency of the cationic (z.sup.+) and anionic (z.sup.-) species
present in solution. Indeed, Eq. 1 predicts that the rejection
should increase rapidly with the increase of the ratio of
z.sup.-/z.sup.+. This is a consequence of the fact that, in this
theory, the ion rejection exhibited by the membrane is due to the
equilibrium partitioning of ions between the solution and membrane
phase under the constraints of electroneutrality. Electrostatic
forces repel anions from the negatively charged CNT tips while
attracting cations. The electroneutrality condition prevents an
independent migration of anions and cations. Thus, the overall
rejection is determined by a balance between two opposite
electrostatic forces: the larger the anion valence relative to the
cation valence, the stronger the net repulsive force and,
therefore, the salt rejection. On the contrary, a larger cation
valence screens more effectively the carboxylic groups on the DWNT
entrance, facilitating anion permeation.
[0318] To test if ion rejection can be described by the Donnan
model, the ion exclusion by the CNT membrane was measured for a
series of salts differing in ion valence at the same equivalent
solution concentration: K.sub.3Fe(CN).sub.6 (cation-anion valence,
z.sup.+-z.sup.-: 1-3), K.sub.2SO.sub.4 (1-2), CaSO.sub.4 (2-2), KCl
(1-1), CaCl.sub.2 (2-1), and Ru(bipy).sub.3Cl.sub.2 (2-1). These
measurements were conducted at low ionic strength
(.lamda..sub.D>>d.sub.CNT) to ensure that the rejection
coefficient stays nearly independent of concentration and close to
its maximum for a 0.69 bar pressure differential used in their
measurements. Remarkably, rejection coefficients measured in these
experiments (FIG. 4) show a significant increase for larger
z.sup.-/z.sup.+ ratios from negligible rejection (CaCl.sub.2 and
Ru(bipy).sub.3.Cl.sub.2) to nearly complete exclusion
(K.sub.3Fe(CN).sub.6). Note also that the rejection of the
symmetric salts CaSO.sub.4 and KCl (z.sup.-/z.sup.+=1) is about the
same (.about.37%), despite the larger charge and size of both the
anion and cation of CaSO.sub.4 relative to KCl. Similarly,
CaCl.sub.2 and Ru(bipy).sub.3.Cl.sub.2 (z.sup.-/z.sup.+=0.5)
permeate almost freely through the DWNT membrane. The measured
rejection for Ru(bipy).sub.3.Cl.sub.2 is slightly lower than that
of calcium chloride, which is a somewhat striking result
considering the much larger size of the Ru(bipy).sub.3.sup.2+
cation.
[0319] A comparison of the measured ion rejection rates with the
prediction of the Donnan model using a reasonable membrane charge
density (see Supporting Information below) provides a strong
argument for the claim that ion rejection in CNT membranes is
dominated by electrostatic interactions (FIG. 4). Moreover, a
comparison of the measured rejection ratios with the predictions of
the hindered transport model that describes the effects of steric
hindrance on the expected ion permeability shows poor correlation
(see Supporting Information). Thus, the data strongly suggest that
the underlying mechanism of ion exclusion in sub-2-nm CNT membranes
is indeed dominated by electrostatic interactions, and that ion
size (relative to the DWNT average diameter, 1.6 nm) is much less
important.
[0320] Molecular dynamics (MD) simulations of uncharged carbon
nanotubes (Park et al. (2006) Nanotechnology 17:895-900; Peter
& Hummer (2005) Biophys. 89:2222-2234; Leung et al. (2006)
Phys. Rev. Lett. 96:4; and Liu et al. (2006) J. Chem. Phys.
125:084713) also show that pores with diameters >1 nm pose
little free-energy barrier for permeation of small ionic species
such as Na.sup.+ or K.sup.+ and that these ions retain their
hydration shell almost entirely in pores of these diameters. On the
contrary, entrance into subnanometer CNT imposes a high energy
penalty because it requires losing part of the hydration shell. MD
simulations for other hydrophobic nanopores used as models for
biological nanochannels (Beckstein & Sansom (2004) Phys. Biol.
1:42-52; and Beckstein et al. (2004) J. Am. Chem. Soc.
126:14694-14695) reach similar conclusions.
[0321] For charged CNTs, theoretical efforts have focused on
understanding ion transport through subnanometer CNT and under an
external electric field. Both cases of tip localized charges
(Joseph et al. (2003) Nano Letters 3:1399-1403) and of distributed
charges along the pore wall (Park et al. (2006) Nanotechnology
17:895-900; Joseph et al. (2003) Nano Letters 3:1399-1403; and
Sumikama et al. (2006) J. Phys. Chem. B 110:20671-20677) have been
considered. Unfortunately, a direct comparison with Applicants
experimental data is difficult because none of these studies
considered pressure-driven filtration and ion valence effects.
Moreover, the diameter of the simulated carbon nanotubes is
significantly smaller than Applicants CNT diameters, making
confinement effects much more important in the simulated
scenario.
[0322] Since gap junction (GJ) membrane channels have pore sizes
similar to those of the CNTs used in this study (1-2 nm) (Hille
(2001) Ion Channel of Excitable Membranes (Sinauer Associates,
Inc., Sunderland)), parallels can be drawn between ion rejection
mechanisms of these channels and the CNTs used here. Interestingly,
small ions are believed to transport through the GJ selectivity
filter with little or no loss of their hydration shell. These
channels often transport preferentially negatively or positively
charged species, and their ion selectivity is also believed to be
primarily determined by the presence of charged residues on the GJ
pores (Kronengold et al. (2003) J. Gen. Physiol. 122:389-405; and
Trexler et al. (2000) Biophys. J. 79:3036-3051). For example, the
cation selectivity of Cx46 hemichannels (1.15 nm wide pores) has
been demonstrated to be strongly influenced by fixed negative
charges located toward the extracellular end of the hemichannel.
Replacement of negatively charged residues with positively charged
groups imparted anion selectivity to the hemichannel (Kronengold et
al and Trexler et al.). Previous studies of GJ pores, together with
the data presented in this study, stress the importance of
electrostatic interactions in ion rejection mechanisms of pores in
the 1-2 nm regime.
[0323] Hydrophobic, 1-2 nm wide CNT pores with negatively charged
functionalities at their entrance exhibit significant ion rejection
when aqueous electrolyte solutions pass through the pore. The
observed sensitivity of the rejection to the solution pH and
electrostatic screening length suggests that electrostatic
interactions dominate over steric effects in governing ion
rejection. The observed trends are in agreement with Donnan
membrane equilibrium theory. The conclusions are consistent with
molecular dynamics studies for ion permeation in uncharged pores,
as well as with experimental work on biological ion channels of
similar pore sizes, such as gap junctions.
[0324] Biological pore channels share a number of structural and
functional features with CNTs that make CNT nanofluidic platforms
ideal candidates for the realization of a robust, biomimetic system
that could exploit the fast transport, selectivity, and gating
properties of biological pores. Possible applications range from
controlled, nanoscale delivery of therapeutics to molecular
sensing. The combination of ultrafast transport and ion exclusion
demonstrated in this work could also lead the way towards efficient
water desalination. Further reductions in CNT diameter, as well as
careful control of the pore surface chemistry, may further improve
the membrane performance.
Supporting Information
[0325] DWNT membranes with 1.6 nm average pore diameter
reproducibly exclude ions. FIG. 5 compare measured rejection
coefficients for two different DWNT membranes and with the same
salt solutions (0.3 mM K.sub.3Fe(CN).sub.6 in FIG. 5a and 1.0 mM
KCl in FIG. 5b), and for the same membrane and salt solution (1.0
mM K.sub.3Fe(CN).sub.6 in FIG. 5c). Inter-membrane variability of
measured rejection coefficients is less than 7%, whereas repeated
experiments for the same membrane agree within 5%.
Calculation of the Ion Rejection Predicted by the Donnan Model
[0326] To calculate the ion exclusion predicted by the Donnan
theory, Eq. 1 of the main text is used. In Eq. 1, the molar
concentration of the feed after a filtration experiment, c.sub.i,
is set equal to the initial concentration. Because of the small
amount of initial salt solution permeated during an ion rejection
measurement, this approximation introduces a negligible error,
estimated to be less than 5%. The unknown molar concentrations
c.sub.i.sup.m and c.sub.x.sup.m in Eq. 1 have been determined as
follows. Eq. 1 is an implicit equation in c.sub.i.sup.m that can be
solved once the membrane charge density is known. The membrane
charge density c.sub.x.sup.m is assumed to be constant and set
equal to 2.0 mM to match, within experimental error, the rejection
measured for 0.3 mM K.sub.3Fe(CN).sub.6 solution (see FIG. 4).
[0327] A membrane charge density of 2 mM is reasonable. A 2 mM
charge density corresponds to .about.7 charged groups for each CNT
since a CNT of 1.6 nm internal diameter and 3 .mu.m length (typical
thickness of Applicants' membranes) has an internal volume equal to
6.03.times.10.sup.-24 m.sup.3. The rim of a (14, 14) SWNT having a
.about.1.6 nm internal diameter contains 29 carbon atoms. Assuming
that the charged groups are only at the tips of the CNT, 1/4 of the
total carbon atoms on the CNT rim are replaced by charged groups in
a membrane with a 2 mM charge density.
Hindered Transport Model
[0328] The hindered transports model states that in liquid-filled
pores of molecular dimensions, a solute experiences hindrance to
diffusion and convection due to a combination of particle-wall
hydrodynamic interactions and steric restrictions (Deen (1987)
AlChE J 33:1409-1425). For uncharged solutes experiencing no other
intermolecular interaction with the pore walls, the hindrance
factors for convection, K.sub.c, and diffusion, K.sub.d, as well as
the equilibrium partition coefficient, .THETA., are fully defined
by the ratio of the solute and pore sizes, r.sub.s/r.sub.p. For
large membrane Peclet number Pe, diffusion is negligible and the
filtrate concentration is determined mainly by the convective
fluxes. Pe is defined as K.sub.cvL/K.sub.dD.sub..infin., where v is
the convective velocity, L the pore length, and D.sub..infin. is
the solute diffusivity in the bulk. Pe is .about.10 in Applicants'
nanofiltration experiments.
[0329] Under this condition, at steady state or pseudo-steady
state, the predicted rejection coefficient R, defined as
(1-c.sub.i.sup.permeat/c.sub.i.sup.feed) is simply given by
R=1-.THETA.K.sub.c Eq. 2
[0330] Expressions for .THETA.Khd c as a function of
r.sub.s/r.sub.p are found in literature for neutral spheres moving
in cylindrical pores (Dechadilok & Deen (2006) Ind. Eng. Chem.
Res. 45:6953-6959). To calculate of the rejection coefficient due
only to size effects, Applicants' model the ions as uncharged
spheres with sizes given by their hydrated radii and assume that
they permeate the DWCN membrane independently. Applicants also
consider the case of the neutral salt (anion+cation) modeled as an
uncharged sphere with a Stoke's radius obtained from its bulk
diffusivity through the Stoke's Einstein relation. Salt diffusion
coefficients are calculated from the ionic diffusivities listed in
Table 1 as D.sub.s=(z.sup.+-z.sub.-)
D.sub.+D.sub.-/(z.sup.+D.sub.+-z.sup.-D.sub.-)(Newman &
Thomas-Alyea (2004) Electrochemical Systems (John Wiley & Sons,
Inc., Hoboken)). The hydrated ion radii used here are those in bulk
solution and, therefore, only an approximation of the actual size
of the ions inside a nanotube. Confinement may affect differently
the hydration of different ions. However, simulations (Liu et al.
(2006) J. Chem. Phys. 125:084713; Peter & Hummer (2005)
Biophys. J. 89:2222-2234; Park et al. (2006) Nanotechnology
17:895-900; and Leung et al. (2006) Phys. Rev. Lett. 96:4) have
shown that small ions are able to retain almost entirely their
hydration shell in CNT pores with relatively large diameter (>1
nm). Thus, Applicants expect that no large errors are introduced in
their calculations by this approximation, and that their
conclusions remain valid.
[0331] FIG. 6 summarizes the predicted and measured rejection
coefficients for the six salts considered previously. Applicants
attribute the slightly negative rejection measured for
Ru(Bipy).sub.3.Cl.sub.2 to a small permeate evaporation before
analysis. Measured impact of evaporation on permeate concentration
is .about.about 4% every 24 h at room temperature. Applicants
expect, therefore, that reported rejection coefficients may be a
few percent lower than the real one. Clearly, steric constraints
and hydrodynamic interactions cannot explain observed trends. In
particular, the calculated cation rejection shows opposite behavior
with respect to the measured one.
On the Difference Between Anion and Cation Rejection for Single
Salt Nanofiltration
[0332] In many nanofiltration experiments Applicants have measured
an anion rejection somewhat larger (.ltoreq.10%) than the
corresponding cation rejection. For several cases, this difference
is a few percent larger than the typical experimental error in
Applicants measurements. Because overall solution electroneutrality
has to be maintained, the excess negative charge associated with
the rejected anions has to be balanced by positive charges. A
possible source of compensating positive charges is the migration
of the highly mobile protons from the permeate to the feed
solution. As a consequence, the filtrate pH should have shifted
toward basic values relative to the feed. Applicants observe about
one unit pH-shift (from pH=6.0-6.5 to pH=7.0-7.5) for the
experiments in FIG. 3, which may explain qualitatively the measured
small differences in anion and cation rejections. Nanofiltration
literature for conventional polymeric and ceramic charged membranes
reports several examples of this pH variation (Childress &
Elimelech (2000) Environ. Sci. Technol. 34:3710-3716; and de Lint
& Benes (2004) J. Membrane Sci. 243:365-377). The effect is
expected to be more important at extreme pHs, where protons or
hydroxyl ions are more abundant.
Example 2
[0333] Preliminary experimental data suggest that the DWNT-SiN
membranes with CNT tip attached with carboxylic groups outperform
typical commercial nanofiltration membranes (without carbon
nanotubes) for water softening by providing much larger fluxes at
similar monovalent salt rejection or, vice versa, by enabling
significantly larger salt rejection at similar water fluxes. For
example, a DWNT-SiN membrane rejected 40% of the ion content when a
1 mM KCl solution was filtered at a feed pressure of 10 psi. The
corresponding water flux was about 0.63 .mu.l/mm.sup.2 min. At the
same conditions, Filmtec NF90 and NF270 rejected 35% and less that
10% of the salt, respectively, while allowing water fluxes 5 and 2
times smaller than for the DWNT-SiN membranes. FIG. 7 shows
nanofiltration of 1 mM KCl solution at 10 psi. a) rejection
coefficient and b) water fluxes measured for DWNT membranes, and
commercial nanofiltration membranes NF90 and NF270.
[0334] The comparatively high rejection of the DWNT-SiN is
unexpected. Ion rejection of nanofiltration membranes is mainly due
to a combination of two mechanisms: 1) electrostatic interactions
between charged groups in the membranes and electrolytes in
solution, and 2) size sieving because of pore dimensions
approaching the radius of the hydrated ions. The pore diameter of
the commercial nanofiltration membranes is much smaller than the
diameters of the DWNT. Reported literature values are about
0.4-0.68 nm (0.54 nm average) for NF90 pore diameters, and
0.57-0.85 nm (0.71 nm average) for NF270, whereas DWNT diameters
range between 1-2 nm. Thus, if rejection is based on a sieving
mechanism, the commercial nanofiltration membrane should outperform
the DWNT-SiN membrane, contrarily to experimental observation.
Because rejection of small monovalent ions is tested, the
charge-based mechanism may dominate rejection for these membranes.
Estimated charge density for the DWNT-SiN is about 1-3 mM. For
commercial nanofiltration membranes, charge density may vary
significantly with salt type, concentration, solution pH, etc. For
1 mM NaCl solution, the estimated charge density of NF90 is about
20 mM (well within the typical charge densities reported in
literature for nanofiltration membranes). Based on these estimates,
ion rejection for commercial nanofiltration membranes should be
greater than for DWNT-SiN membranes. A possible explanation of the
observed better performances of DWNT-SiN membranes is the
inherently different localization of the charged groups responsible
for the ion rejection. For DWNT-SiN membranes, charged carboxylic
groups are concentrated at the pore entrance maximizing their
effectiveness. On the opposite, for the polymeric commercial
membranes, charged groups are distributed uniformly on the entire
membrane volume. Thus, only a fraction of these charges are
actively involved in the ion exclusion mechanism.
Example 3
Nanofiltration Experiment for Binary Salt Solutions
[0335] Binary KCl/K.sub.2SO.sub.4 salt solutions with desired
composition and constant equivalent concentration were prepared by
mixing appropriate amounts of 1 mM KCl and 0.5 mM K.sub.2SO.sub.4
stock solutions.
[0336] The top chamber (feed) of the filtration cell was filled
with about 2 ml of binary salt solution, while the bottom chamber
(permeate) was sealed with a small vial containing 1 ml of
distilled water to limit permeate evaporation before the analysis
of ion concentration. The feed solution was pressurized at 0.69 bar
with a controlled nitrogen gas line, while the permeate was at
atmospheric pressure. After 150-200 .mu.L, of solution had
permeated through the CNT membrane, samples from both feed and
permeate were collected for subsequent analysis by capillary
electrophoresis (CE). Rejection coefficients for Cl.sup.- and
SO.sub.4.sup.2- anions were obtained from the ratio of
resolved-peak area of the corresponding ion in the CE chromatogram
for permeate and feed samples.
[0337] FIG. 17 illustrates the anion rejection for binary
K.sub.2SO.sub.4/KCl salt solutions as a function of chloride anion
mole fraction X.sub.Cl.sub.- in the feed solution. The chloride
mole fraction is defined as the ratio of Cl.sup.- moles and the sum
of SO.sub.4.sup.2- and Cl.sup.- moles. The equivalent anion
concentration of all binary salt solutions is kept constant and
equal to 1.0 mM. Filled circles represent experimental rejections
for sulfate anions, while empty diamonds are for chloride anions.
Sulfate rejection is nearly independent of solution composition,
whereas chloride rejection declines with decreasing chloride
content in the feed solution.
[0338] Experimental results show that sulfate anion rejection is
insensitive to feed composition and is in the range 70-80%. On the
opposite, the exclusion of chloride anion declines significantly at
low chloride mole fractions from about 20% to negative rejections
(i.e., the permeate chloride concentration is larger than in the
feed). This trend can be explained as follows. At low chloride
concentration, a larger proportion of the least rejected anion
(here the chloride anion) has to permeate through the membrane to
balance the permeation of positively charged potassium ions, as
required by the electroneutrality condition. Thus, the lower the
feed chloride content the lower the chloride rejection after
filtration. The observed negative rejection suggests that
monovalent anions (that tend to concentrate in the permeate) can be
effectively separated from multivalent anions (that tend to
concentrate in the feed) for feeds with a low monovalent anion
concentration.
[0339] It is to be understood that while the invention has been
described in conjunction with the above embodiments, that the
foregoing description and examples are intended to illustrate and
not limit the scope of the invention. Other aspects, advantages and
modifications within the scope of the invention will be apparent to
those skilled in the art to which the invention pertains.
* * * * *