U.S. patent application number 14/012224 was filed with the patent office on 2013-12-26 for nanowire preparation methods, compositions, and articles.
The applicant listed for this patent is Carestream Health, Inc.. Invention is credited to Doreen C. Lynch, Richard R. Ollmann, William D. Ramsden.
Application Number | 20130343950 14/012224 |
Document ID | / |
Family ID | 46637014 |
Filed Date | 2013-12-26 |
United States Patent
Application |
20130343950 |
Kind Code |
A1 |
Ollmann; Richard R. ; et
al. |
December 26, 2013 |
NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND ARTICLES
Abstract
Methods of producing metal nanowires employing tubular
continuous-flow reactors and their products are described and
claimed. Such methods can provide superior nanowire uniformity
without agglomeration. Such nanowires are useful for electronic
applications.
Inventors: |
Ollmann; Richard R.;
(Woodbury, MN) ; Ramsden; William D.; (Afton,
MN) ; Lynch; Doreen C.; (Afton, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Carestream Health, Inc. |
Rochester |
NY |
US |
|
|
Family ID: |
46637014 |
Appl. No.: |
14/012224 |
Filed: |
August 28, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13347986 |
Jan 11, 2012 |
8551211 |
|
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14012224 |
|
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|
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61442874 |
Feb 15, 2011 |
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Current U.S.
Class: |
420/501 ;
75/370 |
Current CPC
Class: |
B22F 9/24 20130101; B22F
2998/00 20130101; B22F 1/0025 20130101; B22F 3/003 20130101; B22F
2998/00 20130101; B22F 2998/00 20130101 |
Class at
Publication: |
420/501 ;
75/370 |
International
Class: |
B22F 9/24 20060101
B22F009/24 |
Claims
1. A method comprising: feeding at least one first composition
comprising at least one reducible metal ion and at least one
protecting agent to the contents of at least one continuous-flow
reactor comprising at least one tubular reactor; heating the at
least one first composition prior to reducing the at least one
reducible metal ion to at least one metal nanowire; and withdrawing
at least one second composition comprising the at least one metal
nanowire from the contents of the at least one continuous-flow
reactor.
2. The method according to claim 1, wherein at least some of the
withdrawing of the at least one second composition occurs before at
least some of the feeding of the at least one first
composition.
3. The method according to claim 1, wherein at least some of the
withdrawing of the at least one second composition occurs
simultaneously with at least some of the feeding of the at least
one first composition.
4. The method according to claim 1, wherein the at least one
continuous-flow reactor consists essentially of the at least one
tubular reactor.
5. The method according to claim 1, wherein the at least one first
composition further comprises at least one polyol.
6. The method according to claim 1, wherein the at least one first
reducible metal ion comprises at least one coinage metal ion or at
least one ion from IUPAC Group 11.
7. The method according to claim 1, wherein the reduction is
performed in the presence of at least one second ion or atom
comprising at least one ion or atom from IUPAC Group 8 or at least
one ion or atom from IUPAC Group 14.
8. The method according to claim 1, wherein the reduction is
performed in the presence of at least one halide ion.
9. The method according to claim 1, wherein the at least one metal
nanowire comprises a length of at least about 10 .mu.m.
10. The metal nanowire produced according to the method of claim
1.
11. The method according to claim 1, wherein the at least one
protecting agent comprises at least one polar polymer or at least
one polar copolymer.
12. The method according to claim 1, wherein the at least one
reducible metal ion comprises at least one silver ion.
13. The method according to claim 7, wherein the at least one
second ion or atom comprises at least one tin ion or atom.
14. The method according to claim 1, further comprising heating the
at least one first composition, wherein at least a portion of the
heating the at least one first composition occurs simultaneously
with the reducing the at least one first reducible metal ion.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 13/347,986, filed Jan. 11, 2012, which claimed
the benefit of U.S. Provisional Application No. 61/442,874, filed
Feb. 15, 2011, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS,
AND ARTICLES, which is hereby incorporated by reference in its
entirety.
SUMMARY
[0002] At least a first embodiment provides methods comprising
feeding at least one first composition comprising at least one
first reducible metal ion to the contents of at least one
continuous-flow reactor comprising at least one tubular reactor;
reducing the at least one reducible metal ion to at least one metal
nanowire; and withdrawing at least one second composition
comprising the at least one metal nanowire from the contents of the
at least one continuous-flow reactor. In at least some embodiments,
at least some of the withdrawing of the at least one second
composition occurs before at least some of the feeding of the at
least one first composition, or it occurs simultaneously with at
least some of the feeding of the at least one first composition, or
both. In some cases, the contents of the tubular reactor are not
mixed with a rotating agitator. The at least one continuous-flow
reactor may optionally consist essentially of the at least one
tubular reactor.
[0003] In at least some embodiments, the at least one first
composition further comprises at least one polyol and at least one
of a protecting agent, a polar polymer, or a polar copolymer. In
some cases, all of the components to be fed to the at least one
continuous reactor may, for example, be combined to form a single
feed composition.
[0004] In some cases, the at least one first reducible metal ion
may comprise at least one coinage metal ion, at least one ion from
IUPAC Group 11, or at least one ion of silver. In at least some
embodiments, the reduction may be performed in the presence of at
least one second ion or atom comprising at least one ion or atom
from IUPAC Group 8, at least one ion or atom from IUPAC Group 14,
at least one iron ion or atom, or at least one tin ion or atom. In
some cases, the reduction may be performed in the presence of a
halide ion, such as, for example, a bromide ion, a chloride ion, or
an iodide ion, or the reduction may, in some cases, be performed in
the presence of a chloride ion.
[0005] At least some embodiments provide the metal nanowires
produced according to such methods. The metal nanowires produced
according to such methods may, for example, comprise a length of at
least about 10 .mu.m, or from about 10 .mu.m to about 50 .mu.m, or
of approximately 20 .mu.m.
[0006] At least some other embodiments provide one or more articles
comprising at least one such nanowire. Such articles may, for
example, comprise electronic devices, transparent conductive films,
and the like.
[0007] At least a second embodiment provides methods comprising
providing at least one first composition comprising at least one
first reducible metal ion, and reducing the at least one first
reducible metal ion to at least one first metal in the presence of
at least one first protecting agent and at least one first solvent,
where the reduction is performed in at least one first
continuous-flow reactor comprising at least one tubular reactor. In
at least some embodiments, the at least one first reducible metal
ion comprises at least one coinage metal ion, or at least one ion
from IUPAC Group 11, or at least one ion of silver. In some cases,
the at least one first compound comprises silver nitrate. In at
least some embodiments, the reduction may be carried out in the
presence of at least one element from IUPAC Group 8, such as, for
example, iron or an ion of iron, or in the presence of at least one
element from IUPAC Group 14, such as, for example, tin or an ion of
tin, or in the presence of at least one metal salt, such as, for
example, at least one metal chloride. In at least some embodiments,
the at least one first protecting agent comprises at least one of
one or more surfactants, one or more acids, or one or more polar
solvents, or it may, for example, comprise polyvinylpyrrolidinone.
In at least some cases, the at least one first solvent comprises at
least one polyol, such as, for example, one or more of ethylene
glycol, propylene glycol, glycerol, one or more sugars, or one or
more carbohydrates. In at least some embodiments, the composition
has a ratio of the total moles of the at least one second metal or
metal ion to the moles of the at least one first reducible metal
ion from about 0.0001 to about 0.1. The reduction may be carried
out at one or more temperatures, such as, for example, from about
80.degree. C. to about 190.degree. C. In at least some embodiments,
the second composition comprises at least one coinage metal or
coinage metal ion, or at least one element from IUPAC Group 11,
such as, for example, silver or an ion of silver.
[0008] At least some embodiments provide such methods, where the
reduction is carried out in the presence of at least one second
composition comprising seed particles. The at least one second
composition may comprise at least one coinage metal or coinage
metal ion, or at least one element from IUPAC Group 11, such as,
for example, silver or an ion of silver. In at least some
embodiments, the seed particles are formed by a method comprising
providing at least one third metal ion and contacting the at least
one third metal ion with at least one second protecting agent and
at least one second solvent. Such a method may, for example, be
carried out in at least one second continuous-flow reactor, which
may, for example, comprise at least one tubular reactor.
[0009] Other embodiments provide the first metal product formed by
any of these methods. Such a product may, for example, comprise one
or more of nanowires, nanocubes, nanorods, nanopyramids, or
nanotubes. Such nanowires may have an average diameter of about 30
to about 150 nm, or from about 30 to about 110 nm, or from about 80
to about 100 nm. Some embodiments provide one or more articles
comprising at least one such nanowire. Such articles may, for
example, comprise electronic devices, transparent conductive films,
and the like.
[0010] These embodiments and other variations and modifications may
be better understood from the brief description of figures,
figures, description, exemplary embodiments, examples, and claims
that follow.
BRIEF DESCRIPTION OF FIGURES
[0011] FIG. 1 shows an embodiment of a reaction system with a
continuous-flow tubular reactor.
[0012] FIG. 2 shows an embodiment of a reaction system with two
continuous-flow tubular reactor stages and an inter-stage feed
point.
[0013] FIG. 3 shows a micrograph of the product suspension of
Example 1.
[0014] FIG. 4 shows a micrograph of the product suspension of
Example 2.
[0015] FIG. 5 shows a micograph of the product suspension of
Comparative Example 3 after 1 hr at reaction temperature.
[0016] FIG. 6 shows a micograph of the product suspension of
Comparative Example 3 after 2 hrs at reaction temperature.
[0017] FIG. 7 shows a micograph of the product suspension of
Comparative Example 3 after 3 hrs at reaction temperature.
DESCRIPTION
[0018] All publications, patents, and patent documents referred to
in this document are incorporated by reference herein in their
entirety, as though individually incorporated by reference.
[0019] U.S. Provisional Application No. 61/442,874, filed Feb. 15,
2011, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND
ARTICLES, is hereby incorporated by reference in its entirety.
[0020] U.S. patent application Ser. No. 13/347,986, filed Jan. 11,
2012, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND
ARTICLES, is hereby incorporated by reference in its entirety.
Introduction
[0021] Silver nanowires (AgNW) are a unique and useful wire-like
form of the metal in which the two short dimensions (the thickness
dimensions) are less than 300 nm, while the third dimension (the
length dimension) is greater than 1 micron, preferably greater than
10 microns, and the aspect ratio (ratio of the length dimension to
the larger of the two thickness dimensions) is greater than five.
They are being examined as conductors in electronic devices or as
elements in optical devices, among other possible uses.
[0022] A number of procedures have been presented for the
preparation of AgNW. See, for example, Y. Xia, et al. (Angew. Chem.
Int. Ed. 2009, 48, 60), which is hereby incorporated by reference
in its entirety. These include the "polyol" process, in which a
silver salt is heated in a polyol (typically ethylene glycol (EG))
in the presence of polyvinylpyrrolidone (PVP), yielding a
suspension of AgNW in EG, from which the wires can be isolated
and/or purified as desired.
[0023] Y. Sun, B. Mayers, T. Herricks, and Y. Xia (Nano Letters,
2003, 3(7), 955-960), hereby incorporated by reference in its
entirety, propose that AgNW are the result of the growth of
multiply-twinned particles (MTP) of silver metal. P.-Y. Silvert et
al. (J. Mater. Chem., 1996, 6(4), 573-577 and J. Mater. Chem.,
1997, 7, 293-299, both of which are hereby incorporated by
reference in their entirety) describe the formation of colloidal
silver dispersions in EG in the presence of PVP. Chen et al.
(Nanotechnology, 2006, 7, 466-74), hereby incorporated by reference
in its entirety, describe effects of changing seed concentrations
on morphology.
[0024] US patent publication 2010/0242679 and Japanese patent
publication 2010-255037 describe AgNW synthesis using
continuous-flow stirred tank reactors.
[0025] Applicants have discovered that continuous-flow tubular
reactors may be used to produce high aspect ratio AgNW with narrow
nanowire length distributions. Such tubular reactors can enable
precise control of temperature and reaction time without use of
excessive agitation, thereby improving product uniformity.
[0026] FIG. 1 shows an embodiment of a reaction system with a
continuous-flow tubular reactor. A feed pump [101] supplies raw
materials, catalysts, and solvents to the continuous-flow tubular
reactor [102], a portion of which is contained in a thermostatted
oven [103]. The downstream portion of the tubular reactor is
immersed in a quench bath [104], with the product exiting the
outlet of the reactor [105].
[0027] FIG. 2 shows an embodiment of a reaction system with two
continuous-flow tubular reactor stages and an inter-stage feed
point, where the feed pumps have been omitted from the figure for
clarity. The first tubular reactor stage [201] may, for example, be
used to prepare a seed dispersion, which is fed to the second
reactor stage [202]. The other raw materials, catalysts, and
solvents may also be supplied to the second reactor stage at the
inter-stage feed point [203].
Reducible Metal Ions and Metal Products
[0028] Some embodiments provide methods comprising reducing at
least one reducible metal ion to at least one metal nanowire. A
reducible metal ion is a cation that is capable of being reduced to
a metal under some set of reaction conditions. In such methods, the
at least one first reducible metal ion may, for example, comprise
at least one coinage metal ion. A coinage metal ion is an ion of
one of the coinage metals, which include copper, silver, and gold.
Or such a reducible metal ion may, for example, comprise at least
one ion of an IUPAC Group 11 element. An exemplary reducible metal
ion is a silver cation. Such reducible metal ions may, in some
cases, be provided as salts. For example, silver cations might, for
example, be provided as silver nitrate.
Preparation Methods
[0029] A common method of preparing nanostructures, such as, for
example, nanowires, is the "polyol" process. Such a process is
described in, for example, Angew. Chem. Int. Ed. 2009, 48, 60, Y.
Xia, Y. Xiong, B. Lim, S. E. Skrabalak, which is hereby
incorporated by reference in its entirety. Such processes typically
reduce a metal cation, such as, for example, a silver cation, to
the desired metal nanostructure product, such as, for example, a
silver nanowire. Such a reduction may be carried out in a reaction
mixture that may, for example, comprise one or more polyols, such
as, for example, ethylene glycol (EG), propylene glycol,
butanediol, glycerol, sugars, carbohydrates, and the like; one or
more protecting agents, such as, for example,
polyvinylpyrrolidinone (also known as polyvinylpyrrolidone or PVP),
other polar polymers or copolymers, surfactants, acids, and the
like; and one or more metal ions. These and other components may be
used in such reaction mixtures, as is known in the art. The
reduction may, for example, be carried out at one or more
temperatures from about 80.degree. C. to about 190.degree. C.
Metals, Metals Ions, Halides, and Metal Halides
[0030] In some embodiments, the reduction may be carried out in the
presence of one or more metals or metal ions (different from the at
least one reducible metal ion), or in the presence of one or more
halide ions, or both. The metal ions used to catalyze wire
formation are generally primarily reported to be provided as a
metal halide salt, usually as a metal chloride, for example,
FeCl.sub.2 or CuCl.sub.2. See, for example, J. Jiu, K. Murai, D.
Kim, K. Kim, K. Suganuma, Mat. Chem. & Phys., 2009, 114, 333,
which refers to NaCl, CoCl.sub.2, CuCl.sub.2, NiCl.sub.2 and
ZnCl.sub.2; Japanese patent application publication JP2009155674,
which describes SnCl.sub.4; S. Nandikonda, "Microwave Assisted
Synthesis of Silver Nanorods," M. S. Thesis, Auburn University,
Aug. 9, 2010, which refers to NaCl, KCl, MgCl.sub.2, CaCl.sub.2,
MnCl.sub.2, CuCl.sub.2, and FeCl.sub.3; S. Nandikonda and E. W.
Davis, "Effects of Salt Selection on the Rapid Synthesis of Silver
Nanowires," Abstract INOR-299, 240th ACS National Meeting, Boston,
Mass., Aug. 22-27, 2010, which discloses NaCl, KCl, MgCl.sub.2,
CaCl.sub.2, MnCl.sub.2, CuCl.sub.2, FeCl.sub.3, Na.sub.2S, and NaI;
Chinese patent application publication CN101934377, which discloses
Mn.sup.2+; Y. C. Lu, K. S. Chou, Nanotech., 2010, 21, 215707, which
discloses Pd.sup.2+; and Chinese patent application publication
CN102029400, which discloses NaCl, MnCl.sub.2, and Na.sub.2S. Use
of KBr has been disclosed in, for example, D. Chen et al., J.
Mater. Sci.: Mater. Electron., 2011, 22(1), 6-13; L. Hu et al., ACS
Nano, 2010, 4(5), 2955-2963; and C. Chen et al, Nanotechnology,
2006, 17, 3933. Use of NaBr has been disclosed in, for example, L.
Zhou et al., Appl. Phys. Letters, 2009, 94, 153102. Japanese patent
application publication 2009-155674 discloses use of SnCl.sub.4.
U.S. patent application publication 2010/0148132 discloses use of
NaCl, KCl, CaCl.sub.2, MgCl.sub.2, and ZnCl.sub.2. U.S. patent
application publications 2008/0210052 and 2011/0048170 disclose use
of quaternary ammonium chlorides. See also Z. C. Li et al., Micro
& Nano Letters, 2011, 6(2), 90-93; and B. J. Wiley et al.,
Langmuir, 2005, 21, 8077. These and other compounds will be
understood by those skilled in the art.
Continuous-Flow Reactors and Tubular Reactors
[0031] In at least some embodiments, at least one metal ion is
reduced to at least one metal in a continuous-flow reactor. In such
a continuous-flow reactor, at least one feed composition or
compositions ("feed") comprising the at least one metal ion is
supplied to the reactor and at least one product composition or
compositions ("product") comprising the at least one metal is
withdrawn from the reactor. The feed may, for example, by supplied
at a fixed flow rate, at a time varying flow rate, intermittently,
and so on. The product may, for example, be withdrawn at a fixed
flow rate, at a time varying flow rate, intermittently, and so
on.
[0032] In such a continuous-flow reactor, at least some of the feed
is supplied to the reactor after at least some of the product is
withdrawn from the reactor. This may be contrasted with a batch
reactor, where substantially all of the feed compositions
comprising the at least one metal ion are supplied to the reactor
prior to or at the start of the reduction, and where substantially
all of the product compositions are withdrawn after the feed
compositions are fed. And it may be contrasted with a semi-batch
reactor, where some of the feed compositions are supplied prior to
or at the start of the reduction and some of the feed compositions
are supplied thereafter, and where substantially all of the product
compositions are withdrawn after the feed compositions are fed.
[0033] The temperature of the contents of a continuous-flow reactor
may be uniform or may vary according to location or time. The
pressure of the contents of a continuous-flow reactor may be
uniform or may vary according to location or time. The number of
phases present in the continuous-flow reactor may be uniform or may
vary according to location or time.
[0034] In at least some embodiments, the reduction may be carried
out in at least one continuous-flow reactor comprising at least one
tubular reactor. In such a tubular reactor, at least one feed
composition or compositions ("feed") comprising the at least one
metal ion is supplied to one or more inlets to the reactor and at
least one product composition or compositions ("product")
comprising the at least one metal is withdrawn from one or more
outlets of the reactor. The feed may, for example, by supplied at a
fixed flow rate, at a time varying flow rate, intermittently, and
so on. The product may, for example, be withdrawn at a fixed flow
rate, at a time varying flow rate, intermittently, and so on.
[0035] Such a tubular reactor may be contrasted with a stirred
reactor, which comprises one or more rotating agitators to mix the
reactor's contents. A tubular reactor will have at least one path
between at least one inlet and at least one outlet that does not
contact such a rotating agitator. In some cases, all paths between
inlets and outlets of the reactor will not contact such a rotating
agitator.
[0036] In at least some embodiments, such a tubular reactor may
optionally comprise one or more static mixing elements between at
least some of its inlets and outlets. Such static mixing elements
may, in some cases, improve product homogeneity and increase heat
transfer between the reactor contents and the walls of the
reactor.
[0037] In at least some embodiments, such continuous-flow reactors
may be arranged as parallel or series stages of reactors. The
stages may, for example, be stirred reactors, tubular reactors, or
both. In such cases, feeds may be provided between at least some of
the stages, or products may be withdrawn between at least some of
the stages, or both. Other devices may optionally be provided
between stages, such as, for example, devices for inter-stage
heating or cooling of the material flowing through them.
[0038] In at least some embodiments, the feed composition comprises
the at least one reducible metal ion, at least one polyol, and at
least one of a protecting agent, a polar polymer, or a polar
copolymer. In some cases, all of the components to be fed to the at
least one continuous reactor may, for example, be combined to form
a single feed mixture. Such an arrangement may, for example,
provide improved product uniformity relative to that of a
semi-batch reactor by reducing or eliminating variability due to
changes in timing, quantities, and feed rates of the feeds to the
semi-batch reactor.
[0039] In at least some embodiments, at least a portion of at least
one of the product streams of a continuous-flow reactor may be
provided to at least one of the inlets of the same or a different
continuous-flow reactor using one or more recycle streams. Such a
recycle stream may optionally comprise one or more surge tanks or
compartments to help manage inventories that are not in the reactor
or reactors. These and other variations will be understood by those
skilled in the art.
Nanostructures, Nanostructures, and Nanowires
[0040] In some embodiments, the metal product formed by such
methods is a nanostructure, such as, for example, a one-dimensional
nanostructure. Nanostructures are structures having at least one
"nanoscale" dimension less than 300 nm, and at least one other
dimension being much larger than the nanoscale dimension, such as,
for example, at least about 10 or at least about 100 or at least
about 200 or at least about 1000 times larger. Examples of such
nanostructures are nanorods, nanowires, nanotubes, nanopyramids,
nanoprisms, nanoplates, and the like. "One-dimensional"
nanostructures have one dimension that is much larger than the
other two dimensions, such as, for example, at least about 10 or at
least about 100 or at least about 200 or at least about 1000 times
larger.
[0041] Such one-dimensional nanostructures may, in some cases,
comprise nanowires. Nanowires are one-dimensional nanostructures in
which the two short dimensions (the thickness dimensions) are less
than 300 nm, preferably less than 100 nm, while the third dimension
(the length dimension) is greater than 1 micron, preferably greater
than 10 microns, and the aspect ratio (ratio of the length
dimension to the larger of the two thickness dimensions) is greater
than five. Nanowires are being employed as conductors in electronic
devices or as elements in optical devices, among other possible
uses. Silver nanowires are preferred in some such applications.
[0042] Such methods may be used to prepare nanostructures other
than nanowires, such as, for example, nanocubes, nanorods,
nanopyramids, nanotubes, and the like. Nanowires and other
nanostructure products may be incorporated into articles, such as,
for example, electronic displays, touch screens, portable
telephones, cellular telephones, computer displays, laptop
computers, tablet computers, point-of-purchase kiosks, music
players, televisions, electronic games, electronic book readers,
transparent electrodes, solar cells, light emitting diodes, other
electronic devices, medical imaging devices, medical imaging media,
and the like.
EXEMPLARY EMBODIMENTS
[0043] U.S. Provisional Application No. 61/442,874, filed Feb. 15,
2011, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND
ARTICLES, which is hereby incorporated by reference in its
entirety, disclosed the following 26 non-limiting exemplary
embodiments: [0044] A. A method comprising: [0045] providing at
least one first composition comprising at least one first reducible
metal ion; and [0046] reducing the at least one first reducible
metal ion to at least one first metal in the presence of at least
one first protecting agent and at least one first solvent, [0047]
wherein the reduction is performed in at least one first
continuous-flow reactor comprising at least one tubular reactor.
[0048] B. The method according to embodiment A, wherein the at
least one first reducible metal ion comprises at least one coinage
metal ion. [0049] C. The method according to embodiment A, wherein
the at least one first reducible metal ion comprises at least one
ion from IUPAC Group 11. [0050] D. The method according to
embodiment A, wherein the at least one first reducible metal ion
comprises at least one ion of silver. [0051] E. The method
according to embodiment A, wherein the at least one first compound
comprises silver nitrate. [0052] F. The method according to
embodiment A, wherein the reduction is performed in the presence of
at least one element from IUPAC Group 8 or IUPAC Group 14. [0053]
G. The method according to embodiment A, wherein the reduction is
performed in the presence of iron or an ion of iron. [0054] H. The
method according to embodiment A, wherein the wherein the reduction
is performed in the presence of tin or an ion of tin. [0055] J. The
method according to embodiment A, wherein the reduction is
performed in the presence of at least one metal chloride. [0056] K.
The method according to embodiment A, wherein the at least one
first protecting agent comprises at least one of: one or more
surfactants, one or more acids, or one or more polar solvents.
[0057] L. The method according to embodiment A, wherein the at
least one first protecting agent comprises polyvinylpyrrolidinone.
[0058] M. The method of embodiment A, wherein the at least one
first solvent comprises at least one polyol. [0059] N. The method
of embodiment A, wherein the at least one first solvent comprises
at least one of: ethylene glycol, propylene glycol, glycerol, one
or more sugars, or one or more carbohydrates. [0060] P. The method
of embodiment A, wherein the composition has a ratio of the total
moles of the at least one second metal or metal ion to the moles of
the at least one first reducible metal ion from about 0.0001 to
about 0.1. [0061] Q. The method of embodiment A, wherein the
reduction is carried out at one or more temperatures from about
120.degree. C. to about 190.degree. C. [0062] R. The method of
embodiment A, wherein the reduction is carried out in the presence
of at least one second composition comprising seed particles.
[0063] S. The method of embodiment R, wherein the second
composition comprises at least one coinage metal or coinage metal
ion. [0064] T. The method according to embodiment R, wherein the at
least one second composition comprises at least one element from
IUPAC Group 11. [0065] U. The method according to embodiment R,
wherein the at least one second composition comprises silver or an
ion of silver. [0066] V. The method according to embodiment R,
wherein the seed particles are formed by a method comprising:
[0067] providing at least one third metal ion; and [0068]
contacting the at least one third metal ion with at least one
second protecting agent and at least one second solvent. [0069] W.
The method according to embodiment V, wherein the seed particles
are formed in at least one second continuous-flow reactor. [0070]
X. The method according to embodiment W, wherein the at least one
second continuous-flow reactor comprises at least one tubular
reactor. [0071] Y. At least one first metal product formed by the
method of embodiment A. [0072] Z. The product according to
embodiment Y, comprising one or more of nanowires, nanocubes,
nanorods, nanopyramids, or nanotubes. [0073] AA. The product
according to embodiment Y, comprising at least one nanowire. [0074]
AB. At least one article comprising at least one nanowire of
embodiment AA.
EXAMPLES
Example 1
[0075] 40 mL of a solution of 284.0 g polyvinylpyrrolidone (PVP,
55,000 molecular weight) in 3 L ethylene glycol (EG), 40 mL of a
solution of 144.7 g AgNO.sub.3 in 3 L of EG, 560 mL of EG, and 2.6
mL of a 6 mM solution of FeCl.sub.2 in EG were blended and charged
to an addition funnel equipped to drip into a syringe body that fed
the inlet of a peristaltic pump (MASTERFLEX.RTM. 7518-10 pump head
equipped with 0.188 in ID/0.375 in OD flexible tubing and driven by
a 6-to-600 RPM MASTERFLEX.RTM. 7521-40 Console Drive). The outlet
of the pump fed the inlet of a ca. 200 ft long run of 0.25 in OD
stainless-steel tubing (0.049 in wall thickness). Approximately 95%
of the tubing was located in a BLUE M.RTM. oven, with the final 5%
of the tubing being immersed in an ice water bath outside of the
oven. The outlet of the tubing fed a product receiver.
[0076] The oven was heated to 144.5.degree. C., after which the
pump speed control was set to deliver 11.9 mL/min and the addition
funnel drip rate was adjusted to maintain a constant head upstream
of the pump. After 64 min, the pump speed control was increased to
deliver 185 mL/min, with a compensating adjustment in the addition
funnel drip rate. When a brownish grey suspension appeared on the
outlet of the stainless steel tubing, the pump rate was decreased
to deliver 11.9 mL/min, with a compensating adjustment in the
addition funnel drip rate.
[0077] FIG. 3 is a micrograph of the product suspension, showing
silver nanowires and many particles.
Example 2
[0078] 40 mL of a solution of 284.0 g polyvinylpyrrolidone (PVP,
55,000 molecular weight) in 3 L ethylene glycol (EG), 40 mL of a
solution of 144.7 g AgNO.sub.3 in 3 L of EG, 560 mL of EG, and 2.6
mL of a 13.6 mM solution of SnCl.sub.2.2H.sub.2O in EG were blended
and charged to the addition funnel of the apparatus of Experiment
1. The oven was heated to 165.degree. C., after which the pump
speed control was set to deliver 11.9 mL/min and the addition
funnel drip rate was adjusted to maintain a constant head upstream
of the pump. After 95 min, the oven temperature was decreased to
145.degree. C. A grey product suspension was collected from the
outlet of the stainless steel tubing.
[0079] FIG. 4 is a micrograph of the product suspension, showing
many ca. 20 nm long silver nanowires, some shorter silver
nanowires, and a few particles.
Example 3 (Comparative)
[0080] 40 mL of a solution of 284.0 g polyvinylpyrrolidone (PVP,
55,000 molecular weight) in 3 L ethylene glycol (EG), 40 mL of a
solution of 144.7 g AgNO.sub.3 in 3 L of EG, 560 mL of EG, and 8 mg
of SnCl.sub.2.2H.sub.2O in 2.6 mL EG were blended and charged to a
1 L round-bottom flask. This mixture was mechanically agitated at
100 rpm and heated to 165.degree. C. over 59 min. The reaction
mixture was held between 163.degree. C. and 166.degree. C. and
sampled hourly after 1 hr, 2 hr, and 3 hr at temperature. Each of
these 1 g samples were examined microscopically at 500.times.. In
each case, only a few short wires were observed visually and were
not easily photographed.
[0081] In order to photograph these products, 3 drops of each were
diluted with 1 mL of acetone, centrifuged at 500 G for 30 min, the
clear supernatant decanted, and the residue dispersed in
isopropanol by shaking. These dispersions were applied to glass
slides and the liquid evaporated. Photo micrographs were taken of
each of these treated glass slides, as shown in FIGS. 5, 6, and 7,
showing microparticles with low aspect ratios and very few
nanowires.
[0082] It is surprising that a batch reactor supplied with the
identical feed composition of Example 2 did not produce the same
silver nanowire product as that of the continuous-flow reactor of
Example 2.
[0083] The invention has been described in detail with particular
reference to a presently preferred embodiment, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention. The presently disclosed
embodiments are therefore considered in all respects to be
illustrative and not restrictive. The scope of the invention is
indicated by the appended claims, and all changes that come within
the meaning and range of equivalents thereof are intended to be
embraced therein.
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