U.S. patent application number 14/013135 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, William D. Ramsden, David R. Whitcomb.
Application Number | 20130340570 14/013135 |
Document ID | / |
Family ID | 46064537 |
Filed Date | 2013-12-26 |
United States Patent
Application |
20130340570 |
Kind Code |
A1 |
Whitcomb; David R. ; et
al. |
December 26, 2013 |
NANOWIRE PREPARATION, METHODS, COMPOSITIONS, AND ARTICLES
Abstract
Nanowire preparation methods, compositions, and articles are
disclosed. Such nanowires may be thicker than other nanowires and
may be useful in devices requiring high electrical current
densities.
Inventors: |
Whitcomb; David 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: |
46064537 |
Appl. No.: |
14/013135 |
Filed: |
August 29, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13275496 |
Oct 18, 2011 |
|
|
|
14013135 |
|
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Current U.S.
Class: |
75/370 |
Current CPC
Class: |
B22F 1/0025 20130101;
B82Y 30/00 20130101; B22F 9/18 20130101; B22F 2001/0037 20130101;
B22F 9/24 20130101 |
Class at
Publication: |
75/370 |
International
Class: |
B22F 9/18 20060101
B22F009/18 |
Claims
1. A method of producing metal nanowires with reduced nanoparticle
coproduction comprising: providing a composition comprising: a
first molar quantity of at least one first reducible metal ion, a
second molar quantity of at least one second metal or metal ion,
said at least one second metal or metal ion comprising germanium or
an ion of germanium, and a third molar quantity of at least one
third metal or metal ion, said at least one third metal or metal
ion comprising tin or an ion of tin; and reducing the at least one
first reducible metal ion to at least one first metal nanowire,
wherein the ratio of (1) the sum of the second molar quantity and
the third molar quantity to (2) the first molar quantity is from
about 0.0001 to about 0.1.
2. The method according to claim 1, wherein the composition further
comprises at least one compound comprising the at least one first
reducible metal ion.
3. The method according to claim 1, wherein the composition further
comprises at least one solvent comprising at least one polyol.
4. The method according to claim 1, wherein the composition further
comprises at least one of: one or more surfactants, one or more
acids, or one or more polar polymers.
5. The method according to claim 1, wherein the at least one first
reducible metal ion comprises at least one of: at least one coinage
metal ion, at least one ion of an element from IUPAC Group 11, or
at least one ion of silver.
6. The method according to claim 1, wherein the at least one second
metal or metal ion comprises the at least one second metal in its
0, +1, +2, +3, +4, +5, or +6 oxidation state.
7. The method according to claim 1, wherein the at least one third
metal or metal ion comprises the at least one third metal in its 0,
+1, +2, +3, +4, +5, or +6 oxidation state.
8. The method according to claim 1, wherein the ratio of the second
molar quantity to the third molar quantity is from about 0.01 to
about 100.
9. The method according to claim 1, wherein the at least one first
metal nanowire comprises one or more silver nanowires.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 13/275,496, filed Oct. 18, 2011, which claimed benefit of U.S.
Provisional Application No. 61/416,425, filed Nov. 23, 2010,
entitled MIXED METAL OR METAL ION CATALYSIS OF METAL ION REDUCTION,
METHODS, COMPOSITIONS, AND ARTICLES, which is hereby incorporated
by reference in its entirety.
BACKGROUND
[0002] The general preparation of silver nanowires (10-200 aspect
ratio) is known. See, 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 preparations
typically employ Fe.sup.2+ or Cu.sup.2+ ions to "catalyze" the wire
formation over other morphologies. The controlled preparation of
silver nanowires having desired lengths and widths, however, is not
known. For example, the Fe.sup.2+ produces a wide variety of
lengths or thicknesses and the Cu.sup.2+ produces wires that are
too thick for many applications.
[0003] 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.
SUMMARY
[0004] At least some embodiments provide a method comprising:
providing a composition comprising at least one first reducible
metal ion, at least one second metal or metal ion, and at least one
third metal or metal ion, where the at least one second metal or
metal ion differs in atomic number from that of the at least one
first reducible metal ion, and the at least one third metal or
metal ion differs in atomic number from both the at least one first
reducible metal ion and the at least one second metal or metal
ion.
[0005] In at least some embodiments, the composition further
comprises at least one compound comprising the at least one first
reducible metal ion.
[0006] In some cases, the composition further comprises one or more
of:
[0007] at least one solvent, or one or more surfactants, or one or
more acids, or one or more polar polymers. Such solvents, when
used, may, for example, comprise at least one polyol. Such polar
polymers, when used, may, for example, comprise
polyvinylpyrrolidinone.
[0008] In at least some embodiments, the at least one first
reducible metal ion comprises at least one of: at least one coinage
metal ion, at least one ion of an element from IUPAC Group 11, or
at least one ion of silver.
[0009] In some such methods, the at least one second metal or metal
ion comprises the at least one second metal in its 0, +1, +2, +3,
+4, +5, or +6 oxidation state. In some cases, the at least one
third metal or metal ion comprises the at least one third metal in
its 0, +1, +2, +3, +4, +5, or +6 oxidation state.
[0010] In at least some embodiments, the at least one second metal
or metal ion or the at least on third metal or metal ion may
comprise at least one transition metal or ion of a transition
metal. In at least some embodiments, both the at least one second
metal or metal ion and the at least one third metal or metal ion
each comprise at least one transition metal or ion of a transition
metal.
[0011] In some such methods, the at least one second metal or metal
ion comprises at least one transition metal or ion of a transition
metal and the at least one third metal or metal ion comprises at
least one element from IUPAC Group 14 or ion of an element from
IUPAC Group 14.
[0012] In at least some embodiments, the at least one second metal
or metal ion comprises at least one of: iron, an ion of iron,
cobalt, an ion of cobalt, manganese, an ion of manganese, tin, an
ion of tin, germanium, or an ion of germanium.
[0013] Other embodiments provide the at least one first metal
produced by such methods. In at least some embodiments, such an at
least one first metal may comprise one or more nanowires,
nanocubes, nanorods, nanopyramids, or nanotubes.
[0014] Still other embodiments provide articles comprising the at
least one first metal produced by such methods.
[0015] These embodiments and other variations and modifications may
be better understood from the brief description of figures,
description, exemplary embodiments, examples, figures, and claims
that follow. Any embodiments provided are given only by way of
illustrative example. Other desirable objectives and advantages
inherently achieved may occur or become apparent to those skilled
in the art. The invention is defined by the appended claims.
BRIEF DESCRPTION OF FIGURES
[0016] FIG. 1 shows an optical micrograph of the product of
comparative Example 1.
[0017] FIG. 2 shows a scanning electron micrograph of the product
of comparative Example 1.
[0018] FIG. 3 shows an optical micrograph of the product of Example
2.
[0019] FIG. 4 shows a scanning electron micrograph of the product
of Example 2.
[0020] FIG. 5 shows an optical micrograph of the product of
comparative Example 3.
[0021] FIG. 6 shows an optical micrograph of the product of
comparative Example 4.
[0022] FIG. 7 shows an optical micrograph of the product of Example
5.
DESCRIPTION
[0023] 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.
[0024] U.S. application Ser. No. 13/275,496, filed Oct. 18, 2011,
entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND ARTICLES,
is hereby incorporated by reference in its entirety.
[0025] U.S. Provisional Application No. 61/416,425, filed Nov. 23,
2010, entitled MIXED METAL OR METAL ION CATALYSIS OF METAL ION
REDUCTION, METHODS, COMPOSITIONS, AND ARTICLES, is hereby
incorporated by reference in its entirety.
[0026] Applicants have recognized that a mixture of metals or metal
ions, such as, for example, Fe.sup.2+ with Co.sup.2+, or Sn.sup.2+
with Mn.sup.2+, or Sn.sup.2+ with Ge.sup.2+,can be used to control
the aspect ratios of silver nanowires. Nanowires made in the
presence of such a mixture of metals or metal ions may be thicker
than other nanowires and may be useful in devices requiring high
electrical current densities.
[0027] The methods are also believed to be applicable to reducible
metal cations other than silver cations, including, for example,
reducible cations of other IUPAC Group 11 elements, reducible
cations of other coinage metals, and the like. The methods may, in
some embodiments, employ a mixture of more than two metals or metal
ions, such as, for example, a mixture of three, four, or more
metals or metal ions. The metals or metal ions may be in the same
or different oxidation states from each other. For example, one or
more metals or metal ions may be in their 0, +1, +2, +3, +4, +5,
+6, or higher oxidation states, while one or more other metal ions
may be in the same or different oxidation states.
[0028] The methods may also be used to prepare products other than
nanowires, such as, for example, nanocubes, nanorods, nanopyramids,
nanotubes, and the like. Such products may be incorporated into
articles, such as, for example, transparent electrodes, solar
cells, light emitting diodes, other electronic devices, medical
imaging devices, medical imaging media, and the like.
[0029] Reducible Metal Ions and Metal Products
[0030] Some embodiments provide methods comprising reducing at
least one reducible metal ion to at least one metal. 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.
[0031] In such embodiments, the at least one metal is that metal to
which the at least one reducible metal ion is capable of being
reduced. For example, silver would be the metal to which a silver
cation would be capable of being reduced.
[0032] Mixtures of Metals or Metal Ions
[0033] In some embodiments, the reduction of the reducible metal
ion occurs in the presence of at least one second metal or metal
ion and at least one third metal or metal ion, where the at least
one second metal or metal ion differs in atomic number from the at
least one first reducible metal ion, and where the at least one
third metal or metal ion differs in atomic number from both the at
least one first reducible metal ion and the at least one second
metal or metal ion.
[0034] In general, the at least one second metal or metal ion and
the at least one third metal or metal ion may, by themselves or in
combination with other metals or metal ions, be referred to as a
mixture of metals or metal ions. Such a mixture of metals or metal
ions may comprise only metals, or only metal ions, or both metals
and metal ions. Non-limiting examples of such mixtures include
Fe.sup.2+ with Co.sup.2+, or Sn.sup.2+ with Mn.sup.2+, or Sn.sup.2+
with Ge.sup.2+. The mixture may comprise more than two metals or
metal ions, such as, for example, a mixture of three, four, or more
metals or metal ions. The metals or metal ions may be in the same
or different oxidation states from each other. For example, one or
more metals or metal ions may be in their 0, +1, +2, +3, +4, +5,
+6, or higher oxidation states, while one or more other metals or
metal ions may be in the same or different oxidation states.
[0035] In some embodiments, the mixture of metals or metal ions may
comprise no metal ions but only metals that are not ions, such as,
for example, metal carbonyls. In still other cases, the mixture of
metals or metal ions may comprise only metal ions. In yet still
other cases, the mixture of metals or metal ions may comprise both
metals and metal ions. For example, the one or more metals or metal
ions may all be in their +1, +2, +3, +4, +5, +6 or higher oxidation
states, or the one or more metals or metal ions may all be metals
in their 0 oxidation state, or the one or more metal or metal ions
may comprise one or more metal ions in their +1, +2, +3, +4, +5, +6
or higher oxidation states and one or more metals in their 0
oxidation state.
[0036] Nanowires made in the presence of such a mixture of metals
or metal ions may be thicker than other nanowires and may be useful
in devices requiring high electrical current densities.
[0037] Preparation Methods
[0038] 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 120.degree. C. to about 190.degree. C., or
from about 80.degree. C. to about 190.degree. C.
[0039] 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 61/416,425, filed Nov. 23,
2010, entitled MIXED METAL OR METAL ION CATALYSIS OF METAL ION
REDUCTION, METHODS, COMPOSITIONS, AND ARTICLES, which is hereby
incorporated by reference in its entirety, disclosed the following
39 non-limiting exemplary embodiments:
[0044] A. A method comprising: [0045] providing a composition
comprising: [0046] at least one compound comprising at least one
first reducible metal ion, [0047] at least one second metal or
metal ion, said at least one second metal or metal ion differing in
atomic number from said at least one first reducible metal ion,
[0048] at least one third metal or metal ion, said at least one
third metal or metal ion differing in atomic number from said at
least one first reducible metal ion and from said at least one
second metal or metal ion, [0049] and at least one solvent; and
[0050] reducing the at least one first reducible metal ion to at
least one first metal.
[0051] B. The method of embodiment A, wherein the composition
further comprises at least one protecting agent.
[0052] C. The method of embodiment B, wherein the at least one
protecting agent comprises at least one of: one or more
surfactants, one or more acids, or one or more polar polymers.
[0053] D. The method of embodiment B, wherein the at least one
protecting agent comprises polyvinylpyrrolidinone.
[0054] E. The method of embodiment B, further comprising inerting
the at least one protecting agent.
[0055] F. The method of embodiment A, wherein the composition
further comprises at least one fourth metal or metal ion, said at
least one fourth metal differing in atomic number from said at
least one first reducible metal ion, from said at least one second
metal or metal ion, and from at least one third metal or metal
ion.
[0056] G. The method of embodiment A, wherein the at least one
first reducible metal ion comprises at least one coinage metal
ion.
[0057] H. The method of embodiment A, wherein the at least one
first reducible metal ion comprises at least one ion of an element
from IUPAC Group 11.
[0058] J. The method of embodiment A, wherein the at least one
first reducible metal ion comprises at least one ion of silver.
[0059] K. The method of embodiment A, wherein the at least one
compound comprises silver nitrate.
[0060] L. The method of embodiment A, wherein the at least one
second metal or metal ion comprises the at least one second metal
in its 0, +1, +2, +3, +4, +5, or +6 valence state.
[0061] M. The method of embodiment L, wherein the at least one
third metal or metal ion comprises the at least one third metal in
its 0, +1, +2, +3, +4, +5, or +6 valence state.
[0062] N. The method of embodiment A, wherein the at least one
compound comprises at least one salt of said at least one second
metal or metal ion or of said at least one third metal or metal
ion.
[0063] P. The method of embodiment N, wherein the at least one salt
comprises at least one chloride.
[0064] Q. The method of embodiment A, wherein the at least one
second metal or metal ion comprises at least one transition metal
or ion of a transition metal.
[0065] R. The method of embodiment Q, wherein the at least one
third metal or metal ion comprises at least one transition metal or
ion of a transition metal.
[0066] S. The method if embodiment Q, wherein the at least one
third metal comprises at least one element or ion of an element
from IUPAC Group 14.
[0067] T. The method of embodiment A, wherein the at least one
second metal or metal ion or the at least one third metal or metal
ion comprises iron or an ion of iron.
[0068] U. The method of embodiment A, wherein the at least one
second metal or metal ion or the at least one third metal or metal
ion comprises cobalt or an ion of cobalt.
[0069] V. The method of embodiment A, wherein the at least one
second metal or metal ion comprises iron or an ion of iron and the
at least one third metal or metal ion comprises cobalt or an ion of
cobalt.
[0070] W. The method of embodiment A, wherein the at least one
second metal or metal ion or the at least one third metal or metal
ion comprises manganese or an ion of manganese.
[0071] X. The method of embodiment A, wherein the at least one
second metal or metal ion or the at least one third metal or metal
ion comprises tin or an ion of tin.
[0072] Y. The method of embodiment A, wherein the at least one
second metal or metal ion comprises manganese or an ion of
manganese and the at least one third metal or metal ion comprises
tin or an ion of tin.
[0073] Z. The method of embodiment A, wherein the at least one
solvent comprises at least one polyol.
[0074] AA. The method of embodiment A, wherein the at least one
solvent comprises at least one of: ethylene glycol, propylene
glycol, glycerol, one or more sugars, or one or more
carbohydrates.
[0075] AB. 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 and the at least one third metal or metal ion to the
moles of the at least one first reducible metal ion from about
0.0001 to about 0.1.
[0076] AC. The method of embodiment A, wherein the composition has
a molar ratio of the at least one second metal or metal ion to the
at least one third metal or metal ion from about 0.01 to about
100.
[0077] AD. 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.
[0078] AE. The method of embodiment A, further comprising inerting
one or more of: the composition, the at least one compound
comprising at least one first reducible metal ion, the at least one
second metal or metal ion, the at least one third metal or metal
ion, or the at least one solvent.
[0079] AF. The at least one first metal produced according to the
method of embodiment A.
[0080] AG. At least one article comprising the at least one first
metal produced according to the method of embodiment A.
[0081] AH. The at least one article of embodiment AG, wherein the
at least one first metal comprises one or more nanowires,
nanocubes, nanorods, nanopyramids, or nanotubes.
[0082] AJ. The at least one article of embodiment AG, wherein the
at least one first metal comprises at least one object having an
average diameter of between about 10 nm and about 500 nm.
[0083] AK. The at least one article of embodiment AG, wherein the
at least one first metal comprises at least one object having an
aspect ratio from about 50 to about 10,000.
[0084] AL. At least one metal nanowire with an average diameter of
between about 10 nm and about 150 nm, and with an aspect ratio from
about 50 to about 10,000.
[0085] AM. The nanowire of embodiment AL, wherein the at least one
metal comprises at least one coinage metal.
[0086] AN. The nanowire of embodiment AL, wherein the at least one
metal comprises at least one element of IUPAC Group 11.
[0087] AP. The nanowire of embodiment AL, wherein the at least one
metal comprises silver.
[0088] AQ. At least one article comprising the at least one metal
nanowire of embodiment AL.
EXAMPLES
Example 1 (Comparative)
[0089] To a 500 mL reaction flask containing 200 mL ethylene glycol
(EG), 1.2 mL of 7.0 mM FeCl.sub.2 in EG was added and degassed with
argon using a glass pipette. Stock solutions of 0.77 M
polyvinylpyrrolidinone (PVP, 55,000 molecular weight) in EG and
0.25 M AgNO.sub.3 in EG were also degassed with argon. 60 mL
syringes of the PVP and AgNO.sub.3 solutions were then prepared.
The reaction mixture was heated to 145.degree. C. under N.sub.2
and, after the reaction mixture was held 10 minutes at the set
point temperature, the AgNO.sub.3 and PVP solutions were added at a
constant rate over 25 minutes via a 20 gauge TEFLON.RTM.
fluoropolymer syringe needle. The reaction mixture was held at
145.degree. C. for 90 minutes, after which samples were taken for
optical microscopy. The reaction mixture was then quenched in an
ice bath, after which samples were taken for scanning electron
microscopy.
[0090] FIG. 1 shows an optical micrograph of the reaction product,
while FIG. 2 shows a scanning electron micrograph of the reaction
product. Based on the measurements of at least 100 wires, the
product had an average diameter of 123.+-.34 nm.
Example 2
[0091] To a 500 mL reaction flask containing 280 mL EG, 1.1 mL of
7.7 mM FeCl.sub.2 in EG and 1.0 mL of 7.3 mM CoCl.sub.2 in EG was
added. The reaction mixture was stirred and degassed with nitrogen
using a glass pipette for 2 hrs. Stock solutions of 0.77 M PVP in
EG and 0.25 M AgNO.sub.3 in EG were also degassed with nitrogen for
60 min. 20 mL syringes of the PVP and AgNO.sub.3 solutions were
then prepared. The reaction mixture was heated to 145.degree. C.
under N.sub.2 and, after the reaction mixture was held 10 minutes
at the set point temperature, the AgNO.sub.3 and PVP solutions were
added at a constant rate over 25 minutes via a 12 gauge TEFLON.RTM.
fluoropolymer syringe needle. The reaction mixture was held at
145.degree. C. for 90 minutes, after which samples were taken for
optical microscopy. The reaction mixture was then allowed to cool
to ambient temperature. 15 mL of the cooled reaction mixture was
diluted with 35 mL of isopropanol (IPA), centrifuged for 15 minutes
at 1500 rpm, decanted, then re-dispersed in 5 mL IPA. The resulting
mixture was sampled for scanning electron microscopy.
[0092] FIG. 3 shows an optical micrograph of the reaction product,
while FIG. 4 shows a scanning electron micrograph of the reaction
product. Based on the measurements of at least 100 wires, the
product had an average diameter of 160 .+-.58 nm. These wires were
thicker than those of Example 1.
Example 3 (Comparative)
[0093] To a 500 mL reaction flask containing 280 mL EG, 2.0 g of 17
mM of freshly prepared 15 mM GeCl.sub.2dioxane in EG was added. The
reaction mixture was stirred and degassed with nitrogen using a
TEFLON.RTM. fluoropolymer tube for 2 hrs. Stock solutions of 0.84 M
PVP in EG and 0.25 M AgNO.sub.3 in EG were also degassed with
nitrogen for 60 min. 20 mL syringes of the PVP and AgNO.sub.3
solutions were then prepared. The reaction mixture was heated to
145.degree. C. under 0.5 L/min N.sub.2, then the AgNO.sub.3 and PVP
solutions were added at a constant rate over 25 minutes via a 12
gauge TEFLON.RTM. fluoropolymer syringe needle. The reaction
mixture was held at 145.degree. C. for 90 minutes, after the
reaction mixture was allowed to cool to ambient temperature. 15 mL
of the cooled reaction mixture was diluted with 35 mL of IPA,
centrifuged for 15 minutes at 1500 rpm, decanted, then re-dispersed
in 5 mL IPA.
[0094] FIG. 5 shows an optical micrograph of the reaction product,
which had copious non-nanowire nanoparticles.
Example 4 (Comparative)
[0095] To a 500 mL reaction flask containing 280 mL EG, 4.4 g of
6.9 mM SnCl.sub.2 in EG was added. The reaction mixture was stirred
and degas sed with nitrogen using a TEFLON.RTM. fluoropolymer tube
for 2 hrs. Stock solutions of 0.84 M PVP in EG and 0.25 M
AgNO.sub.3 in EG were also degassed with nitrogen for 60 min. 20 mL
syringes of the PVP and AgNO.sub.3 solutions were then prepared.
The reaction mixture was heated to 145.degree. C. under 0.5 L/min
N.sub.2, then the AgNO.sub.3 and PVP solutions were added at a
constant rate over 25 minutes via a 12 gauge TEFLON.RTM.
fluoropolymer syringe needle. The reaction mixture was held at
145.degree. C. for 90 minutes, after the reaction mixture was
allowed to cool to ambient temperature. 15 mL of the cooled
reaction mixture was diluted with 35 mL of IPA centrifuged for 15
minutes at 1500 rpm, decanted, then re-dispersed in 5 mL IPA.
[0096] FIG. 6 shows an optical micrograph of the reaction product,
which had copious non-nanowire nanoparticles.
Example 5
[0097] To a 500 mL reaction flask containing 280 mL EG, 2.1 g of
9.3 mM SnCl.sub.2 in EG and 1.4 g of freshly prepared 15 mM
GeCl.sub.2dioxane in EG was added. The reaction mixture was stirred
and degassed with nitrogen using a TEFLON.RTM. fluoropolymer tube
for 2 hrs. Stock solutions of 0.84 M PVP in EG and 0.25 M
AgNO.sub.3 in EG were also degassed with nitrogen for 60 min. 20 mL
syringes of the PVP and AgNO.sub.3 solutions were then prepared.
The reaction mixture was heated to 145.degree. C. under 0.5 L/min
N.sub.2, then the AgNO.sub.3 and PVP solutions were added at a
constant rate over 25 minutes via a 12 gauge TEFLON.RTM.
fluoropolymer syringe needle. The reaction mixture was held at
145.degree. C. for 90 minutes, after the reaction mixture was
allowed to cool to ambient temperature. 15 mL of the cooled
reaction mixture was diluted with 35 mL of IPA centrifuged for 15
minutes at 1500 rpm, decanted, then re-dispersed in 5 mL IPA.
[0098] FIG. 7 shows an optical micrograph of the reaction product,
which had fewer non-nanowire nanoparticles than either of the
reaction products of comparative Examples 3 or 4. By comparing FIG.
7 to FIGS. 5 and 6, it is apparent that the Sn.sup.2+/Ge.sup.2+
mixed metal ion catalyst was more selective toward nanowire
production than either of the equivalent molarity Sn.sup.2+ or
Ge.sup.2+ non-mixed metal ion catalysts.
[0099] The invention has been described in detail with reference to
particular embodiments, 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.
* * * * *