U.S. patent application number 14/521074 was filed with the patent office on 2015-02-05 for dispersion and retrieval of de-bundled nanotubes.
This patent application is currently assigned to KANEKA NORTH AMERICA LLC. The applicant listed for this patent is KANEKA NORTH AMERICA LLC, THE TEXAS A&M UNIVERSITY SYSTEM. Invention is credited to Riichi NISHIMURA, Hung-Jue SUE, Xi ZHANG.
Application Number | 20150037239 14/521074 |
Document ID | / |
Family ID | 44307479 |
Filed Date | 2015-02-05 |
United States Patent
Application |
20150037239 |
Kind Code |
A1 |
SUE; Hung-Jue ; et
al. |
February 5, 2015 |
DISPERSION AND RETRIEVAL OF DE-BUNDLED NANOTUBES
Abstract
A method for dispersing nanotubes, comprising forming a
nanocomposite solution with associated nanotubes and nanoplatelets,
mixing a surfactant to the nanocomposite solution, separating the
nanocomposite in solution, wherein the nanotubes remain suspended
in the surfactant solution, and isolating the nanotubes in
solution. In certain instances, the method further comprises
functionalizing the nanotubes in solution.
Inventors: |
SUE; Hung-Jue; (College
Station, TX) ; ZHANG; Xi; (College Station, TX)
; NISHIMURA; Riichi; (Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KANEKA NORTH AMERICA LLC
THE TEXAS A&M UNIVERSITY SYSTEM |
Pasadena
College Station |
TX
TX |
US
US |
|
|
Assignee: |
KANEKA NORTH AMERICA LLC
Pasadena
TX
THE TEXAS A&M UNIVERSITY SYSTEM
College Station
TX
|
Family ID: |
44307479 |
Appl. No.: |
14/521074 |
Filed: |
October 22, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12979945 |
Dec 28, 2010 |
8894963 |
|
|
14521074 |
|
|
|
|
61297986 |
Jan 25, 2010 |
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Current U.S.
Class: |
423/447.2 ;
423/447.1; 516/9; 977/742; 977/845 |
Current CPC
Class: |
B82Y 30/00 20130101;
Y10S 977/845 20130101; C01B 32/174 20170801; B82Y 40/00 20130101;
Y10S 977/742 20130101; C01B 2202/02 20130101; Y10S 977/786
20130101 |
Class at
Publication: |
423/447.2 ;
423/447.1; 516/9; 977/742; 977/845 |
International
Class: |
C01B 31/02 20060101
C01B031/02 |
Claims
1-20. (canceled)
21: A composition comprising: an exfoliated nanotube, wherein the
composition is produced by a process comprising: preparing a
mixture including at least one surfactant and at least one nanotube
associated with at least one nanoplatelet; and separating the
nanoplatelet such that 98.6% or more of the nanoplatelet is removed
from the mixture, wherein an amount of the exfoliated nanotube
remaining in the composition after the separating of the
nanoplatelet is 61% or more based on a content of the nanotube in
the mixture.
22: The composition of claim 21, wherein the at least one
surfactant comprises at least one selected from the group
consisting of an anionic surfactant, a cationic surfactant, and a
non-ionic surfactant.
23: The composition of claim 21, wherein the mixture includes the
at least one surfactant at a concentration of between 0.01 wt % and
10 wt %.
24: The composition of claim 21, wherein the separating of the
nanoplatelet comprises mixing at least one ionic solution
comprising an acid solution with the mixture.
25: The composition of claim 24, wherein the acid solution is mixed
at a concentration of between 0.1 mM and 900 mM.
26: The composition of claim 21, wherein the separating of the
nanoplatelet comprises at least one of filtering and
centrifuging.
27: The composition of claim 21, wherein the separating of the
nanoplatelet comprises performing centrifuging under a relative
centrifugal force of at least about 1,000 G.
28: An exfoliated nanotube obtained from the composition of claim
21.
29: A method of producing a composition, comprising: preparing a
mixture including at least one surfactant and at least one nanotube
associated with at least one nanoplatelet; and separating the
nanoplatelet such that 98.6% or more of the nanoplatelet is removed
from the mixture and that 61% or more of exfoliated nanotube
included in the mixture remains after the separating of the
nanoplatelet.
30: A composition produced by the method of claim 29.
31: A method of producing a nanotube, comprising: preparing a
composition by the method of claim 29; and isolating the exfoliated
nanotube from the composition.
32: The method of claim 31, wherein the isolating of the nanotube
comprises at least one of filtering, centrifuging, and drying.
33: A method of producing a nanotube, comprising: preparing a
nanocomposite mixture comprising a nanocomposite including at least
one nanotube and at least one nanoplatelet; mixing at least one
surfactant with the nanocomposite mixture to obtain a surfactant
composition including the nanotube suspended in the surfactant
composition; separating the nanocomposite such that the nanotube
remains suspended in the surfactant composition and that the
nanoplatelet is precipitated from the surfactant composition; and
isolating the nanotube from the surfactant composition, wherein the
preparing of the nanocomposite mixture comprises: preparing a first
composition including at least one nanotube oxidized in the first
composition; isolating the nanotube from the first composition;
re-suspending the nanotube in an aqueous solvent to obtain an
oxidized nanotube composition; mixing at least one nanoplatelet
with a second composition such that the nanoplatelet is exfoliated
in the second composition and that an exfoliated nanoplatelet
composition is obtained; and mixing the oxidized nanotube
composition and the exfoliated nanoplatelet composition to obtain
the nanocomposite mixture, and the surfactant comprises at least
one selected from the group consisting of an anionic surfactant and
a cationic surfactant.
34: The method of claim 33, wherein the surfactant is mixed in an
amount of between about 0.01 wt % and about 10 wt %.
35: The method of claim 33, wherein the mixing of the at least one
surfactant comprises mechanically agitating the nanocomposite
mixture.
36: The method of claim 33, wherein the separating of the
nanocomposite comprises mixing at least one ionic solution with the
composition.
37: The method of claim 33, wherein the isolating of the nanotube
comprises: functionalizing the nanotube to obtain a functionalized
nanotube; and dispersing the functionalized nanotube in a
solvent.
38: The method of claim 37, wherein the functionalizing of the
nanotube comprises mixing the surfactant composition with a
compound having at least one of an amine group and an amide
group.
39: The method of claim 37, wherein the functionalizing of the
nanotube comprises mixing the surfactant composition with a
compound having an amide group.
40: The method of claim 37, wherein the functionalizing of the
nanotube comprises mixing the surfactant composition with a
composition including sulfanilamide.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of and claims the
benefits of priority to U.S. Ser. No. 12/979,945, filed Dec. 28,
2010, which claims benefit under 35 USC .sctn.119 of U.S.
provisional application No. 61/297,986 filed Jan. 25, 2010,
entitled "Dispersion and Retrieval of De-bundled Nanotubes". All of
the above applications are incorporated herein by reference in
their entireties for all purposes.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND
[0003] 1. Field of the Invention
[0004] This invention relates generally to the methods of
manipulating nanotubes. More specifically, the invention relates to
a method of retrieving and isolating nanotubes dispersed in
solution.
[0005] 2. Background of the Invention
[0006] Nanotubes are a novel class of nanostructures that exhibit
significant mechanical, electrical, and thermal properties, thus
having potential applications such as nanoscale probe devices,
energy storage components, sensors, flame retardant materials,
conductive ink, and electrical conductors in the aerospace,
automotive, micro-electric, photovoltaic, and energy transmission
industries. In addition, nanotubes may be constructed of a variety
of different materials, including carbon, silicon, metal-oxide and
other inorganic compounds. Nanotubes may be classified as
multi-walled nanotubes (MWNT) and single walled nanotubes (SWNT).
SWNT in particular exhibit remarkable properties, but are difficult
to manipulate individually.
[0007] Specifically, after synthesis SWNT nanotubes demonstrate an
affinity for forming into roped, bundled or entangled
configurations. The aggregated nanotube bundles do not yield the
theoretically advantageous properties expected by calculations. The
technical advantage of dispersing nanotubes for use in organic and
inorganic media has implications in creating material with uniform
nanotube distribution acting as a structural, mechanical,
conductive or thermal component of the material.
[0008] Aggregation and bundling of nanotubes represents a
constraint for implementation of these structures to maximize their
advantageous properties in nanoscale applications. Previous
attempts to disperse nanotubes have included covalent and
noncovalent functionalization, including long term
ultra-centrifugation. The covalent functionalization is highly
efficient, but results in significantly degraded physical and
electrical properties. Ultra-centrifugation may produce intact and
individually dispersed nanotubes, but due to the low yields of
dispersed nanotubes it is inefficient.
[0009] Due to the difficulty in completely dispersing nanotube
bundles, the differential control over the location and orientation
of the individual nanotubes represent an additional hurdle to
commercial applications. As such, the homogeneous incorporation of
nanotubes in compositions has been restricted for use in macroscale
materials. Methods utilizing high temperatures and lasers for
post-deposition alignment have been academically tested but
commercial-scale applications have not been realized. Additionally,
these methods are impractical for fabricating polymer
nanocomposites and microelectronics with nanotubes, as the
techniques ablate, damage, or alter the nanotubes or the supporting
substrate irreversibly
[0010] Consequently, there is a need for a physical method suitable
for dispersing and retrieving nanotubes from suspensions for the
placement, alignment with high precision and order on a substrate
or embedded therein.
BRIEF SUMMARY
[0011] A method for dispersing nanotubes, comprising forming a
nanocomposite solution, having associated nanotubes and
nanoplatelets, mixing a surfactant to the nanocomposite solution,
separating the nanocomposite in solution, wherein the nanotubes
remain suspended in the surfactant solution, and isolating the
nanotubes in solution.
[0012] In certain instances, the method further comprises
functionalizing the nanotubes in solution, isolating the nanotubes
from solution and dispersing the nanotubes in a solvent.
[0013] The method further comprises forming a nanocomposite by:
adding at least one nanotube to a first solution, wherein the first
solution oxidizes the nanotube, isolating the nanotube from the
first solution and resuspending the nanotube in aqueous solvent to
form an oxidized nanotube solution, adding at least one
nanoplatelet to a second solution, wherein the second solution
exfoliates the nanoplatelet, to form an exfoliated nanoplatelet
solution, and mixing the oxidized nanotube solution and exfoliated
nanoplatelet solution to form a nanocomposite solution comprising
at least one exfoliated or disentangled nanotube associated with
the at least one nanoplatelet.
[0014] The foregoing has outlined rather broadly the features and
technical advantages of the invention in order that the detailed
description of the invention that follows may be better understood.
Additional features and advantages of the invention will be
described hereinafter that form the subject of the claims of the
invention. It should be appreciated by those skilled in the art
that the conception and the specific embodiments disclosed may be
readily utilized as a basis for modifying or designing other
structures for carrying out the same purposes of the invention. It
should also be realized by those skilled in the art that such
equivalent constructions do not depart from the spirit and scope of
the invention as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a detailed description of the preferred embodiments of
the invention, reference will now be made to the accompanying
drawings in which:
[0016] FIG. 1 illustrates a schematic of a method for dispersing
and retrieving nanotubes according to one embodiment of the present
disclosure.
[0017] FIG. 2 illustrates a schematic of proposed mechanisms for
separating ZrP nanoplatelets from exfoliated nanotubes according to
one embodiment of the present disclosure, where (A) is large
aggregate of pre-treated nanotubes in aqueous medium, (B)
positively charged nanoplatelets are added and electrostatically
bound to the negatively charged nanotube aggregates, (C) shows
nanotubes are tethered into small bundles and then into individual
tubes by nanoplatelets under sonication, (D) the nonionic or ionic
surfactants are added to stabilize nanotubes, (E) the ZrP
nanoplatelets are precipitated by carefully adjusting the ionic
strength or the pH value of the system while the surfactants
stabilize nanotubes in the solution, and (F) shows nanotubes remain
individually dispersed in aqueous medium, stabilized by surfactants
and free of ZrP nanoplatelets.
[0018] FIG. 3 illustrates UV absorption spectra of the dispersion
of (A) SWNTs and (I) MWNTs at different concentrations with the
corresponding calibrated curves for concentration and absorption
intensity.
[0019] FIG. 4 illustrates the conceptual and realistic illustration
of functionalization and transfer of individual CNTs from aqueous
solutions to organic systems, where (A) concentrated acetone
solution of sulfanilamide are added into SDS aqueous solution to
functionalize individual CNTs, (B) the CNTs functionalized with
sulfanilamide become insoluble in water and are condensed into
acetone phase to form flocculation and (C) the CNT aggregates are
redispersed into acetone under sonication.
[0020] FIG. 5 illustrates the analysis curves including (A)
UV-vis-NIR, (B) Raman spectra, and (C) the RBM region of SWNTs
Raman spectra before and after nanoplatelets-assisted debundling.
Black lines represent pre-treated SWNTs bundles. Gray lines
represent SWNTs exfoliated with ZrP nanoplatelets. The weight ratio
of CNTs and ZrP is 1 to 5.
[0021] FIG. 6 illustrates (A) exfoliated ZrP nanoplatelets in
CNT-nanoplatelet mixture aggregate under the effect of (B) strong
ionic strength or (C) acidic condition, (D) the separation of
ion-induced precipitates, or (E) acid-induced precipitates of
nanoplatelets through centrifugation.
[0022] FIG. 7 illustrates EDS patterns and elemental mapping of (A)
SWNTs and (B) MWNTs before and after ZrP separation using the
HCl/SDS method. The dark dots indicate the signal from C-element
and bright dots from P-element, wherein the background of the
specimen mount has a gray color and should not be mixed with the
bright dots.
[0023] FIG. 8 illustrates EDS patterns and elemental mapping of (A)
SWNTs and (B) MWNTs before and after ZrP separation using the
KCl/Triton method, and the dark dots indicate the signal from C
element and bright dots from P element
[0024] FIG. 9 illustrates (A) Raman spectra and (B) RBM region of
SWNTs stabilized in SDS aqueous solution after ZrP-assisted
exfoliation and ZrP removal compared with those of pre-treated
SWNTs.
[0025] FIG. 10 illustrates Raman spectra (A) and RBM region (B) of
SWNTs transferred into piperidine and CTAB solutions after
ZrP-assisted exfoliation and ZrP and SDS removal, compared with
those of pre-treated SWNTs.
[0026] FIG. 11 illustrates the visual appearance of purified ZrP
dispersions in different ratio concentrations of water to
ethanol.
[0027] FIG. 12 illustrates the Raman spectra of supernatant and
aggregated separated from a mixture containing SWNTs, Triton and
exfoliated, purified ZrP nanoplatelets.
[0028] FIG. 13 illustrates TEM micrographs of (A) SWNTs exfoliated
with ZrP nanoplatelets and (B) SWNTs separated from nanoplatelets,
(C) SEM micrographs of SWNTs transferred into PSS aqueous
solution.
[0029] FIG. 14 illustrates TEM micrographs of disentangled MWNTs
before (A) and after (B) ZrP separation. For clarity, two of the
many ZrP nanoplatelets are circled in FIG. 14A.
[0030] FIG. 15 illustrates TEM micrographs of SWNT and K.sup.+
ionized ZrP nanoplatelets in a 1:5 mass ratio.
[0031] FIG. 16 illustrates (A) TEM micrograph of individual XD-CNTs
separated from nanoplatelets and dispersed in SDS aqueous solution,
(B) OM image of sulfanilamide-functionalized XD-CNTs dispersed in
acetone, (C) low magnification TEM and (D) high magnification TEM
micrographs of functionalized XD-CNTs.
NOTATION AND NOMENCLATURE
[0032] Certain terms are used throughout the following descriptions
and claims to refer to particular system components. This document
does not intend to distinguish between components that differ in
name but not function.
[0033] As used herein, the term "nanotube(s)" or NT(s) refers to
any cylindrical atomic allotrope or polyatomic molecule with a
diameter of about at least 0.2 nm, a length greater than about 20
nm, an aspect ratio (length to diameter ratio) of at least about 10
and outer walls comprising one or more layers.
[0034] As used herein, the term "carbon nanotube(s)" or CNT(S)
refers to any cylindrical carbon allotrope, with a diameter of
greater than about 0.2 nm, and outer walls comprising one or more
graphene layers.
[0035] As used herein the term "single walled nanotube(s)" or
"SWNT(s)" refers to any nanotube with outer walls comprising one
layer. Additionally, the term "multi-walled nanotube(s)" or
"MWNT(s)" refers to any nanotube with outer walls comprising at
least 2 layers, as used herein. It may be understood that the
"SWNT(s)" and "MWNT(s)" of the present disclosure are "single
walled carbon nanotube(s)" and "multi-walled carbon nanotube(s),"
although the present disclosure is not limited to carbon
nanotube(s) applications exclusively.
[0036] Also, as used herein, the terms "disperse", "de-rope" or
"de-bundle" refer to the substantial separation or disentanglement
of individual nanotubes from a bundle, rope, aggregate, clump,
intertwined, or similar conformation compromising one or more
nanotubes in association with each other.
[0037] Additionally, as used herein, the term "exfoliate" relates
to the process of removing a layer from a material. "Exfoliated" as
used herein refers to a nanostructure that has been stripped to one
layer. Alternatively, "exfoliated" as used herein refers to
partially dispersed, individually dispersed, or monodisperse
nanomaterials, having been stripped in layers from a bundle, rope,
or aggregate of similar nanomaterials.
[0038] In addition, as used herein, the term "nanocomposite" or
"hybrid" refers to a combination of, mixture of, or composite of
the materials preceding or proceeding the term but is not limited
to only the included materials.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Overview
[0039] FIG. 1 illustrates a schematic according to one embodiment
of the disclosure. In instances, the method comprises a nanotube
debundling and retrieval process, including pre-treatment of the
nanotubes, exfoliation of nanoplatelets, nanoplatelet-assisted
dispersion of CNT, retrieval of nanotubes from the
nanotube-nanoplatelet mixture using acid/ion solutions and
surfactants, and recycling of nanoplatelets to be re-used for
additional rounds of nanotube dispersion. While, methods for
dispersing and depositing carbon nanotubes by chemical methods have
been previously disclosed, for instance in U.S. application Ser.
No. 12/112,675 to "Dispersion. Alignment and Deposition of
Nanotubes" and U.S. Prov. App. No. 61/150,192 "Preparation of
Isolated Nanotubes and Related Polymer Nanocomposites", both of
which are hereby incorporated herein by reference in entirety for
all purposes, the present disclosure is drawn to alternate methods
of isolating nanotubes and retrieving them from a nanocomposite in
solution.
[0040] Nanotubes
[0041] The nanotubes manipulated in this disclosure are any
commercially available. The nanotubes employed in embodiments of
the disclosed method are of any synthetic classification, as
understood by those skilled in the art. The nanotubes are comprised
of any materials such as, but not limited to carbon, silicon,
metals or inorganic compounds. The nanotubes comprise, without
limitation, single walled nanotubes, multi-walled nanotubes or
combinations thereof. The nanotubes have a diameter of between
about 0.2 nm and about 30 nm, preferably between about 1 nm and
about 10 nm. The nanotubes have an aspect ratio, or length to
diameter ratio, of at least about 20, preferably the nanotubes
aspect ratio is at least about 30, and most preferably the aspect
ratio is at least about 1,000.
[0042] In instances, the nanotubes are carbon nanotubes. The carbon
nanotubes have a diameter of between about 0.2 nm and about 20 nm.
The carbon nanotube length is at least about 100 nm. In certain
embodiments, the length is at least 1,000 nm. The carbon nanotube
aspect ratio is at least 20, in certain embodiments the aspect
ratio is at least 1,000. The carbon nanotubes comprise single
walled carbon nanotubes (SWNTs) or multi-walled carbon nanotubes
(MWNTs). In certain instances, the nanotubes comprise XD-Grade
nanotubes or HIPCO.RTM. SWNT, such as those available from Carbon
Nanotechnologies, INC and UNIDYM.TM.. In certain instances, the
SWNTs comprise a mixture of metallic SWNTs and semiconducting
SWNTs. Without wishing to be limited by theory, the wrapping
directionality of a SWNT graphene lattice determines multiple
properties of the nanotube, including without limitation
conductivity and semi-conductivity. In instances, nanotubes that
have a high conductivity may be considered metallic SWNTs and the
nanotubes with a low conductivity may be considered semiconducting
SWNTs. As may be understood by a skilled artisan, the nanotubes may
be a mixture of conducting and semi-conducting nanotubes.
[0043] In embodiments, the nanotubes are functionalized nanotubes.
Functionalized nanotubes comprise nanotubes that have chemically
treated outer walls, such that the outer walls include functional
groups. In certain embodiments, functionalized nanotubes comprise
oxidized nanotubes. Without limitation by theory, it may be
difficult to determine the percentage of oxidized carbons within a
nanotube solution. However, it should be noted that the method of
the present disclosure is applicable to a wide range of oxidation
levels, including minimal oxidation. As such the oxidation of the
nanotubes is at least about 1%; alternately, the oxidation is at
least at about 4%; and in certain instances, the oxidation is at
least about 10%. Chemical treatment comprises exposure to a
chemically active media, a photo-chemically or an
electro-chemically active environment. The chemically active media
or environment can be oxyacids, peroxides, oxygen plasma,
microwave, voltaic pulse, combinations thereof, or others known to
a skilled artisan. In embodiments, one or more nanotubes are
admixed into a chemically active media comprising an acid solution
to form oxidized nanotubes. The acid solution comprises any acid
known to those skilled in the art. Preferably, the acid solution is
a strong acid. Further, the acid solution comprises a mixture of
strong acids. Non-limiting examples, suitable acids include
concentrated sulfuric acid, concentrated nitric acid, and
combinations thereof. In certain embodiments, the strong acid
solution comprises a concentrated sulfuric acid to concentrated
nitric acid in a volume ratio of about 3:1. The nanotubes are
oxidized in the strong acid solution by mixing the nanotubes using
an ultrasonicator for between about half hour and about five hours,
preferably between about two hours and about five hours, and most
preferably for about two hours to about three hours. In instances,
SWNTs are ultrasonicated for at least about 3 hours in the
chemically active media. In alternative instances, MWNTs are
ultrasonicated for at least about 2 hours in the chemically active
media. The nanotubes are ultrasonicated at about room temperature
to reduce or prevent severe oxidation. After sonication in acid,
the oxidized nanotube aggregates may be splayed at the ends into
negatively charged carboxylic groups. As may be understood by a
skilled artisan, the method and duration of the oxidation steps may
be dependent on the source, batch, and nanotube defects. In certain
instances, the nanotubes comprise enough carboxylic functionality
for implementation in the present process.
[0044] The oxidized nanotubes are isolated from the acid, for
example the nanotubes are isolated by filtration under vacuum. In
further instances, the oxidized nanotubes are isolated using a
filter or membrane, for instance a PVDF (polyvinylidone fluoride)
membrane filter. A non-limiting exemplary filter may be any
produced by Millipore.TM.. In certain instances, the oxidized
nanotubes are washed during filtration with a mild solution. In
instances, a mild solution comprises a neutral solution, a weak or
diluted basic solution, or combinations thereof. The diluted basic
solution comprises any base, for instance sodium hydroxide,
potassium hydroxide, calcium hydroxide, and others known to a
skilled artisan without limitation. In instances, a diluted basic
solution comprises an aqueous solution, such that the base has a
concentration between about 5 mM and about 900 mM; alternatively
about 50 mM and about 500 mM. In certain instances, a 100 mM
aqueous potassium hydroxide solution is used to filter and wash the
oxidized nanotubes.
[0045] After filtering and isolating, the nanotubes may be further
washed with another acid to restore carboxylic groups. As may be
understood by a skilled artisan, washing in a dilute basic solution
may at least partially remove or neutralize the oxidized carboxylic
groups. Without limitation by theory, washing the nanotubes with an
acid prior to re-suspending, restores the oxidized carboxylic
groups on the isolated nanotubes. In instances, the acid comprises
hydrochloric acid and in alternative instances, sulfuric or nitric
acid.
[0046] The isolated nanotubes are re-suspended in an aqueous
solution. The aqueous solution may be any of those known to one
skilled in the art such as, but not limited to, de-ionized water
(DI H.sub.2O). The weight percent (wt %) concentration of nanotubes
in aqueous solution ranges from 0.001% to 5%, more preferably 0.1%
to 0.3%, and most preferably from 0.1% to 0.2%. The isolated
nanotubes may be resuspended by agitation, shaking, or sonication,
without limitation.
[0047] Nanoplatelets.
[0048] Nanoplatelets are nanoparticles having a thin, planar
geometry. The nanoplatelets have a diameter range from about 10 nm
to about 20,000 nm, and preferably the nanoplatelet diameter is
between about 100 nm and 1000 nm. Nanoplatelets have an aspect
ratio, defined as the diameter to thickness ratio, of between about
10 to about 20,000; preferably the aspect ratio is between about
100 and about 4,000; and most preferably between about 100 and 500.
Additionally, the nanoplatelets may comprise any suitable shape
without limitation, such as circular, rectangular, triangular, or
combinations thereof. Furthermore, the nanoplatelets may comprise
any suitable material, as known to one skilled in the art without
limitation, such as graphite, inorganic crystal, organic crystal,
montmorillonite clay (nanoclay), or combinations thereof. In
certain embodiments nanoplatelets are comprised of an inorganic
crystal, such as alpha-zirconium phosphate
Zr(HPO.sub.4).sub.2.H.sub.2O, hereinafter ZrP.
[0049] In embodiments, the nanoplatelets are exfoliated. Exfoliated
nanoplatelets are nanoplatelets that are or have been chemically
separated into individual crystalline layers. Exfoliated
nanoplatelets are created in a chemically active media. In
instances, the chemically active media comprises a basic-aqueous
solution. The aqueous solution may comprise any solution known to
those skilled in the art that will exchange protons. Examples of
suitable solutions that may be used include alcohol-water, amine
bases, hydrocarbon solutions, salt solutions, aqueous base
solutions or combinations thereof. In certain instances, the
solution is an aqueous tetra-n-butylammonium hydroxide
(TBA.sup.+OH.sup.-) solution. The aqueous solution comprises DI
H.sub.2O. The molar weight ratio of nanoplatelets to base in
aqueous solution ranges from about 1:0.05 to about 1:2, preferably
from about 1:0.05 to about 1:1, and more preferably from about
1:0.8 to about 1:1
[0050] In instances, exfoliated nanoplatelets have a positive
electrostatic charge on the surface of both sides. Without wishing
to be limited by theory, the nanoplatelet with a positive
electrostatic charge on the surface of both sides may be considered
a deprotonated, exfoliated nanoplatelet. Without being limited by
theory, in the exfoliated nanoplatelet solution, a base covers the
surface of the platelets and forms highly charged ion pairs. In
instances, the positive ions are bulky with a diameter of about 1
nm, which is much larger than the inter-platelet spacing. The
positive charge comes from ions within the base. When paired with
the P--O.sup.- ions on the surface of the platelets, the positive
ion does not come close to the negative charge due to the hindrance
of the butyl chains, thus allowing the plate-like surface to
exhibit strong positive charge. The reaction time and/or
concentrations of reactants may be varied to obtain ZrP with the
designed range of aspect ratios.
[0051] In further embodiments, the exfoliated nanoplatelets may be
re-aggregated and re-dispersed a plurality of times. In instances,
the nanoplatelets are re-protonated to re-aggregate in solution. In
certain instances, the exfoliated nanoplatelets are re-protonated
by an acid solution, or an acidic-aqueous solution. Without
limitation by theory, the conjugation of freshly synthesized
nanoplatelet Zr(HPO.sub.4).sub.2.H.sub.2O with a base (e.g.,
TBA.sup.+OH.sup.-) is a reversible acid-base reaction because of
the weak acidity of the HPO.sub.4.sup.2- (pKa=12.3). Therefore, the
addition of a strong acid (e.g., HCl (pKa.apprxeq.-6) is likely to
break the conjugation and causes the detachment of TBA.sup.+ from
the surface of the nanoplatelets. Consequently, the surface of
nanoplatelets is neutralized. In instances, the neutralized
nanoplatelet tends to loosely re-aggregate in solution. As above,
without limitation by theory, the neutralized nanoplatelets may
have a similar charge state as newly synthesized, un-exfoliated
nanoplatelets. However, the neutralized nanoplatelets may not form
a close-packed structure as found in new nanoplatelets. In further
instances, maintaining the neutralized nanoplatelets in solution or
another wet state that permits repeated de-protonation and
re-dispersion. Thus, the nanoplatelets are indefinitely recyclable
between a dispersed exfoliated state and an aggregated state.
[0052] In certain instances, the exfoliated nanoplatelets are
reaggregated by another ionic solution. Without limitation by
theory, the ionic solution screens out the positive charge on the
surface of the exfoliated nanotubes, such that they are
destabilized. In instances, the destabilized nanoplatelet tends to
loosely re-aggregate in solution. In further instances, maintaining
the destabilized nanoplatelets in solution or another wet state
permits de-protonation (if needed), and re-dispersion. Thus, the
nanoplatelets are indefinitely recyclable between a dispersed
exfoliated state and an aggregated state.
[0053] Exfoliated Nanotubes.
[0054] In embodiments, in order to exfoliate and disperse the
oxidized nanotubes, the aqueous-oxidized nanotube solution and
aqueous-exfoliated nanoplatelet solution are admixed. In instances,
the weight ratio of nanotubes to nanoplatelets is between about 1:1
to about 1:5. As may be understood by one skilled in the art, the
weight ratio may change depending on the type, length, diameter,
and defect level of the nanotubes. Alternatively, the weight ratio
may change dependent on the desired exfoliation efficiency, the end
product, the intended applications, and the processes of
exfoliation. In instances, the combined nanotube/nanoplatelet
solution is mechanically agitated for a period of time ranging from
about 10 minutes to about 60 minutes. Examples of mechanical
agitation methods that may be used include without limitation
shaking, stirring, sonication or other mechanical means. In certain
instances, the nanotube/nanoplatelet solution is stirred. After
initial mechanical agitation, the mixture is homogenized, for
example by ultra-sonication. The temperature during homogenization
is from about 4.degree. C. to about 80.degree. C., preferably from
about 20.degree. C. to about 40.degree. C. and most preferably from
about 20.degree. C. to about 30.degree. C. In certain instances,
the solution is ultrasonicated at approximately room temperature
for homogenization. In instances, the solution is ultrasonicated
for about 0.5 hour to about 12 hours, preferably from about 1 hour
to about 12 hours, and most preferably 1 hour to about 8 hours. In
certain conditions, the time and temperature are dependent on
sonicator power and bath efficiency. In alternate conditions, the
source, batch, and carboxylic functionalities may dictate the
sonicator bath, time temperature, and power. After ultra-sonication
the aqueous nanotube/nanoplatelet solution is a homogenous solution
of dispersed nanotubes and associated nanoplatelets.
[0055] The exfoliation and dispersion of nanotubes is attributed to
the presence of the nanoplatelets. Without being limited by theory,
the negatively charged surface of nanotubes attracts the positively
charged surface of the nanoplatelets. By mixing the positively
charged nanoplatelets with negatively-charged bundled nanotubes,
the nanoplatelets are attached onto the nanotube side walls and
forcing nanotube bundles into individual tubes during
ultra-sonication. In instances, the nanoplatelets are
electrostatically tethered to the nanotubes during and after
sonication. After the dispersion of the nanotubes, the individual
tubes have at least one nanoplatelet attached on their surfaces.
The nanoplatelets cannot be re-stacked together to form regular
layered structures due to the presence of nanotubes. In certain
instances, it can be envisioned a plurality of nanoplatelets are
electrostatically tethered to the nanotubes. Thus each nanoparticle
interferes with the re-aggregation of the other by a steric or
physical hindrance effect. The hindering effect comes from the
two-dimensional heterogeneous shapes of the nanoplatelets
interfering with other nanoplatelets associated with nearby
nanotubes. The surface charge and two-dimensional nature of
exfoliated nanoplatelets disperse the nanotubes and hinder the
re-aggregation thereof. The nanotubes dispersed by the
nanoplatelets are exfoliated. The nanotubes and nanoplatelets are
electrostatically associated. The nanotubes associated with the
nanoplatelets comprise a nanocomposite.
[0056] A surfactant is added to the nanocomposite solution to
stabilize the exfoliated nanotubes. Adding the surfactant forms a
nanocomposite-surfactant solution. The surfactant is added until
the nanotubes reach a concentration of at least about 5 ppm;
alternatively, the surfactant is added until the nanotubes reach a
concentration of at least about 80 ppm; and in certain instance the
surfactant is added until the nanotubes of a concentration of about
240 ppm. Surfactants may be anionic surfactants, cationic
surfactants, non-ionic surfactants, zwitterionic surfactants, and
combinations thereof, without limitation. Examples of suitable
surfactants include polyvinylpyrrolidone (PVP), sodium dodecyl
sulfate (SDS), and hydrophilic polyethylene oxides (TRITON.TM.
X-100). The surfactant may be any known to one skilled in the art
for suspending oxidized and exfoliated nanotubes. The surfactant is
added until the surfactant concentration is between about 0.1 wt %
and about 10 wt % and in certain instances the surfactant
concentration is kept at about 1.0 wt %. Further, the
nanocomposite-surfactant solution is mechanically agitated, and in
certain instances, stirred for at least about 5 minutes.
Alternatively, the nanocomposite-surfactant solution is stirred for
at least about 30 minutes and in further instances for about 60
minutes. As understood by one skilled in the art, the final,
combined volume of aqueous surfactant and exfoliated-nanotube
solution may vary with the original nanotube mass, the final
concentration, or dispersion needed for a pre-determined
application. In alternative instances, volume of aqueous surfactant
and exfoliated-nanotube solution may be altered for scaled up or
commercial purposes. Additionally, the method and period of time
for mechanically agitating the nanocomposite-surfactant solution
may be adjusted.
[0057] Nanotube Dispersion and Retrieval.
[0058] The nanocomposite is separated and the exfoliated nanotubes
are retrieved as dispersed nanotubes. The nanocomposite, comprising
the nanotubes and associated nanoplatelets is separated by altering
the ionic balance or pH of the nanocomposite-surfactant solution.
In instances, after adding surfactants, an aqueous acid solution is
added to the nanocomposite-surfactant solution. Without limitation
by theory, the addition of an acid disrupts the electrostatic
tethering of the nanocomposite and causes the re-aggregation of
nanoplatelets. The surfactant in the solution stabilizes the
dispersed nanotubes and resists nanotube agglomeration, bundling,
roping, or other forms of re-aggregation, without limitation.
Further, the nanoplatelets are retrieved as aggregates and recycled
for additional nanotube dispersions.
[0059] In embodiments, the aqueous acid comprises any known to one
skilled in the art. In instances the aqueous acid comprises
hydrochloric acid, acetic acid, sulfuric acid, or phosphoric acid.
In certain instances, the aqueous acid comprises hydrochloric acid.
The aqueous acid solution has a concentration of between about 0.1
mM and about 900 mM; alternatively, between about 50 mM and about
250 mM; and in certain instances, the concentration is about 100
mM. Further, after the acid is added to the
nanocomposite-surfactant solution the concentration of hydrogen
ions in the nanocomposite-surfactant solution is between about 0.01
mM and about 5 mM; alternatively, between about 0.5 mM and about
2.5 mM; and in certain instances, between about 0.75 mM and about
1.5 mM. As may be understood by one skilled in the art, the
concentration of the aqueous acid and the hydrogen ions may be
altered with the concentration of nanocomposites, the concentration
of surfactants, the surfactant used, the original nanotube mass,
the final concentration, the dispersion needed for a pre-determined
application, or combinations thereof. In alternative instances, the
concentration of the aqueous acid and the hydrogen ions may be
altered for scaled up or commercial purposes.
[0060] In embodiments, the aqueous acid is added to the
nanocomposite-surfactant solution. In instances, the acid is added
to the nanocomposite-surfactant solution incrementally. The acid
may be added to the nanocomposite-surfactant solution in any
incremental method known to an artisan, without limitation. For
instance, drop-wise, trickling, seeping, or any other method to add
the acid in a slow flow rate, or small volume is acceptable.
Additionally, the nanocomposite-surfactant solution may be
mechanically agitated, such as described herein previously, to
increase the rate of nanocomposite dissociation. In certain
instances, the nanocomposite-surfactant solution is stirred.
[0061] In instances, the addition of the aqueous acid and the
stirring induces the nanocomposite dissociation. The nanotubes
separate from the nanoplatelets and remain stabilized in solution.
In instances, the nanoplatelets re-aggregate and partially
precipitate. In certain instances, the re-aggregation of
nanoplatelets forms higher molecular weight nanoplatelet
nanoparticles. The separation of nanotubes and nanoplatelets forms
a dissociated nanoparticle solution.
[0062] Alternatively, the nanocomposite is separated and the
exfoliated nanotubes are retrieved as dispersed nanotubes by adding
a salt or salt solution. The nanocomposite, comprising the
nanotubes and associated nanoplatelets is separated by altering the
ionic balance of the nanocomposite-surfactant solution by adding a
salt. In instances, after adding surfactants, an aqueous salt
solution is added to the nanocomposite-surfactant solution. Without
limitation by theory, the addition of a salt disrupts the
electrostatic tethering of the nanocomposite. In instances, the
surfactant in the solution stabilizes the dispersed nanotubes and
resists agglomeration, bundling, or roping of the nanotubes,
without limitation.
[0063] The aqueous salt comprises any known to one skilled in the
art, such as, without limitation, sodium chloride, potassium
chloride, magnesium chloride, aluminum chloride, sodium hydroxide,
or sodium acetate. In certain instances, the aqueous salt comprises
potassium chloride. The aqueous salt solution has a concentration
of between about 1 mM and about 500 mM; alternatively, between
about 10 mM and about 250 mM; and in certain instances, the
concentration is about 100 mM. Further, after the aqueous salt is
added, the ion concentration in the nanocomposite-surfactant
solution is between about 0.01 mM and about 80 mM; alternatively,
between about 0.1 mM and about 35 mM; and in certain instances
(e.g., monovalent salt) between about 21 mM and about 26 mM. As may
be understood by one skilled in the art, the concentration of the
aqueous salt ions may be altered with the types of salts,
concentration of nanocomposites, the concentration of surfactants,
the surfactant used, the original nanotube mass, the final
concentration or dispersion needed for a pre-determined
application, or alternatively, for scaled up and/or commercial
purposes.
[0064] In instances, the aqueous salt is added to the
nanocomposite-surfactant solution incrementally. The salt may be
added to the nanocomposite-surfactant solution in any incremental
method known to an artisan, without limitation. For instance,
drop-wise, trickling, seeping, or any other method to add the salt
in a slow flow rate, or small volume manner is acceptable.
Additionally, the nanocomposite-surfactant solution may be
mechanically agitated, such described herein previously, to
increase the rate of nanocomposite dissociation.
[0065] In instances, the addition of the aqueous salt and the
stirring induces the nanocomposite dissociation. The nanotubes
separate from the nanoplatelets and the nanotubes remain stabilized
in solution. In instances, the nanoplatelets re-aggregate and at
least partially precipitate. In certain instances, the
re-aggregation of nanoplatelets forms higher molecular weight
nanoplatelet nanoparticles. The separation of nanotubes and
nanoplatelets forms a dissociated nanoparticle solution.
[0066] In embodiments, the dissociated nanoparticle solution is
separated to form a dispersed nanotube solution. The dissociated
nanoparticle solution is separated by settling, filtering,
centrifugation, or other processes without limitation. In
instances, the dissociated nanoparticle solution is settled. In
alternate instances, the dissociated nanoparticle solution is
centrifuged. The nanoplatelets, and a portion of trapped nanotubes,
are pelleted from solution by centrifugation. In certain instances,
the centrifuge is operated to produce a relative centrifugal force
(RCF) of at least about 5,000 G. Alternatively, the centrifuge
maintains RCF of between about 10,000 G and about 20,000 G.
Further, the dissociated nanoparticle solution is centrifuged for
between about 1 minute and about 20 minutes. In certain instances,
the dissociated solution is centrifuged at about 16,800 G for about
10 min. As understood by one skilled in the art, the centrifuging
step may be conducted for an alternate period and rotational
frequency in order to obtain RCF suitable for pelleting the
nanoplatelets and trapped nanotubes. In certain instances, the
diameter of the rotor and rotational frequency may dictate the
relative centrifugal force applied to the surfactant and the period
of time required for removing the re-aggregated nanoplatelets from
the dispersed nanotube solution.
[0067] In embodiments, the supernatant is retrieved to form the
dispersed nanotube solution. In instances, supernatant may be
retrieved by decanting, sipping or other methods known to a skilled
artisan. In certain instances, the supernatant comprises the
dispersed nanotube solution and may be readily used for certain
applications. Furthermore, after exfoliation, dissociation, and
separation, the nanotubes dispersed in the supernatant solution may
be destabilized and separated from surfactants by filtration and/or
centrifugation; additional solvent during filtration or repeated
centrifugation and re-suspension may be needed to remove impurity.
Without limitation by theory, the surfactant may determine the
solvent used to destabilize the nanotubes. Depending on the type of
surfactant used to dissociate the nanocomposite, organic solvents
(e.g., acetone), or salt-organic solvent combinations are used to
destabilize the nanotubes. In non-limiting examples, acetone may be
used if SDS/acid have been used to separate nanotubes from the
nanoplatelets, or acetone and salt maybe used together if
Triton/ion have been used to separate nanotubes from the
nanoplatelets. Alternatively, the destabilized nanotubes may be
maintained in solution or a wet state for redispersion into various
solutions and solvents of different compositions or dried for
applications in different matrices or substrates.
[0068] In certain embodiments, the dispersed nanotubes may be
functionalized, or re-functionalized, after separation from the
nanoplatelets. In instances, a functionalizing substance or
solution is added to the dispersed nanotube solution. The
functionalizing solution comprises any solution or reactant that
may render the nanotubes insoluble in water. The functionalizing
solution comprises any compound that will react with the nanotubes
to add amine groups, amide groups, ions or other organic and
inorganic groups without limitation. In certain instances, a
solution of sulfanilamide is added to the dispersed nanotube
dispersion. Additionally, a solvent that is miscible in water may
be used to increase the rate of functionalization. In instances,
acetone with a concentration of between about 5% and about 20%, and
in certain instance the acetone concentration is about 10%. The
concentration of sulfanilamide is sufficient to form a 1:1
stoichiometry of the amine groups on sulfanilamide and carboxylic
groups of the nanotubes to form a functionalized nanotube solution.
Without limitation by theory, the desired functionalization
stoichiometry of the nanotubes may be controlled by the
concentration of the functionalizing solution. The functionalizing
solution and dispersed nanotube solution mixture is kept at a
temperature from about 40.degree. C. to about 200.degree. C.; from
about 60.degree. C. to about 100.degree. C., and in certain
instances at about 70.degree. C. Alternatively, the functionalizing
solution and dispersed nanotube solution mixture is kept at about
room temperature. In another instance, in order to control
functionalization, the time that the mixture is kept at may be
altered. In certain instances, to achieve a functionalized nanotube
solution, the functionalizing solution and dispersed nanotube
solution mixture is allowed to react for at least 30 minutes;
alternatively, for at least 240 minutes; and in certain instances,
the mixture is allowed to react overnight. In further instances,
the mixture is allowed to react until the nanotubes form a
flocculation. Without limitation by theory, the formation of a
nanotube flocculation indicates the surface functionalization of
the nanotubes by sulfanilamide, rendering the nanotubes insoluble
in an aqueous solution and indicates the formation of
functionalized nanotubes.
[0069] Retrieval and re-suspension of the nanotubes from the
functionalized nanotube solution may be done by any method
previously discussed herein, such as by drying, filtration, or
centrifugation. After retrieval the functionalized nanotubes may be
washed to remove residues of surfactant and chemicals. In
instances, the functionalized nanotubes are washed with alcohol,
acetone, toluene, or other organic solvents without limitation. As
a non-limiting example, the sulfanilamide-functionalized nanotubes
are washed with water or alcohol at least once to remove surfactant
residues. The washed nanotubes are resuspended with sonication in
an organic solvent, such as acetone. In instances, the
functionalized and resuspended nanotubes comprise a concentration
of at least about 1 ppm; further a concentration of at least about
200 ppm; alternatively a concentration of at least about 600 ppm.
As may be understood by one skilled in the art, the step of washing
the nanotubes may be excluded for certain applications or end
products. The step of washing the nanotubes may be altered
depending on the purity requirements of the application or end
products.
[0070] Nanotubes after destabilization or functionalization may be
in an aggregation or flocculation form. But, they do not reform a
tightly bound nanotube-bundle structure as the pristine nanotubes
so long as they are kept in solution or in a wet state. The
individual exfoliation state of nanotubes may be easily
re-established by re-suspending the flocculated nanotubes in
solution under ultra-sonication.
[0071] Nanoplatelet Recycling and Applications:
[0072] In embodiments, the re-aggregated nanoplatelets may be
recycled to form further nanocomposite solutions. Without
limitation by theory, the nanoplatelets may be recycled accordingly
for an indefinite number of cycles, such that the same mass,
volume, or other quantity of nanoplatelets may be used to create
multiple batches of exfoliated and dispersed nanotubes. In
instances, the re-aggregated nanoplatelets are re-dispersed or
re-exfoliated in a chemically active media to form de-protonated,
exfoliated nanoplatelets for re-suspension in an aqueous solution
as described herein previously. In certain instances, a portion of
the re-aggregated nanoplatelets may be associated with nanotubes.
Without limitation, the chemically active media may be any
described previously, including the media used in the primary
exfoliation of nanoplatelets. Alternatively, the chemically active
media may comprise an aqueous solution of small or low molecular
weight bases. Without limitation by theory, bases with relatively
small sizes (e.g., KOH, NaOH, etc) are applicable since the
re-aggregated nanoplatelets are not as closely-packed as newly
synthesized nanoplatelets. The re-exfoliated, aqueous nanoplatelet
solution may be used to form further exfoliated nanotubes by the
pathway described herein previously.
[0073] The re-aggregated nanoplatelets, whether associating with
nanotubes or not, may be re-exfoliated in an appropriate media
without using additional active chemicals. The loosely-aggregated
nanoplatelets may be exfoliated in a polarity-matched media. In
instance that the re-aggregation of nanoplatelets is induced by
ions, the nanoplatelets may be directly redispersed in DI H.sub.2O
or other solvents with similar polarity depending on how much TBA
is stripped off from the surface of the nanoplatelets. In instances
that a large amount of acid is used to strip off a significant
fraction of TBA from the surface of the nanoplatelets during the
re-aggregation of nanoplatelets or afterwards, the re-aggregated
nanoplatelets can be considered as neutralized (i.e., not charged)
and may be redispersed in a mixture of de-ionized water and ethanol
with a volume ratio of between about 1:5 and about 5:1;
alternatively between about 1:1 and about 5:1; and further a volume
ratio of water to ethanol of about 3:1. The composition of the
media may be varied by those skilled in the art but the principle
of dispersing the nanoplatelets without de-protonating is to match
the polarity (e.g., by matching the dielectric constant) of the
solvent to that of the nanoplatelet. In certain instances, the
re-exfoliation is carried out under ultra-sonication. The
preferable sonication time is at least 1 hr and may vary depending
on the concentration of nanoplatelets and the power of the
sonicator. The neutralized nanoplatelet stabilized solely by
solvent shows different stability to the positively charged
nanoplatelets (e.g., nanoplatelets associated with TBA.sup.+)
stabilized by electrostatic repulsion. While the neutralized
nanoplatelet, if undisturbed, can be stabilized in a
polarity-matched solvent for several months without precipitation,
they can be easily re-aggregated by centrifugation. On the other
hand, the charged nanoplatelets remain stable during
centrifugation.
[0074] In further instances, the neutralized nanoplatelets with the
TBA.sup.+ groups on the surface almost completely stripped off by a
sufficient amount of acid, may be used for sorting nanotubes. To
maximize the sorting efficiency, the neutralized nanoplatelets may
be redispersed and re-exfoliated in a mixture of DI H.sub.2O and
ethanol. It is found that neutralized nanoplatelets have better
affinity to certain species of SWNTs. When mixing with oxidized
HiPco SWNT solution, the neutralized re-exfoliated nanoplatelets
preferentially associate with conducting or metallic SWNT
bundles.
[0075] In further embodiments, the nanotubes may be sorted after
nanoplatelet-assisted exfoliation. After the nanotubes are
exfoliated by deprotonated, exfoliated nanoplatelets via
electrostatic tethering, the nanotubes and nanoplatelets in the
nanocomposite solution may be co-precipitated by an acid, salt, an
acidic or an ionic solution, as described herein previously. No
surfactant is needed beforehand to stabilize nanotubes. In
instances, the co-precipitated nanotubes and nanoplatelets
partition from the solvent to form a gel, for example by settling
or centrifugation without limitation, also as described previously.
The gel comprises the exfoliated nanotubes and nanoplatelets, and
in certain instances a portion of the aqueous solution described
herein previously. In embodiments, the gel is immersed in an acidic
solution for the nanoplatelets inside to be neutralized (i.e.,
stripping off TBA.sup.+). Extra acid is then removed by
centrifugation and suspension. The nanotube-nanoplatelet gel may be
redispersed in a solution, for example an aqueous solution or a
solvent-aqueous solution. In instances, the solution comprises DI
H.sub.2O and ethanol. In certain instances, the solution comprises
a volume ratio of water to alcohol of between about 1:5 and about
5:1; alternatively between about 1:1 and about 5:1; and further a
volume ratio of water to ethanol of about 3:1. In embodiments, the
re-suspended gel solution comprises re-exfoliated nanoplatelets and
nanotubes.
[0076] In embodiments, re-exfoliated nanoplatelets differentially
associate with nanotubes having different chiralities. More
specifically, the re-exfoliated nanoplatelets preferentially
associate with conducting or metallic SWNTs. In instances,
re-exfoliated nanoplatelets associated with metallic SWNTs forms a
metallic nanocomposite. The metallic nanocomposite may be separated
from the semiconducting SWNTs by settling or expedited by
centrifugation. In certain instances, the centrifuge is operated
after surfactants (e.g., Triton) are added and the mixture is
sonicated for surfactants to stabilize semiconducting SWNT. The
centrifuge is operated to produce a relative centrifugal force
(RCF) of at least about 5,000 G. Alternatively, the centrifuge
maintains RCF of between about 10,000 G and about 20,000 G.
Further, the dissociated nanoparticle solution is centrifuged for
between about 1 minute and about 120 minutes; alternatively,
between about 30 minutes and about 90 minutes. In certain
instances, the dissociated solution is centrifuged at about 16,800
G for about 60 min. Without limitation by theory the supernatant
substantially comprises the semiconducting SWNTs and the pellet
substantially comprises the metallic SWNTs. The semiconducting
SWNTs may be retrieved from the supernatant and the metallic SWNTs
may be resuspended, dissociated from the exfoliated nanoplatelets,
and functionalized by any of the applicable processes described
herein.
[0077] The recyclable nanoplatelets are additionally, suitable for
application in composites, metals, liquids, or other applications
known to a skilled artisan. Further, the recycling of the
nanoplatelets through multiple nanotube dispersion represents a
cost reduction for the industrial scale application of the
disclosed process. The materials and steps needed for the synthesis
and primary or first exfoliation of the nanoplatelets may be
reduced in frequency and quantity. Small size and molecular weight
bases can be used to exfoliate the re-aggregated nanoplatelets as a
cost reduction. In certain applications, the recyclable
nanoplatelets may be stored in solution for indefinite periods for
use in future nanotube dispersions, thereby reducing the cost of
re-starting exfoliated nanotube production in the event of a
stoppage or production shutdown.
[0078] Dispersed Nanotube Applications:
[0079] The resuspended, isolated nanotubes, whether functionalized
or not, are suitable for applications in composites, metals,
liquids, or other applications known to a skilled artisan. In
non-limiting examples, the isolated nanotubes may be incorporated
in a matrix such as liquids, oils, inks, polymers, epoxies, resins,
waxes, alloys, nanoclays, or combinations thereof. Without
limitation by theory, the dispersed, exfoliated, and/or
functionalized nanotubes may be directly mixed into any matrix or
suspension. In a non-limiting example, the exfoliated nanotubes are
mixed in a suspension of a nanoclay.
[0080] In certain applications, the isolated nanotubes may be
deposited on a surface or substrate from the resuspended, isolated
nanotube solution. In embodiments, the dispersed nanotubes may be
used as an ink to form a thin film. In instances, an aqueous
dispersion of nanotubes may be deposited on a substrate. In certain
instances, the nanotubes are deposited on a substrate as an ink. In
alternate instances, the nanotubes are deposited on the substrate
as a coating. Further, the nanotubes may be deposited on the
substrate during heating, under vacuum, during deposition of other
materials, or combinations thereof. In embodiments, the solution is
removed from the nanotubes deposited on the substrate. In certain
instances, the solution may be removed by evaporation, vacuum,
heating, or combinations thereof. Without limitation by theory, the
dried nanotubes may comprise a thin film.
[0081] At least one embodiment is disclosed and variations,
combinations, and/or modifications of the embodiment(s) and/or
features of the embodiment(s) made by a person having ordinary
skill in the art are within the scope of the disclosure.
Alternative embodiments that result from combining, integrating,
and/or omitting features of the embodiment(s) are also within the
scope of the disclosure. Where numerical ranges or limitations are
expressly stated, such express ranges or limitations should be
understood to include iterative ranges or limitations of like
magnitude falling within the expressly stated ranges or limitations
(e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater
than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a
numerical range with a lower limit, R.sub.l, and an upper limit,
R.sub.u, is disclosed, any number falling within the range is
specifically disclosed. In particular, the following numbers within
the range are specifically disclosed:
R=R.sub.l+k*(R.sub.u-R.sub.l), wherein k is a variable ranging from
1 percent to 100 percent with a 1 percent increment, i.e., k is 1
percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . 50
percent, 51 percent, 52 percent . . . 95 percent, 96 percent, 97
percent, 98 percent, 99 percent, or 100 percent. Moreover, any
numerical range defined by two R numbers as defined in the above is
also specifically disclosed. Use of the term "optionally" with
respect to any element of a claim means that the element is
required, or alternatively, the element is not required, both
alternatives being within the scope of the claim. Use of broader
terms such as comprises, includes, and having should be understood
to provide support for narrower terms such as consisting of,
consisting essentially of, and comprised substantially of.
Accordingly, the scope of protection is not limited by the
description set out above but is defined by the claims that follow,
that scope including all equivalents of the subject matter of the
claims. Each and every claim is incorporated as further disclosure
into the specification and the claims are embodiment(s) of the
present invention. The discussion of a reference in the disclosure
is not an admission that it is prior art, especially any reference
that has a publication date after the priority date of this
application. The disclosure of all patents, patent applications,
and publications cited in the disclosure are hereby incorporated by
reference, to the extent that they provide exemplary, procedural or
other details supplementary to the disclosure.
[0082] To further illustrate various illustrative embodiments of
the present invention, the following examples are provided:
EXAMPLES
Overview
[0083] FIG. 1 gives an overview illustration of the CNT debundling
and retrieval process, including pre-treatment of CNT, exfoliation
of nanoplatelets using tetra-butyl ammonium hydroxide
(TBA.sup.+OH.sup.-), nanoplatelet-assisted dispersion of CNT (step
1), retrieval of CNT from the CNT-nanoplatelet mixture using
acid/ion and surfactants (step 2), and recycling of nanoplatelets
to be re-used for CNT dispersion again (step 3).
[0084] Preparation of Alpha-Zirconium Phosphate Nanoplatelets (ZrP)
and CNTs and Dispersion of CNTs Using Exfoliated Nanoplatelets.
[0085] Synthesis of ZrP Nanoplatelets and Pre-Treatment of
CNTs:
[0086] The diameter of the ZrP nanoplatelets is around 100 nm. ZrP
nanoplatelets were de-protonated and fully exfoliated by tetrabutyl
ammonium hydroxide (TBA.sup.+OH.sup.-) in water with a molar ratio
of ZrP:TBA=1:1.
[0087] Purified HiPco SWNTs and XD-CNTs were obtained from Carbon
Nanotechnologies, Inc. TBA.sup.+OH.sup.- and MWNTs were purchased
from Sigma-Aldrich. CNTs were first oxidized in a mixture of
concentrated sulfuric acid and concentrated nitric acid with a
volume ratio of 3:1 by ultra-sonication in a sonication bath
(BRANSONIC.RTM. 2510) at room temperature for 3 hours for SWNTs and
XD-CNTs and for 2 hours for MWNTs, respectively. Then, de-ionized
water (DI-H.sub.2O) was added to dilute the acids and the mixture
was sonicated for another 1 hour. After the above steps, the
oxidized CNTs were isolated by using a PVDF filter membrane
(MILLIPORE.TM., 0.45 .mu.m pore size) under vacuum. The CNTs were
washed several times with de-ionized water alone during filtration
or repeated use of 100 mM KOH aqueous solution and DI-H.sub.2O
during filtration to further remove the intercalated acid residue.
The carboxylic groups on CNTs can be recovered later with HCl if
needed. The CNTs collected were then re-dispersed in water by
sonication.
[0088] Dispersion of Pre-Treated CNTs with Exfoliated
Nanoplatelets:
[0089] Two aqueous solutions containing oxidized CNTs and fully
exfoliated ZrP nanoplatelets were directly mixed. The weight ratio
of CNTs to ZrP nanoplatelets is 1:5. The finial concentrations of
CNTs and ZrP in the CNTs/ZrP solution are 100, and 500 ppm,
respectively. The mixture was sonicated in a sonication bath at
room temperature for 30 min.
[0090] It is noted that both the HiPco grade SWNTs and XD grade
SWNTs are treated the same and designated as SWNTs in this research
because of the similarity in their surface functionalization, and
their behavior in subsequent exfoliation, nanoplatelets removal,
and redispersion processes.
[0091] Separation of Nanoplatelets from Exfoliated CNTs.
[0092] Use of surfactants for stabilizing CNTs after ZrP-assisted
exfoliation in solution: A schematic illustration of the process of
ZrP-assisted exfoliation of CNTs and ZrP separation is shown in
FIG. 2. Positively charged ZrP nanoplatelets that contain TBA bind
to negatively charges CNTs through electrostatic binding and
localize sonication energy from the nanoplatelets onto the surfaces
of CNTs, resulting in individually dispersed CNTs (FIG. 2A-C).
After dispersion, ionic and nonionic surfactants such as sodium
dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and TRITON.TM.
X-100 (Triton), were added to reach a surfactant concentration of
1.0 wt. % and a CNTs concentration of 80 ppm in a solution with a
final total volume of 10 ml. The solution was then stirred for 1
hour (FIG. 2D).
[0093] Use of Acid for Separation of CNTs and Nanoplatelets:
[0094] After adding SDS or Triton surfactants, aqueous solution of
HCl with a concentration of 100 mM was added dropwise into the
CNTs/ZrP/surfactants mixture during stirring to introduce
agglomeration of the detached nanoplatelets through pH tuning. The
CNTs remained stable in the solution due to the presence of anionic
or nonionic surfactant (FIG. 2E). The concentration of [H.sup.+]
introduced in CNTs/ZrP/SDS solution was 0.75 mM and 1.5 mM in
CNTs/ZrP/Triton solution, respectively. The solutions were then
centrifuged at 16,800 G (THERMO IEC CL31) for 10 min. ZrP
nanoplatelets together with a certain amount of trapped CNTs were
precipitated at the bottom of the centrifugation tubes while most
of the surfactant stabilized CNTs were left behind in the
supernatant (FIG. 2F). Afterwards, 1 ml of supernatant was diluted
for 10 times for yield determination, or the percentage of CNTs
maintained in the supernatant after ZrP separation.
[0095] Use of Salts for Separation of CNTs and Nanoplatelets:
[0096] After adding Triton surfactants, aqueous solution of KCl
salt with a concentration of 100 mM was added dropwise into the
CNTs/ZrP/surfactants mixture during stirring to introduce
agglomeration of the nanoplatelets. The ion concentration in
SWNTs/ZrP and MWNTs/ZrP solutions are kept at 21 and 26 mM,
respectively. The solutions were then centrifuged at 16,800 G for
10 min. ZrP nanoplatelets together with a certain amount of CNTs
were precipitated at the bottom of the centrifugation tubes while
most of the Triton-treated CNTs were left behind in the supernatant
(FIG. 2F). Afterwards, 1 ml supernatant was diluted for 10 times
for yield determination.
[0097] Table 1 lists the experimental conditions, the results of
separation efficiency, and yields for the various methods described
above. The separation efficiency is determined by the amount of
nanoplatelets removed from the CNT-nanoplatelet mixture.
TABLE-US-00001 TABLE 1 Conditions, Yields, and Separation
Efficiency. Sepa- Surfactants [H.sup.+] or 1.sup.st cycle ration
Method removal [KCl] (mM) yield efficiency Ionic screening (SW) NA
10 NA Up to 85% Ionic screening plus Acetone both >90% 100%
HCl/SDS (SW) HCl/SDS (SW) 0.75 75% 100% HCl/SDS (MW) 0.75 69% 100%
HCl/Triton (SW) Acetone & 1.5 63% 100% HCl/Triton (MW) [KCl]
1.5 63% 100% KCl/Triton (SW) 21 61% 98.6% KCl/Triton (MW) 26 61%
99.5%
[0098] Evaluation of Separation Efficiency:
[0099] Energy Dispersive X-ray Spectroscopy (EDS) analysis was used
to evaluate the separation efficiency. To obtain surfactant-free
CNTs from the surfactant-stabilized dispersions, CNTs stabilized by
SDS were destabilized with acetone at 1:1 volume ratio of CNTs/SDS
solution to acetone. For CNTs stabilized by Triton, acetone and KCl
solution of a concentration of 100 mM were used together to
precipitate CNTs. The volume ratio of CNTs/Triton solution,
acetone, and KCl solution was kept at 2:2:1. After precipitation,
CNTs were collected by centrifugation at 16.800 G for 10 min and
then washed with ethanol or methanol for three times by repeated
dispersion and centrifugation processes. CNTs were transferred on
an aluminum stub and dried at 70.degree. C. for SEM
observation.
[0100] The content of ZrP nanoplatelets and C element in TBA were
calculated based on EDS intensity of P element and the 1:1
stoichiometry of ZrP:TBA. The content of C element in CNTs was
calculated from the total content of C element minus that of
TBA.
[0101] Evaluation of Yields:
[0102] Yields were determined by absorption spectra. Standard
solutions of CNTs exfoliated by nanoplatelets were prepared with
systematically increased CNT concentration from 2.5 to 12.5 ppm.
According to Beer-Lambert law, A=.di-elect cons.lc (A: absorption
intensity: .di-elect cons.: constant; l: light path length; c:
solutes concentration); the absorption intensity is linearly
dependent on the concentration of solutes. By comparing the
absorption intensity of the diluted CNTs dispersion mentioned
previously and that of the standard solution at 400 nm, where the
light is transparent to the surfactants used, the yields of CNTs
retrieved from nanoplatelets separation in the solution can be
determined accurately. FIG. 3 shows the UV absorption spectra of
dispersion of (A) HiPco SWNTs and (B) MWNTs at different
concentrations. The standardized linear fitting curves showing the
linear relationship between CNT concentration and absorption
intensity is also given.
[0103] Transfer of Stabilized Individual SWNTs into Other Systems
of Interest
[0104] General Process of Transfer and Stabilization of Individual
SWNTs:
[0105] After exfoliation and ZrP removal, isolated SWNTs were
separated from surfactants by the same method as the preparation of
the EDS sample mentioned above. Instead of drying SWNTs for
carrying out the EDS experiment, SWNTs in their wet state were
re-dispersed into various solutions and solvents of different
compositions. In such a fashion, the dispersion of SWNTs becomes
stable and the exfoliation state can be maintained, as can be
supported by Raman characterization to be shown in the next
section.
[0106] A 2-in-1 Step of Functionalization and Stabilization of
Individual CNTs into Organic Media:
[0107] The functionalization mechanisms and processes are depicted
in FIG. 4. Concentrated solution of sulfanilamide in acetone
(10%)%) or other functionalizing agents were added into the
SWNTs/SDS solutions based on a 1:1 stoichiometry of the amine
groups on sulfanilamide and carboxylic groups on SWNTs (FIG. 4A).
The carbon and oxygen chemistry of CNTs were roughly determined by
EDS and XPS. The mixture was kept at 70.degree. C. overnight and
SWNTs form flocculation, indicating the surface functionalization
rendering them insoluble in water phase (FIG. 4B). SWNTs were then
retrieved by filtration or centrifugation and extra SDS and
unreacted sulfanilamide were washed away with alcohol. Acetone was
used to re-disperse SWNT with sonication (FIG. 4C). SWNTs
dispersion is found to be stable for at least two months. The CNT
concentration in the dispersion remains stable at concentrations
greater than about 600 ppm.
[0108] Incorporation of Exfoliated CNT in Epoxy:
[0109] Individual CNT were functionalized with sulfanilamide, or
other types of surfactants or curing agents, and dispersed in
acetone. Additional curing agents and stoichiometric amount of
epoxy were then added and sonicated. Acetone was removed using
rotary evaporator after a stable dispersion of CNT in epoxy was
achieved. The mixture was then cured for 8 hr at 140.degree. C. and
2 hr at 180.degree. C. (EPON.TM. Resin 862 epoxy cured with
sulfanilamide).
[0110] Neutralization (Re-Protonation) and Purification of ZrP
Nanoplatelets
[0111] After TBA.sup.+OH.sup.-, or other efficient basic
exfoliating agents were used to exfoliate ZrP nanoplatelets, a
sufficient amount of acid (e.g., HCl) was added in the dispersion
to fully neutralize TBA, to re-protonate ZrP and to cause
precipitation of nanoplatelets. The coagulated nanoplatelets were
washed 3 or 4 times with DI H.sub.2O to remove additional
acids.
[0112] Solvent Stabilization of Purified ZrP Nanoplatelets
[0113] After the nanoplateles were neutralized and purified, the
re-aggregated nanoplatelets were re-dispersed into mixtures of
ethanol and D H.sub.2O with various volume ratios. A good solvent
of DI H.sub.2O and ethanol with volume ratio of 3:1 has been found
to stabilize purified ZrP well without a need for additional
additives, including surfactants.
[0114] Sorting of SWNT Using Purified ZrP Nanoplatelets
[0115] Using the similar approaches described above to get the
purified .alpha.-ZrP, a mixture of exfoliated SWNT and purified
nanoplatelets was obtained and aggregated. A sufficient amount of
HCl was used in the re-aggregation process or afterwards to strip
off most TBA. The SWNT-ZrP aggregates were washed with DI H.sub.2O
for 3 or 4 times and redispersed into 1% Triton containing
solution, which was comprised of a mixture of ethanol and DI
H.sub.2O with a volume ratio of 1:3. The SWNT-ZrP dispersion was
then centrifuged at 16,800 G for 1 hr. Supernatant and precipitates
were collected separately after centrifugation and characterized
with Raman spectroscopy.
[0116] Debundling/Disentanglement of CNT Using ZrP Nanoplatelets
Deprotonated by KOH(ZrP-K) and Recycling of ZrP Nanoplatelets
[0117] Preparation of ZrP-K Nanoplatelets and
Debundling/Disentanglement of CNT
[0118] After purification, the neutralized ZrP nanoplatelets were
immersed in 100 mM KOH aqueous solution for 30 min and washed with
DI H.sub.2O for 3 or 4 times to remove additional KOH. The modified
nanoplatelets containing the K.sup.+ in the ZrP structure were then
redispersed into DI H.sub.2O via sonication. SWNT and K.sup.+
functionalized ZrP nanoplatelets were mixed at a mass ratio of 1:5,
followed by sonication. TEM was used to characterize the
exfoliation state of SWNT.
[0119] Recycling of ZrP Nanoplatelets for CNT Dispersion
[0120] As illustrated in FIG. 1, step 3, the CNT-nanoplatelet
mixture was separated into two phases after addition of acid/ion
and surfactant with centrifugation. Most CNT were retrieved in the
supernatant phase. The precipitant phase has a gel-like appearance,
which contains precipitated nanoplatelets and a small amount of
CNT. The gel-like phase was washed with D H.sub.2O for 3 or 4 times
to remove residue of acid/ion and surfactants, followed by
immersion in 100 mM KOH aqueous solution of 30 min. Afterwards,
extra KOH was removed by washing again with DI H.sub.2O and the
nanoplatelets de-protonated again with the assistance of KOH, were
redispersed in DI H.sub.2O via sonication. Oxidized CNT bundles
were then added to the reactor to begin another cycle of CNT
debundling and disentanglement process.
[0121] Characterization and Analysis.
[0122] Spectroscopic Characterization of the Dispersion State of
HiPco SWNTs Exfoliated by ZrP Nanoplatelets:
[0123] The absorption spectra of the CNTs in water were recorded on
a Hitachi (Model U-4100) UV-vis-NIR spectrophotometer. Raman
spectra of CNTs were carried out using a Horiba JY LabRam
spectrometer. EDS pattern and SEM images were obtained on a FEI
Quanta 600 field emission SEM (FE-SEM). TEM micrographs were
acquired with a high resolution JEOL 2010 microscope.
[0124] UV-vis-NIR Spectroscopy of HiPco SWNTs Before and after
ZrP-Assisted Exfoliation:
[0125] UV-vis-NIR spectroscopy is one of the most widely used tools
to study SWNTs. FIG. 5A shows the UV-vis-NIR spectra of SWNTs
before and after ZrP-assisted exfoliation. The more distinct and
narrower van Hove transition peaks with increased intensity in the
NIR range and the blue-shifted absorption peaks in UV-visible range
of SWNTs after ZrP-assisted exfoliation suggest that SWNTs are most
likely individually dispersed.
[0126] Raman Spectroscopy of HiPco SWNTs Before and after
ZrP-Assisted Exfoliation:
[0127] The Raman spectra of SWNTs comprises three distinguished
regions: 180-300 cm.sup.-1, the Radial Breathing Modes (RBM);
.about.1300 cm.sup.-1, the defect band (D-band); and .about.1600
cm.sup.-1, the tangential G-mode (G-band). D-band indicates the
defects on the sidewalls of SWNTs. FIG. 5B shows the Raman spectra
of SWNTs before and after ZrP-assisted debundling. The intensity of
D-band of SWNTs increases after debundling and the peak is
sharpened, suggesting that more surface area of SWNTs are exposed
to Raman laser after exfoliation. The blue-shifting (around 5
cm.sup.-1) of G-band of ZrP-treated sample indicates that the
side-walls are relatively free of vibration compared with their
bundled form, which means SWNTs are most likely exfoliated. The
blue-shifting is also observed in RBM (Radial Breathing Mode)
region as shown in FIG. 5C.
[0128] Separation Efficiency of Ionic Screening Method:
[0129] Table 1 lists the experimental conditions, separation
efficiency, and yield of different methods. Ionic screening method
uses low concentration of ions (10 mM for monovalent ions) to
precipitate SWNTs while ZrP is left in the supernatant and no
surfactant is involved. SWNTs were then collected by low-speed
centrifugation (1,500 G for 5 minutes) and dispersed via
sonication. Then, another cycle of ion addition, centrifugation,
and dispersion were carried out. Based on weighing the ZrP residue
left in the supernatant, the separation efficiency of the ionic
screening method was measured to be larger than 90% in our previous
report. However, EDS shows that the separation efficiency of the
first screening cycle was only 55% and was increased to 85% after
the second screening cycle. There was no significant improvement of
the separation efficiency after the second cycle.
[0130] Separation Efficiency and Yield of Salts/Surfactants
Method:
[0131] When using salts and surfactants to re-aggregate ZrP
nanoplatelets, the surfactants used to stabilize CNTs must not be
sensitive to ionic strength. As a result, nonionic surfactants like
Triton and PVP are preferred, because most ionic surfactants are
not stable at high ionic concentrations. When 1% Triton was used,
the separation efficiency was almost 100% with a yield of 61%. The
ability of PVP to stabilize CNTs is not as good as that of Triton,
especially with MWNTs. When using the KCl/PVP method to separate
ZrP nanoplatelets from MWNTs, at least a surfactant concentration
of 2.5% is suggested for 80 ppm of MWNTs dispersion.
[0132] Ionic surfactants were found to be inefficient to separate
CNT and ZrP when combined with ions. They either are not able to
stabilize CNT in an ionic environment (e.g., sodium
dodecylbenzenesulfonate (SDBS) at high ionic strength, cetrimonium
bromide (CTAB) and SDS) or stabilize both CNT and ZrP at the same
time (e.g., SDBS at low ionic strength). Multi-valent ions are
known to be more effective for the ionic screening effect. High
yield and high separation efficiency of CNT-nanoplatelet mixture
are expected if divalent or trivalent ions and combined surfactants
are used in the salts/surfactants method.
[0133] Separation Efficiency and Yield of Acid/Surfactants
Method:
[0134] The efficiency of HCl/surfactants approach is even better
than the above, with 100% separation efficiency and a higher yield.
The improvement lies in the difference of the mechanism between
ion-induced and acid-induced separation, as shown in FIG. 6.
Exfoliated ZrP nanoplatelets are coated with TBA molecules and
surrounded by an electrostatic sphere (FIG. 6A), which prevents
nanoplatelets from aggregation. The presence of added ions shrinks
the electrostatic spheres and causes the reaction-limited
aggregation of ZrP nanoplatelets. However, TBA molecules are still
likely bound onto the surfaces of ZrP nanoplatelets through ionic
bonding, making the aggregates loosely packed (FIG. 6B). On the
other hand, the scenario for HCl is very different. The acidity of
HCl (pKa.apprxeq.-6) is much stronger than that of
Zr(HPO.sub.4).sub.2 (pKa=12.3), TBA.sup.+OH.sup.- is inclined to
react with HCl rather than ZrP. Therefore, when HCl was added into
a solution containing exfoliated ZrP nanoplatelets, TBA molecules
would detach themselves from the nanoplatelets, rendering a more
close-packed agglomeration of the nanoplatelets (FIG. 6C) and a
more thorough separation from CNTs (100%, FIG. 6E), when compared
with that of the KCl method (<100%, FIG. 6D).
[0135] Another advantage of the HCl/surfactants method is that the
concentration of HCl used here is much lower (<2 mM) than the
KCl concentration (>20 mM) used in the KCl/surfactants method.
The low ionic strength makes this method not only applicable to
nonionic surfactants, such as PVP and Triton, but also anionic
surfactants that are sensitive to ionic strength, like SDS and
SDBS. Cationic surfactants like CTAB have a tendency to bind with
ZrP nanoplatelets, instead of CNTs; therefore it is not effective.
Theoretically, the maximum amount of HCl required to fully separate
the ZrP nanoplatelets should not be more than the amount of TBA in
the solution. However, other factors can affect the outcome and may
require a higher concentration of HCl to show effectiveness.
[0136] When Triton is used to stabilize CNTs, the molar ratio of
the actual HCl used to TBA for achieving 100% separation efficiency
is slightly larger (1.13:1) than the theoretical value of 1:1, with
a yield of 63%. This is possibly due to the composition complexity
of the whole system with carboxylic groups of SWNTs (pKa
(CH.sub.3COOH)=4.75) and possible presence of residual metal
catalysts from SWNTs synthesis, which will neutralize with the
added acid.
[0137] When using SDS and HCl to separate ZrP and to stabilize
CNTs, the molar ratio of the actual HCl to TBA used in the
dispersion to achieve 100% separation efficiency is only 0.56:1,
which is much less than that with Triton. We have noticed that when
SDS was added to the CNT-ZrP mixture, a small amount of
precipitates would form before acid was added. This phenomenon is
not seen when Trition is used. SDS is a type of ion composed of a
weak dodecanol base and a relatively strong NaHSO.sub.4 acid
(pKa=1.9) and will hydrolyze to become acidic when dissolved in
water when compared with Zr(HPO.sub.4).sub.2. It is likely that SDS
can cause partial detachment of TBA from the nanoplatelets before
acid is added. Another possible reason is that the addition of SDS
increases the ionic strength in the CNT-ZrP mixture and
destabilizes the ZrP before acid is added. Consequently, a
considerable increase in the yield (up to 80%) of CNTs is achieved
with only half of the theoretic and actual amount of HCl needed
when Triton is used as the stabilizing surfactant.
[0138] FIG. 7 shows the EDS data and the elemental mapping of CNTs
before and after ZrP separation using the HCl/SDS method for HiPco
SWNTs (A) and MWNTs (B), respectively. The energy signal of the Zr
(L.alpha..sub.1=2.042 keV, online database of X-ray transition
energies from National Institute of Standards and Technology) and P
(K.alpha..sub.1=2.014 keV) elements in the CNTs/ZrP mixture
disappeared after the nanoplatelets separation procedure. The
separation efficiency is 100% with a yield of over 70% after one
cycle. There is no signal of Na (k.alpha..sub.1=1.041 keV) element
of SDS either, suggesting a complete SDS removal after washing CNTs
with acetone and alcohols.
[0139] FIG. 8 shows the EDS data and elemental mapping of HiPco
SWNTs (A) and MWNTs (B) after ZrP removal using the KCl/triton
method. The separation efficiency is nearly 100%, indicated by a
very weak signal from Zr and P elements. Yet, the yield is 61%,
which is less than that of the HCl/SDS method and is similar to
HCl/Triton method.
[0140] Separation Efficiency and Yield of the Combination of Ionic
Screening and Acids/Surfacants (or Ions/Surfacants) Methods:
[0141] One phenomena we have noticed is that when the first cycle
yield increase with decreasing nanoplatelets amount in the
SWNT-nanoplatelet mixture. For example, when the weight ratio of
SWNT and ZrP are reduced to 1 to 1 instead of 1 to 5, the first
cycle yield to retrieve CNTs using the HCl/SDS method can be
greatly improved to over 90%. However, it is also noted that full
exfoliation of SWNTs is more likely when more nanoplatelets are
incorporated. In order to achieve a high yield and good CNTs
exfoliation, we first use the ionic screening approach to remove
most of the nanoplatelets from a mixture of SWNTs and ZrP with a
weight ratio of 1 to 5. SWNTs aggregates with trapped nanoplatelet
were then collected and redispersed in SDS solution, followed by
ZrP precipitation using HCl. In this fashion, over 90% of
individual SWNTs can be stabilized by SDS in the supernatant.
Compared with using multiple cycles to achieve higher yield for
SWNT retrieval, the above combined process is more simple and
effective. The ionic screening method can also be combined with the
salts/surfactants method to increase the 1.sup.st cycle yield, in
which case the SWCNT precipitated by ions, along with trapped ZrP,
were redispersed in aqueous solutions of nonionic surfactants and
additional ions were used to remove ZrP completely.
[0142] Raman Spectra of Individual HiPco SWNTs after Nanoplatelets
Separation:
[0143] FIG. 9 shows the (A) Raman spectra and (B) RBM region of
HiPco SWNTs stabilized in SDS aqueous solution after ZrP-assisted
exfoliation and ZrP removal compared with those of pre-treated
SWNTs. FIG. 10 shows the (A) Raman spectra and (B) RBM region of
HiPco SWNTs transferred into piperidine and CTAB solutions after
ZrP-assisted exfoliation, ZrP removal and SDS removal, compared
with those of pre-treated SWNTs bundles. From the blue-shifting of
G-band and in the RBM region, we can tell that the dispersion state
obtained through ZrP-assisted exfoliation is well maintained after
ZrP separation.
[0144] Elemental Analysis of ZrP Nanoplatelet and its
Derivatives
[0145] XPS was used to quantify the chemical composition of the
functionalized ZrP nanoplatelets and their derivatives. Table 2
lists the atomic ratio of Zr, P, K (if any). O, and C elements of
differently treated nanoplatelets, while normalized by the amount
of Zr element. The superscripts "e" denote the experimental value
and the superscripts "t" denote the theoretical value of the
chemical structures of Zr(PO.sub.4).sub.2K.sub.2 (ZrP--K),
Zr(HPO.sub.4)(PO.sub.4)--C.sub.16H36 (ZrP-TBA conjugated at molar
ratio of 1:1), and Zr(HPO.sub.4).sub.2.H.sub.2O (i.e., purified
ZrP) nanoplatelets. The large C content in ZrP-TBA nanoplatelet is
obviously from the TBA molecule. After using a sufficient amount of
acid to neutralize TBA, the C content is significantly reduced in
the purified ZrP nanoplatelets, indicating the detachment of a
significant portion of TBA molecules from the nanoplatelet
surfaces. A comparable amount of K to that of P and Zr in ZrP-K
nanoplatelet verifies the presence of K.sup.+ on the nanoplatelet
structure. The chemical structure of the product is likely to be
Zr(PO.sub.4).sub.2K.sub.2 after the HPO.sub.4.sup.2- reaction with
KOH. The quantification of chemical structure of different treated
nanoplatelets allows the comparison of their mechanisms to
exfoliate CNT. It is noted that the mass ratio of CNT and
nanoplatelets in this work refers only to the content of ZrP
(Zr(HPO.sub.4).sub.2.H.sub.2O) whether or not ion or TBA molecule
is incorporated.
TABLE-US-00002 TABLE 2 Chemical Composition of Different
Nanoplatelets. Atomic ratio P.sup.e/P.sup.t Zr K.sup.e
O.sup.e/O.sup.t C.sup.e/C.sup.t ZrP-K 1.5/2 1 1.6 7.4/9 3.4/0
ZrP-TBA 2.0/2 1 -- 8.7/9 13/12.8 ZrP 1.9/2 1 -- 8.4/9 5.6/0
[0146] Solvent-Stabilization of Derivatives of ZrP
[0147] FIG. 11 shows visual image of purified ZrP nanoplatelet
dispersion (500 ppm) in water prepared by exfoliating ZrP
nanoplatelet with TBA, TBA neutralization with acid, and
redispersion in mixtures of DI H.sub.2O and ethanol with different
volume ratios after sonication. It has been found that with 3:1
volume ratio of DI H.sub.2O and ethanol, the dispersion has the
best transparency and stability. Pristine ZrP nanoplatelets,
without TBA-assisted exfoliation, however, cannot be dispersed and
stabilized in this mixture even its chemical composition is the
same as that of purified nanoplatelets. The results indicate that
exfoliated nanoplatelets do not restack into a highly ordered
layered structure even after the removal of the dispersing ligand.
On the contrary, the ligand-free nanoplatelet aggregate forms
loosely packed structure in its wet state. The composition of the
dispersing media may be varied but the principle of dispersing the
nanoplatelets without using surfactants is to match the polarity
(e.g., by matching the dielectric constant) of the solvent to that
of the nanoplatelet. Similar principle can also be applied to
surfactant-free ZnO quantum dots and CNT. The neutralized
nanoplatelet stabilized solely by solvent shows different stability
to the positively charged nanoplatelet (e.g., nanoplatelets
associated with TBA.sup.+) stabilized by electrostatic repulsion.
While the neutralized nanoplatelet, if undisturbed, can be
stabilized in a polarity-matched solvent for months without
precipitation, they can be easily re-aggregated by centrifugation.
This phenomenon allows for sorting of SWNT based on the neutralized
nanoplatelets mentioned above.
[0148] Affinity of CNT to Different Derivative Nanoplatelets and
SWNT Sorting
[0149] The purified ZrP nanoplatelets tend to interact differently
with CNT of different chirality. While ZrP-TBA can be used to
obtain fully debundled SWNT dispersion, we have discovered that the
purified nanoplatelets will only interact with a fraction of
oxidized SWNT and form a stable solution. Raman spectroscopy shows
that the stabilized portion of the solution and the non-interacted
portion SWNT exhibit different electronic structures. However, the
sorting effect is not very obvious, possibly because most SWNT are
still in the bundled form.
[0150] In order to examine the nanoplatelet sorting effect on
individually dispersed SWNT, ZrP-TBA nanoplatelet dispersion was
used to exfoliate SWNT first and then purified with acid. After
centrifugation, all SWNT and nanoplatelets precipitate into a gel
form, containing mainly exfoliated SWNT and purified ZrP
nanoplatelets. Similar to purified ZrP nanoplatelets alone, the
gel-like mixture of exfoliated SWNT and purified nanoplatelets can
be redispersed in a mixture of DI H2O and ethanol with volume ratio
of 3:1. Triton was then added to stabilize certain types of SWNT
before centrifugation; while the SWNT with better affinity to
purified ZrP nanoplatelets would precipitate under centrifugation.
Raman spectra of the supernatant portion and the precipitated
portion after 1 hr centrifugation at 16,800 G show the distinct
electronic structure of metallic SWNT attached to the purified ZrP
nanoplatelets, and most of the semiconducting SWNT remained in the
supernatant as shown in FIG. 12.
[0151] ZrP-TBA and ZrP--K nanoplatelets behave very similarly in
dispersing CNT. The easy preparation of ZrP--K nanoplatelets from
other derivatives of nanoplatelets gives rise to the recyclability
of ZrP in dispersing CNT. Preliminary results show that after CNT
retrieval from CNT-ZrP(-TBA) mixture using ion/acid and
surfactants, the precipitated nanoplatelet gel can be used to
prepared ZrP--K nanoplatelets (or a mixture of ZrP--K and ZrP-TBA
nanoplatelets, depending how much TBA is removed during the
re-aggregation of nanoplatelets) and re-used to disperse CNT.
Preliminary results show that after CNT retrieval from
CNT-ZrP(-TBA) mixture using ion/acid and surfactants, the
precipitated nanoplatelet gel can be isolated and deprotonated
again even with the CNT trapped inside. Since the nanoplatelet in
the gel-from aggregate is not likely to restack into a close-packed
structure, exfoliation agent with a big molecular sized like
TBA.sup.+OH.sup.- is no longer necessary. Small basic molecules
like KOH have then been used to prepare exfoliated ZrP--K
nanoplatelets to disperse more CNT. To be noticed is that the
nanoplatelets separated from CNT by ion/surfactant method should be
easier to redisperse than those separated using acid/surfactant
method since the former is likely to have more TBA molecules
attached to the nanoplatelet surface than the latter.
[0152] Microscopy of Exfoliated HiPco SWNTs Before and after
Nanoplatelets Removal:
[0153] FIGS. 13A and 13B show the TEM micrographs of individual
SWNTs before and after ZrP separation using HCl/SDS method, SWNTs
exhibit individually exfoliated state and has a diameter of about
1.5 nm. The nanoplatelets bound to SWNTs (FIG. 13A) are completely
removed after ZrP separation (FIG. 13B). FIG. 13C shows the SEM of
individual SWNTs transferred into 0.25% polystyrene sulfonate
sodium (PSS) solution. SWNTs in the image have a defused morphology
and appear broader in diameter because of the PSS coating on the
SWNTs surface. Similarly, FIG. 14 illustrates TEM micrographs of
disentangled MWCNT before (FIG. 14A) and after ZrP separation (FIG.
14B).
[0154] Microscopy of SWNT Dispersed Using ZrP--K Nanoplatelets:
[0155] FIG. 15 presents the morphology of the mixture of SWNT and
ZrP--K nanoplatelets with a 1:5 calculated mass ratio of SWNT and
ZrP (Zr(HPO.sub.4).sub.2.H.sub.2O), with most SWNT debundled and a
small fraction of bundled SWNT. With further optimization, ZrP--K
nanoplatelet is expected to be able to fully debundle CNT.
[0156] Microscopy of Exfoliated XD-CNTs after Nanoplatelets Removal
and Sulfanilamide Functionalization:
[0157] All the work described above about HiPco SWNTs has been
extended to the case of XD-CNTs and MWNTs with equal success.
XD-CNTs are suitable for visualization after
sulfanilamide-functionalization with a diameter of around 5 nm and
are economical for preparing polymer nanocomposites. To make an
XD-CNTs/epoxy nanocomposite, pre-treated XD-CNTs has been
exfoliated with and then separated from ZrP nanoplatelets using the
HCl/SDS method, followed by sulfanilamide treatment in SDS solution
and redispersion into acetone. One advantage of this
functionalization procedure is that the removal of SDS and
functionalization of exfoliated CNTs can be achieved at the same
time, avoiding extra steps of surfactants removal. The use of
sulfanilamide and acetone here is a representation of a simple
method of functionalization and transferring individual CNTs into
organic and polymeric media. Another example is by functionalizing
CNTs with alkylamine or alkanol, individual CNTs can become soluble
even in nonpolar solvents.
[0158] FIG. 16A shows TEM of isolated XD-CNTs dispersed in SDS
solution; no nanoplatelet is observed. The inset is a high
magnification image, illustrating the overlap of two individual
XD-CNTs with a SDS layer coated on the nanotube surfaces. FIG. 16B
is OM of isolated XD-CNTs in acetone; no micro-sized aggregates can
be seen. TEM (FIGS. 16C and 16D) also show that XD-CNTs are
individually exfoliated in acetone with amine coating of several
sites. The dispersion of XD-CNTs in acetone is then mixed with
epoxy containing acetone for making epoxy nanocomposites.
[0159] Fluorescent Epoxy-SWNT Nanocomposites:
[0160] Fluorescence of SWNT in polymer matrix is usually suppressed
due to the fact that current techniques of fabrication polymer-SWNT
composite often involve severe chemical treatment of SWNT, which
damages their electronic structure. The epoxy/SWNT nanocomposites
fabricated using our approaches have been demonstrated to show
fluorescent signal, suggesting minimal damage of the SWNT
structure.
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