US20140178247A1 - Process for making silver nanostructures and copolymer useful in such process - Google Patents
Process for making silver nanostructures and copolymer useful in such process Download PDFInfo
- Publication number
- US20140178247A1 US20140178247A1 US14/040,406 US201314040406A US2014178247A1 US 20140178247 A1 US20140178247 A1 US 20140178247A1 US 201314040406 A US201314040406 A US 201314040406A US 2014178247 A1 US2014178247 A1 US 2014178247A1
- Authority
- US
- United States
- Prior art keywords
- copolymer
- silver
- meth
- constitutional repeating
- repeating units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- ANIGWHXSCLKNMZ-VXYBFGIDSA-L C.C.C.CC(C)(C#N)/N=N/C(C)(C)C#N.CC(C)C#N.CCC(=O)OC.CCC(=O)OC.CCOC(=S)SC.CCOC(=S)SC.CCOC(=S)SC(C)C(=O)OC.CCOC(=S)S[Pm].CCOC(SC)SC(C)C(=O)OC.CCOC(SC)S[Pm].COC(=O)C(C)C.N#N Chemical compound C.C.C.CC(C)(C#N)/N=N/C(C)(C)C#N.CC(C)C#N.CCC(=O)OC.CCC(=O)OC.CCOC(=S)SC.CCOC(=S)SC.CCOC(=S)SC(C)C(=O)OC.CCOC(=S)S[Pm].CCOC(SC)SC(C)C(=O)OC.CCOC(SC)S[Pm].COC(=O)C(C)C.N#N ANIGWHXSCLKNMZ-VXYBFGIDSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/762—Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
- Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
Definitions
- the present invention relates to a process for making silver nanostructures and a copolymer useful in such process.
- Transparent conductors such as Indium Tin Oxide (ITO) combine the electrical conductivity of metal with the optical transparency of glass and are useful as components in electronic devices, such as in display devices. Flexibility is likely to become a broader challenge for ITO, which does not seem well suited to the next generation of display, lighting, or photovoltaic devices. These concerns have motivated a search for replacements using conventional materials and nanomaterials. There is variety of technical approaches for developing ITO substitutes and there are four areas in which the alternative compete: price, electrical conductivity, optical transparency, and physical resiliency.
- ITO Indium Tin Oxide
- Electrically conductive polymers such as polythiophene polymers, particularly a polymer blend of poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (“PEDOT-PSS”) have been investigated as possible alternatives to ITO.
- the electrical conductivity of electrically conductive polymers is typically lower than that of ITO, but can be enhanced through the use of conductive fillers and dopants.
- the present invention is directed to a process for making silver nanostructures, comprising reacting at least one polyol and at least one silver compound that is capable of producing silver metal when reduced, in the presence of:
- the present invention is directed to a copolymer, comprising, based on 1000 constitutional repeating units of the copolymer:
- first constitutional repeating units each independently comprising at least one pendant saturated or unsaturated, five-, six-, or seven-membered, acylamino- or diacylamino-containing heterocylic ring moiety per constitutional repeating unit, and
- the present invention is directed to a process for making silver nanostructures, comprising reacting at least one polyol and at least one silver compound that is capable of producing silver metal when reduced, in the presence of:
- FIGS. 1( a ) and 1 ( b ) show representative 1H NMR and FTIR spectra of the poly(vinylpyrrolidone-co-diallyldimethylammonium nitrate) random copolymers (“poly(VP-co-DADMAN)” copolymers) of Examples 1A-1E.
- FIG. 2 shows characteristics of the silver nanostructures of Examples 2A-2G and Comparative Examples C1-C3, as a function of the amount of silver nitrate added and the composition of the polymeric protectant, wherein each cross corresponds to one of the Examples.
- FIG. 3 shows length distributions of the nanowire products obtained using poly(VP-co-DADMAN) copolymer with 16 percent by weight (“wt %”) DADMAN content at different concentrations of silver nitrate.
- FIG. 4 shows arithmetic average length distribution of nanowire products obtained using poly(VP-co-DADMAN) copolymer with 1 wt % DADMAN content at different concentrations of the copolymer at two different amounts of silver nitrate.
- FIG. 5 shows the titration curve of the “Lot A” ethylene glycol used in Examples 2, 3, 4, and comparative examples C2A-C2C.
- FIG. 6 shows a TEM image of the silver nanowires of Example 2A.
- FIG. 7 shows the titration curve of the “Lot B” ethylene glycol used in Examples 7, 8, and 9.
- FIG. 8 shows an SEM image of the silver nanowires of Example 7 produced with the addition of lithium hydroxide.
- FIG. 9 shows an image of the silver nanowires of Example 7 produced with the addition of lithium hydroxide as seen with an optical microscope.
- FIG. 10 shows an image of the silver nanowires of Example 8 produced with the addition of potassium hydroxide as seen with an optical microscope.
- FIG. 11 shows an image of the silver nanowires of Example 9 produced with the addition of sodium hydroxide as seen with an optical microscope.
- doped as used herein in reference to an electrically conductive polymer means that the electrically conductive polymer has been combined with a polymeric counterion for the electrically conductive polymer, which polymeric counterion is referred to herein as “dopant”, and is typically a polymeric acid, which is referred to herein as a “polymeric acid dopant”,
- doped electrically conductive polymer means a polymer blend comprising an electrically conductive polymer and a polymeric counterion for the electrically conductive polymer
- electrically conductive polymer means any polymer or polymer blend that is inherently or intrinsically, without the addition of electrically conductive fillers such as carbon black or conductive metal particles, capable of electrical conductivity, more typically to any polymer or oligomer that exhibits a bulk specific conductance of greater than or equal to 10 ⁇ 7 Siemens per centimeter (“S/cm”), unless otherwise indicated, a reference herein to an “electrically conductive polymer” include any optional polymeric acid dopant,
- electrically conductive includes conductive and semi-conductive
- “electronic device” means a device that comprises one or more layers comprising one or more semiconductor materials and makes use of the controlled motion of electrons through the one or more layers,
- “layer” as used herein in reference to an electronic device means a coating covering a desired area of the device, wherein the area is not limited by size, that is, the area covered by the layer can, for example, be as large as an entire device, be as large as a specific functional area of the device, such as the actual visual display, or be as small as a single sub-pixel.
- alkyl means a monovalent straight, branched or cyclic saturated hydrocarbon radical, more typically, a monovalent straight or branched saturated (C 1 -C 40 )hydrocarbon radical, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, tricontyl, and tetracontyl,
- cycloalkyl means a saturated hydrocarbon radical, more typically a saturated (C 5 -C 22 ) hydrocarbon radical, that includes one or more cyclic alkyl rings, which may optionally be substituted on one or more carbon atoms of the ring with one or two (C 1 -C 6 )alkyl groups per carbon atom, such as, for example, cyclopentyl, cycloheptyl, cyclooctyl,
- heteroalkyl means an alkyl group wherein one or more of the carbon atoms within the alkyl group has been replaced by a hetero atom, such as nitrogen, oxygen, or sulfur,
- heterocyclic means an cyclic hydrocarbon group in which one or more of the ring carbon atoms has been replaced by a hetero atom, such as nitrogen, oxygen, or sulfur,
- alkylene refers to a divalent alkyl group including, for example, methylene, and poly(methylene),
- alkenyl means an unsaturated straight or branched hydrocarbon radical, more typically an unsaturated straight, branched, (C 2 -C 22 ) hydrocarbon radical, that contains one or more carbon-carbon double bonds, including, for example, ethenyl, n-propenyl, and iso-propenyl,
- aryl means an unsaturated hydrocarbon radical that contains one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated carbon-carbon double bonds, wherein one or more of the ring carbons may be substituted with one or more hydroxy, alkyl, alkenyl, alkoxy, halo, or alkylhalo substituents, such as, for example, phenyl, methylphenyl, trimethylphenyl, nonylphenyl, chlorophenyl, trichloromethylphenyl, naphthyl, and anthryl, and
- aralkyl means an alkyl group substituted with one or more aryl groups, more typically a (C 1 -C 18 )alkyl substituted with one or more (C 6 -C 14 )aryl substituents, such as, for example, phenylmethyl, phenylethyl, and triphenylmethyl, and
- (C x -C y ) in reference to an organic group, wherein x and y are each integers, means that the group may contain from x carbon atoms to y carbon atoms per group.
- cationic means that the moiety carries a net positive electrical charge
- anionic means that the moiety carries a net negative electrical charge
- amphoteric and zwitterionic mean that the moiety has no net electrical charge, but carries, or under certain pH conditions, may carry both a localized negative electrical charge and a localized positive electrical charge, and
- nonionic means that the moiety is carries no net electrical charge no localized negative electrical charge and no localized positive electrical charge.
- constitutional repeating unit means the smallest constitutional unit, the repetition of which constitutes a chain or a block of the polymer or copolymer molecule
- constitutional unit means an atom or group of atoms, including pendant atoms or groups, if any, comprising a part of the essential structure of the polymer or copolymer molecule or of a block or chain of the polymer or copolymer molecule,
- chain means the whole or a portion of the polymer or copolymer molecule, comprising a linear or branched sequence of one or more constitutional units between two boundary constitutional units, each of which may be either an end-group, a branch point or an otherwise-designated characteristic feature of the polymer or copolymer molecule, and
- block means, in reference to a copolymer, a portion of the copolymer, comprising two or more constitutional units that has at least one feature which is not present in the adjacent portions of the copolymer.
- the dimensions referred to herein in regard to bulk nanostructure materials are averaged dimensions obtained by sampling individual nanostructures contained in the bulk material wherein the lengths are obtained using optical microscopy, and the diameters are determined using electron microscopy. Using this process, a sample of about 150 nanostructures are measured to determine the lengths, and a sample of about 10 nanostructures are measured to determine the diameters. An average diameter, average length, and average aspect ratio are then determined for the nanostructures examined as follows. Unless otherwise indicated, nanostructure dimensions are given as arithmetic averages of the measured nanowire population.
- lengths may also be given as length weighted average lengths, as determined by first taking the length of each nanowire and dividing it by the sum of the lengths of all nanowires measured to derive a quantity W 1 , which is the percent contribution of the single nanowire to the sum length of all nanowires, then, for each of the measured nanowires, deriving a weighted length by multiplying the length of the nanowire by its respective W 1 value, and finally taking the arithmetic average of the weighted lengths of the measured nanowires to derive the length weighted average length of the nanowire population.
- Aspect ratios of anisotropic nanostructures are determined by dividing the length weighted average length of the nanowire population by the average diameter of the anisotropic nanostructure population.
- nanostructures generally refers to nano-sized structures, at least one dimension of which is less than or equal to 2000 nm, more typically less than or equal to 500 nm, even more typically, less than or equal to 250 nm, or less than or equal to 100 nm, or less than or equal to 50 nm, or less than or equal to 25 nm.
- the anisotropic electrically conductive nanostructures can be of any anisotropic shape or geometry.
- the terminology “aspect ratio” in reference to a structure means the ratio of the structure's longest characteristic dimension to the structure's next longest characteristic dimension.
- the anisotropic electrically conductive nanostructures have an elongated shape with a longest characteristic dimension, i.e., a length, and a next longest characteristic dimension, i.e., a width or diameter, with an aspect ratio of greater than 1.
- the at least one polyol serves as liquid medium in which to conduct the reaction and as a reducing agent that reduces the silver compound to silver metal.
- Suitable polyols are organic compounds having a core moiety comprising at least 2 carbon atoms, which may optionally further comprise one or more heteroatoms selected from N and O, wherein the core moiety is substituted with at least 2 hydroxyl groups per molecule and each hydroxyl group is attached to a different carbon atom of the core moiety.
- Suitable polyols are known and include, for example, alkylene glycols, such as ethylene glycol, propylene glycols, and butanediols, alkylene oxide oligomers, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and polyalkylene glycols, such as polyethylene glycol and polypropylene glycol, provided that such polyalkylene glycol is liquid at the reaction temperature, triols, such as, for example, glycerol, trimethylolpropane, triethanolamine, and trihydroxymethylaminomethane, and compounds having more than 3 hydroxyl groups per molecule, as well as mixtures of two or more of any of such compounds.
- the polyol comprises ethylene glycol.
- Suitable silver compounds that are capable of producing silver metal when reduced include silver oxide, silver hydroxide, organic silver salts, and inorganic silver salts, such as silver nitrate, silver nitrite, silver sulfate, silver halides such as silver chloride, silver carbonates, silver phosphate, silver tetrafluoroborate, silver sulfonate, silver carboxylates, such as, for example, silver formate, silver acetate, silver propionate, silver butanoate, silver trifluoroacetate, silver acetacetonate, silver lactate, silver citrate, silver glycolate, silver tosylate, silver tris(dimethylpyrazole)borate, as well as mixtures of two or more of such compounds.
- the silver compound capable of producing silver metal when reduced comprises silver nitrate (AgNO 3 ).
- Suitable sources of chloride and/or bromide ions include hydrochloric acid, chloride salts, such as ammonium chloride, calcium chloride, ferric chloride, lithium chloride, potassium chloride, sodium chloride, triethylbenzyl ammonium chloride, tetrabutyl ammonium chloride, hydrobromic acid, and bromide salts, such as ammonium bromide, calcium bromide, ferric bromide, lithium bromide, potassium bromide, sodium bromide, triethylbenzyl ammonium bromide, tetrabutyl ammonium bromide, or, in a case wherein the copolymer comprises a chloride or bromide counterion, the chloride or bromide counterion of the copolymer.
- the source of chloride ions comprises lithium chloride.
- the source of chloride or bromide ions comprises silver chloride and/or silver bromide, which may be added to the reaction mixture in the form of colloidal particles.
- the colloidal particles of silver chloride and/or silver bromide may have a particle size of from about 10 nm to about 10 ⁇ m, more typically of from about 50 nm to about 10 ⁇ m.
- the pH of the at least one polyol may be any pH at room temperature (25° C.).
- the pH of the at least one polyol may be determined by conventional analytical methods known in the art, including, for example, colorimetric titration, potentiometric titration, direct measurement using a pH meter, and the like.
- the pH of the at least one polyol is from about 1 to about 14. More typically, the pH of the at least one polyol is from about 5 to about 12. Even more typically, the pH of the at least one polyol is from about 7 to about 10.
- the at least one base is any compound that increases the pH of the reaction mixture in which the at least one base is dissolved, dispersed, or suspended.
- Suitable bases include alkali metal hydroxides, such as, for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof.
- the at least one base comprises sodium hydroxide, lithium hydroxide, potassium hydroxide, or mixtures thereof.
- the amount of the at least one base is typically from about 5.39 ⁇ 10 ⁇ 5 to about 3.47 ⁇ 10 ⁇ 4 pbw of the at least one base per 1 pbw of the total amount of the at least one polyol used in the reaction. More typically, the amount of the at least one base is typically from about 5.39 ⁇ 10 ⁇ 5 to about 1.30 ⁇ 10 ⁇ 4 pbw of the at least one base per 1 pbw of the total amount of the at least one polyol used in the reaction.
- the total amount of silver compound added to the reaction mixture over the entire course of the reaction, based on one liter of reaction mixture, is typically from about 1.5 ⁇ 10 ⁇ 3 mole to about 1 mole of the silver compound (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to about 0.026 wt % to about 17 wt % AgNO 3 in ethylene glycol), more typically from greater than or equal to 3 ⁇ 10 ⁇ 2 mole to about 1 mole of the silver compound (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to about 0.51 wt % to about 17 wt % AgNO 3 in ethylene glycol).
- the silver compound may be introduced to the reaction mixture as a solid powder, the total amount of which may be introduced at one time or which may introduced in a series of portion of the total amount.
- the silver compound may be fed to the reaction mixture as a dilute solution of the silver compound in the polyol comprising from about 10 g to about 100 g of the silver compound per 1000 g polyol at a rate that is sufficiently slow as to avoid reducing the temperature of the reaction mixture.
- the total amount of silver compound added to the reaction mixture is, based on one Liter of reaction mixture, typically from about 0.02 moles to about 0.22 moles (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to from about 0.3 wt % to about 3.75 wt % AgNO 3 in ethylene glycol), more typically from about 0.06 moles to about 0.18 moles (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to from about 1 wt % to 3 wt % AgNO 3 in ethylene glycol), even more typically from about 0.07 moles to about 0.18 moles (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to from about 1.25 wt % to about 3 wt % AgNO 3 in ethylene glycol).
- the total amount of silver compound added to the reaction mixture is, based on one Liter of reaction mixture, from greater than 0.1 moles to about 0.22 moles (corresponding, in the case of AgNO 3 as the silver compound and ethylene glycol as the polyol, to from about 1.7 wt % to about 3.75 wt % AgNO 3 in ethylene glycol).
- the nanostructures are made in the presence of from about 5.4 ⁇ 10 ⁇ 5 moles to about 5.4 ⁇ 10 ⁇ 3 moles of particles of silver chloride and/or particles of silver bromide per Liter of reaction mixture. While not wishing to be bound by theory, it is believed that the particles of silver chloride and/or particles of silver bromide catalyze growth of the silver nanostructures, but do not participate as a reactive “seeds” that become incorporated within the silver nanostructures.
- the at least one polyol and at least one silver compound are reacted at a temperature of from about 100° C. to about 210° C., more typically from about 130 to about 185° C.
- At least a portion of the polyol is preheated to a temperature of from about 100° C. to about 210° C., more typically from about 130° C. to about 185° C., typically for a period of greater than about 1 minute, more typically for a period of greater than about 5 minutes prior to introduction of the source of chloride or bromide ions, and/or the silver compound.
- particles of silver chloride or silver bromide are formed in the polyol in a preliminary step, wherein a silver compound and polyol are reacted in the presence of a source of chloride or bromide ions, typically in with the silver compound in an excess of from greater than 1, more typically from about 1.01 to about 1.2 moles, of silver compound per mole chloride or bromide ions.
- from about 5.4 ⁇ 10 ⁇ 5 to about 5.4 ⁇ 10 ⁇ 4 moles silver compound per liter of reaction mixture are reacted in the presence of from about 5.4 ⁇ 10 ⁇ 5 to about 5.4 ⁇ 10 ⁇ 4 moles of the source of chloride and/or bromide ions per liter of reaction mixture to form silver chloride and/or silver bromide seed particles in the reaction mixture.
- particles of silver chloride or silver bromide are formed at a temperature of from about 100° C. to about 210° C., more typically from about 130° C. to about 185° C.
- the formation of the silver chloride or silver bromide particles is typically conducted over a time period of greater than or equal to about 1 minute, more typically of from about 1 minute to about 10 minutes.
- from about 1.5 ⁇ 10 ⁇ 3 to about 1 mole of the silver compound per Liter of reaction mixture are added in a second reaction step.
- the growth step is conducted at a temperature of about 100° C. to about 210° C., more typically from about 130° C. to about 185° C.
- the second reaction step of the reaction is typically conducted over a time period of greater than or equal to about 5 minutes, more typically from about 5 minutes to about 4 hours, and even more typically from about 10 minutes to 1 about hour.
- particles of silver chloride or silver bromide are formed in the polyol simultaneously with the formation of the silver nanostructures in a single step, wherein a silver compound and polyol are reacted in the presence of a source of chloride or bromide ions, typically in with the silver compound in very large molar excess.
- the single step formation reaction is conducted at a temperature of from about 100° C. to about 210° C., more typically from about 130° C. to about 185° C.
- the single step formation reaction is typically conducted over a time period of greater than or equal to about 5 minutes, more typically from about 5 minutes to about 4 hours, and even more typically from about 10 minutes to about 1 hour.
- the reaction may be conducted under an air atmosphere or under an inert atmosphere, such as a nitrogen or argon atmosphere. In one embodiment, the reaction is conducted under a nitrogen atmosphere.
- the copolymer is believed to function as an organic protective agent.
- the amount of copolymer is typically from about 0.1 to about 20 parts by weight (“pbw”), more typically from about 1 to about 5 pbw, of the copolymer per 1 pbw of silver compound, based on the total amount of the silver compound added to the reaction mixture.
- the reaction is conducted in the presence of, based on the weight of the reaction mixture, from about 0.01 wt % to about 50 wt %, more typically from about 0.1 wt % to about 20 wt %, and even more typically from about 0.5 wt % to 8 wt %, of the copolymer.
- the at least one silver compound comprises silver nitrate
- the at least one polyol comprises ethylene glycol
- the total amount of silver nitrate added to the reaction mixture is from 1.5 ⁇ 10 ⁇ 3 mole to about 1 mole silver nitrate per Liter of reaction mixture
- the reaction is conducted in the presence of, based on the weight of the reaction mixture, from about 0.01 wt % to about 50 wt %, more typically from about 0.1 wt % to about 20 wt %, and even more typically from about 0.5 wt % to 8 wt %, of the copolymer.
- Saturated or unsaturated five-, six-, or seven-membered acylamino- or diacylamino-containing heterocylic ring moieties suitable as the at least one pendant group of the first constitutional repeating unit of the copolymer include, for example, pyrrolidonyl, pyrrolidinedionyl, azacyclohexanoyl, azacyclohexadionyl, azacycloheptanonyl, and azacycloheptadionyl.
- the first constitutional repeating units of the copolymer each independently comprise a pyrrolidonyl moiety or a pyrrolidinedionyl moiety. In one embodiment, each of the first constitutive units of the copolymer comprises a pyrrolidonyl moiety.
- the first constitutional repeating units each independently comprise a pendant group according to structure (I):
- the first constitutional repeating units may be made by known synthetic techniques, such as, for example, by grafting of one or more five-, six-, or seven-membered saturated or unsaturated acylamino- or diacylamino-containing heterocylic ring moieties onto a polymer backbone, such as a hydrocarbon polymer backbone, a polyester polymer backbone, or a polysaccharide polymer backbone, or by copolymerization of a nonionic monomer, as described below, with, for example, an ionic monomer, as described below.
- a polymer backbone such as a hydrocarbon polymer backbone, a polyester polymer backbone, or a polysaccharide polymer backbone
- a nonionic monomer as described below
- an ionic monomer as described below.
- the first constitutional repeating units of the copolymer of the present invention are derived from a first monomer comprising at least one reactive functional group and at least one five-, six-, or seven-membered saturated or unsaturated acylamino- or diacylamino-containing heterocylic ring moiety per molecule of the monomer.
- Suitable reactive functional groups include, for example, hydroxyl groups, isocyanate groups, epoxide groups, amino groups, carboxylate groups, and ⁇ , ⁇ -unsaturated groups, such as —CH 2 ⁇ CH 2 , or —H(CH 3 )C ⁇ CH 2 .
- the first monomer comprises one or more compounds according to structure (II):
- the first constitutional repeating units of the copolymer of the present invention are derived from a first monomer selected from vinyl pyrrolidone. vinyl caprolactam, and mixtures thereof. More typically, each of the first constitutional repeating units of the copolymer of the present invention is derived from vinylpyrrolidone.
- Constitutional repeating units suitable as the second constitutional repeating units of the copolymer of the present invention may be any constitutional repeating units that differ in composition from the first constitutional repeating units.
- the second constitutional repeating units each comprise at least one pendant moiety per second constitutional repeating unit that: (i) is selected from ionic organic moieties and nonionic organic moieties, and (ii) is not a saturated or unsaturated, five-, six-, or seven-membered, acylamino- or diacylamino-containing heterocylic ring moiety.
- the second constitutional repeating units each comprise at least one pendant moiety per second constitutional repeating unit that is selected from ionic organic moieties.
- ionic organic moieties include cationic moieties, anionic moieties, and amphoteric/zwitterionic moieties.
- one or more of the second constitutional repeating units comprise at least one pendant cationic moiety.
- Suitable cationic moieties include nitrogenous organic moieties that comprise a primary, secondary, or tertiary amino nitrogen atom, or a quaternary nitrogen atom.
- the, the cationic moiety is typically in the form of a salt that is associated with a counter anion, which may be selected from organic anions, such as sulphonate anions, and inorganic anions, such as halogen anions or nitrate anions.
- one or more of the second constitutional repeating units each comprise at least one pendant cationic moiety that comprises a quaternary ammonium nitrogen atom and counter anion, more typically a chloride, bromide, or nitrate counter anion, or a mixture thereof.
- one or more of the second constitutional repeating units each independently comprise, per second constitutional repeating unit, selected from:
- acyclic groups that comprise at least one primary, secondary, or tertiary amino nitrogen atom or quaternary nitrogen atom per group
- heterocylic ring-containing groups that comprise at least one nitrogen atom, which may be a quaternary nitrogen atom, as a ring member.
- Five or six-membered heterocylic ring-containing groups suitable as the at least one nitrogenous cationic group of the second constitutive unit include, for example, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrrolyl, imidazolyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piperazinyl, pyridinyl, pyrazinyl, pyrimadinyl, or pyridazinyl groups, more typically quaternized pyrrolidinyl, quaternized pyrrolinyl, quaternized imidazolidinyl, quaternized pyrrolyl, quaternized imidazolyl, quaternized pyrazolidinyl, quaternized pyrazolinyl, quaternized piperidinyl, quaternized piperazinyl, quaternized pyridinyl, quaternized pyra
- one or more of the second constitutional repeating units comprise at least one pendant anionic organic moiety.
- Suitable anionic moieties include, for example, carboxylate, sulphonate, sulfate, phosphate, and phosphonate moieties, such as, for example, alkyl carboxylate moieties, alkyl sulphonate moieties, alkaryl sulphonate moieties, and alkyl sulfate moieties, and salts thereof.
- the anionic moiety is in the form of a salt that is associated with a counter cation, which may be an inorganic cation or an organic cation, such as an ammonium cation, a cation comprising a primary, secondary, or tertiary amino nitrogen, a cation comprising a quaternary nitrogen atom, an alkali metal cation, or a mixture thereof.
- a counter cation which may be an inorganic cation or an organic cation, such as an ammonium cation, a cation comprising a primary, secondary, or tertiary amino nitrogen, a cation comprising a quaternary nitrogen atom, an alkali metal cation, or a mixture thereof.
- one or more of the second constitutional repeating units comprise at least one pendant amphoteric/zwitterionic organic moiety.
- Suitable amphoteric/zwitterionic organic moieties include, for example, moieties that comprise both a cationic group, such as a quaternary nitrogen atom, and anionic group, such as a sulphonate group or a carboxylate group, each of which may independently be in the form of a salt associated with an oppositely charged counterion, as part of the same moiety, such as, for example, sulfobetaine moieties or carboxybetaine moieties.
- one or more of the second constitutional repeating units each independently comprise at least one pendant nonionic organic moiety.
- Suitable nonionic moieties include hydrocarbyl moieties, such as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl moieties, hydroxyalkyl moieties, and poly(alkylene oxide) moieties.
- the ionic moiety of the ionic constitutional repeating units each independently comprise an acyclic group that comprises at least one quaternized nitrogen atom, such as a moiety according to formula (III):
- the copolymer comprises one or more second constitutional repeating units that comprise at least one cationic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one anionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one amphoteric/zwitterionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one nonionic moiety per such unit.
- the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one cationic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one anionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one cationic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one amphoteric/zwitterionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one cationic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one nonionic moiety per such unit.
- the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one anionic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one amphoteric/zwitterionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one anionic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one nonionic moiety per such unit. In one embodiment, the copolymer comprises one or more second constitutional repeating units that each independently comprise at least one amphoteric/zwitterionic moiety per such unit and one or more second constitutional repeating units that each independently comprise at least one nonionic moiety per such unit.
- the second constitutional repeating units may be made by known synthetic techniques, such as, for example, by grafting of ionic or nonionic organic moieties onto a polymer backbone, such as a hydrocarbon polymer backbone, a polyester polymer backbone, or a polysaccharide polymer backbone, or by copolymerization of a second monomer, as described below, with, for example, the above-described first monomer.
- a polymer backbone such as a hydrocarbon polymer backbone, a polyester polymer backbone, or a polysaccharide polymer backbone
- the second constitutional repeating units of the copolymer of the present invention are derived from a second monomer that is copolymerizable with the first monomer and comprises, per molecule of the monomer, at least one reactive functional group and at least one nitrogenous cationic group selected from:
- acyclic groups that comprise at least one primary, secondary, or tertiary amino nitrogen atom or quaternary nitrogen atom per group
- heterocylic ring-containing groups that comprise at least one nitrogen atom, which may be a quaternary nitrogen atom, as a ring member, such as, for example, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrrolyl, imidazolyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piperazinyl, pyridinyl, pyrazinyl, pyrimadinyl, or pyridazinyl moiety.
- the acyclic groups that comprise at least one primary, secondary, or tertiary amino nitrogen atom or quaternary nitrogen atom per group is a an acyclic moiety that is cyclizable, either simultaneously with or subsequent to copolymerization with the first monomer, to form a five or six-membered heterocylic ring that comprises at least one nitrogen atom, which may be a quaternary nitrogen atom, as a ring member.
- the second constitutional repeating units of the copolymer of the present invention are derived from a second monomer comprising, per molecule of the monomer, at least one reactive functional group and at least one group that is (i) selected from ionic organic moieties and nonionic organic moieties, and (ii) is not a saturated or unsaturated, five-, six-, or seven-membered, acylamino- or diacylamino-containing heterocylic ring moiety.
- Suitable reactive functional groups are those described above in regard to the first monomer.
- the first monomer comprises one or more compounds according to structure (IV):
- Suitable cationic monomers include, for example, dimethylaminomethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, di(t-butyl)aminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, vinylamine, vinyl imidazole, vinylpyridine, vinylpyrrolidine, vinylpyrroline, vinylpyrazolidine, vinylpyrazoline, vinylpiperidine, vinylpiperazine, vinylpyridine, vinylpyrazine, vinylpyrimadine, vinylpyridazine, trimethylammonium ethyl (meth)acrylate salts, dimethylammonium ethyl (meth)acrylate salts, dimethylbenzylammonium (meth)acrylate salts, benzoylbenzyl dimethylammonium ethyl(meth)acrylate salts
- the second constitutional repeating units of the copolymer of the present invention are derived from a cationic monomer selected from diallyldimethylammonium salts, such as diallyldimethylammonium nitrate, quaternized dimethylaminoethyl(meth)acrylate salts, such as quaternized dimethylaminoethyl(meth)acrylate nitrate, and quaternized vinylimidazole salts, such as quaternized vinylimidazole nitrate.
- diallyldimethylammonium salts such as diallyldimethylammonium nitrate
- quaternized dimethylaminoethyl(meth)acrylate salts such as quaternized dimethylaminoethyl(meth)acrylate nitrate
- quaternized vinylimidazole salts such as quaternized vinylimidazole nitrate.
- Suitable anionic monomers include, for example, acrylic acid, acrylic acid, methacrylic acid, vinyl sulphonic acid, vinylbenzene sulphonic acid, (meth)acrylamidomethylpropane sulphonic acid, 2-sulphoethyl methacrylate, and styrenesulfonate, as well as mixtures of and salts thereof.
- Suitable amphoteric/zwitterionic monomers include, for example, sulfobetaine (meth)acrylates, sulfobetaine (meth)acrylamides, sulfobetaine (meth)allyl compounds, sulfobetaine vinyl compounds, carboxybetaine (meth)acrylates, carboxybetaine (meth)acrylamides, caboxybetaine (meth)allyl compounds and carboxybetaine vinyl compounds, such as for example, N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethyl ammonium betaine, N-(3-acrylamidopropyl)-N,N-dimethylammonioacetate, or N-(3-acryloamidopropyl)-N,N-dimethyl-N-(carboxymethyl)ammonium bromide.
- Suitable nonionic monomers include, for example, (meth)acrylamide, esters of an monoethylenically unsaturated monocarboxylic acids, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl(meth)acrylate, 2-ethyl-hexyl (meth)acrylate, or hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, polyethylene and/or polypropylene oxide (meth)acrylates (i.e.
- esters of an monoethylenically unsaturated monocarboxylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl(meth)acrylate, 2-ethyl-hexyl (meth)acrylate
- hydroxyalkyl esters such as 2-hydroxyethyl
- polyethoxylated and/or polypropoxylated (meth)acrylic acid vinyl alcohol, vinyl acetate, vinyl versatate, vinyl nitriles, acrylonitrile, vinyl aromatic compounds, such as styrene, and mixtures thereof.
- the copolymer comprises, based on 1000 constitutional repeating units:
- the copolymer is made by copolymerizing a mixture of monomers that comprises more first monomers and one or more second monomers that each independently comprise at least one cationic moiety per molecule of such monomer. In one embodiment, the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers and one or more second monomers that each independently comprise at least one anionic moiety per molecule of such monomer. In one embodiment, the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers and one or more second monomers that each independently comprise at least one amphoteric/zwitterionic moiety per molecule of such monomer.
- the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers and one or more second monomers that each independently comprise at least one nonionic moiety per molecule of such monomer. In one embodiment, the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one cationic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one anionic moiety per molecule of such monomer.
- the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one cationic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one amphoteric/zwitterionic moiety per molecule of such monomer. In one embodiment, the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one cationic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one nonionic moiety per molecule of such monomer.
- the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one anionic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one amphoteric/zwitterionic moiety per molecule of such monomer. In one embodiment, the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one anionic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one nonionic moiety per molecule of such monomer.
- the copolymer is made by copolymerizing a mixture of monomers that comprises one or more first monomers, one or more second monomers that each independently comprise at least one amphoteric/zwitterionic moiety per molecule of such monomer, and one or more second monomers that each independently comprise at least one nonionic moiety per molecule of such monomer.
- the copolymer is made by copolymerizing a mixture of monomers, comprising, based on 1000 moles of such monomers:
- the copolymer of the present invention typically has weight average molecular weight of greater than or equal to 5,000 grams per mole (g/mol), more typically, a weight average molecular weight of from about 10,000 to about 2,000,000 g/mol, even more typically from about 10,000 to about 500,000 g/mol, and still more typically from about 10,000 to about 100,000 g/mol.
- the copolymer is a random copolymer, comprising chains of randomly arranged first constitutional repeating units and second constitutional repeating units. In one embodiment, the copolymer is a block copolymer, comprising blocks of two or more consecutive first constitutional repeating units and blocks of two or more consecutive second constitutive units.
- the polymer according to the present invention is made by copolymerization of ethylenically unsaturated monomers according to known free radical polymerization processes.
- the copolymer is made by a controlled free radical polymerization techniques, such as the known controlled free radical polymerization processes of atom transfer radical polymerization (“ATRP”), reversible addition fragmentation transfer (“RAFT” polymerization), or macromolecular design via interchange of xanthates (“MADIX” polymerization).
- ATRP atom transfer radical polymerization
- RAFT reversible addition fragmentation transfer
- MADIX macromolecular design via interchange of xanthates
- the cyclization to form the heterocylic ring structure may be conducted simultaneously with the copolymerization with the first monomer, such as by, for example, simultaneous polymerization and cyclization of a quaternized or quaternizable nitrogen atom-containing diallyl monomer, or conducted subsequent to such polymerization.
- the second monomer comprises a quaternizable nitrogen atom as a ring member, then the nitrogen may be quaternized subsequent to the polymerization reaction.
- the copolymer is a random copolymer made by free radical polymerization of vinyl pyrrolidone, vinyl caprolactam, or vinyl pyrrolidone and vinyl caprolactam with one or more ethylenically unsaturated cationic monomers.
- the copolymer is a random copolymer made by free radical polymerization of a monomer mixture comprising from about 80 pbw to less than 100 pbw, more typically from about 90 pbw to about 99 pbw, of vinyl pyrrolidone and from greater than 0 to about 20 pbw, more typically from about 1 to about 10 pbw, of a diallyldimethylammonium salt.
- the at least one silver compound comprises silver nitrate
- the at least one polyol comprises ethylene glycol
- the total amount of silver nitrate added to the reaction mixture is from 1.5 ⁇ 10 ⁇ 3 mole to about 1 mole silver nitrate per Liter of reaction mixture
- the reaction is conducted in the presence of, based on the weight of the reaction mixture, from about 0.01 wt % to about 50 wt %, more typically from about 0.1 wt % to about 20 wt %, and even more typically from about 0.5 wt % to 8 wt %, of a random copolymer made by free radical polymerization of a monomer mixture comprising from about 80 pbw to less than 100 pbw, more typically from about 90 pbw to about 99 pbw, of vinyl pyrrolidone and from greater than 0 to about 20 pbw, more typically from about 1 to about 10 pbw, of a diallyldimethylammonium salt.
- the process of the present invention typically produces a high yield of silver nanowires.
- greater than or equal to 70 wt % of silver feed is converted to nanowires and less than 30 wt % of silver feed is converted to isotropic nanostructures, more typically greater than or equal to 80 wt % of silver feed is converted to nanowires and less than 20 wt % of silver feed is converted to isotropic nanoparticles, and even more typically more than 90 wt % of silver feed is converted to nanowires and less than 10 wt % of silver feed is converted to isotropic nanostructures.
- greater than or equal to 99 wt % of silver feed is converted to nanowires and less than 1 wt % of silver feed is converted to isotropic nanostructures.
- the silver nanostructures comprise elongated silver nanostructures, known as “silver nanowires” having a diameter of from about 10 nm to about 2 ⁇ m, more typically from about 10 nm to about 150 nm, even more typically from about 10 nm to about 60 nm, and a length of from about 5 ⁇ m to about 300 ⁇ m, more typically from about 10 to about 200 ⁇ m.
- the silver nanostructures comprise silver nanowires having a diameter of from about 10 nm to about 150 nm, even more typically from about 10 nm to about 60 nm, and an aspect ratio, that is, a length to diameter ratio, of greater than 100, or greater than 150, or greater than 200, or greater than 300.
- the nanowires made by the process of the present invention exhibit an aspect ratio that is, on average, greater than that of nanowires made by an analogous product wherein poly(vinyl pyrrolidone) is substituted for the copolymer component of the process of the present invention. In one embodiment, the nanowires made by the process of the present invention exhibit an aspect ratio that is, on average, greater than that of nanowires made by an analogous product wherein poly(vinyl pyrrolidone is substituted for the copolymer component of the process of the present invention by a factor of a least 2, more typically by a factor of at least 3.
- the product mixture comprises polyol, copolymer, and silver nanostructures, wherein the silver nanostructures comprise silver nanowires and may comprise silver nanostructures other than silver nanowires, such as, isotropic silver particles.
- the silver nanostructures may be isolated from the polyol and copolymer components of the product mixture by, for example, gravity separation, centrifugation, or filtration. In one embodiment, the silver nanostructures are then washed in water, an alcohol, typically a (C 1 -C 3 )alkanol, or a mixture of water and alkanol, to remove residues of the polyol and copolymer from the isolated nanowires.
- an alcohol typically a (C 1 -C 3 )alkanol, or a mixture of water and alkanol
- Silver nanowires produced by the process of the present invention may be separated from other non-nanowire silver nanostructure components that may be present in the product mixture by dispersing the silver nanostructures in a polar aprotic organic liquid, such as acetone or acetonitrile, followed by isolation of the nanowires from the liquid by gravity separation or centrifugation.
- a polar aprotic organic liquid such as acetone or acetonitrile
- the product mixture is subjected to gravity separation, the silver nanowire fraction of the separated product mixture is re-dispersed in acetone and subjected to gravity separation and the silver nanowire fraction of the separated acetone dispersion is the re-dispersed in water, alcohol or a mixture thereof.
- the residue of the copolymer used in the process of the present invention is more easily cleaned from the silver nanostructure product than the poly(vinylpyrrolidone) homopolymer of prior art processes, which typically require multiple iterations of water or water and alcohol washing to remove from the silver nanostructure product.
- the copolymer residue may typically be removed from the silver nanostructures in a single water/alkanol washing step, while removal of poly(vinyl pyrrolidone homopolymer residue from silver nanostructures typically requires form 5 to 10 iterations of an analogous water/alkanol washing step.
- the silver nanowires of the dispersion of the present invention can be used to make polymer films having high electrical conductivity without requiring the extra steps required by prior art processes, such as iterative washing steps or heat treating or heating and compressing the silver nanowire network to displace a coating of vinylpyrrolidone residue from the surfaces of the nanowires and allow metal to metal contact between the nanowires of the network.
- silver nanowires are provided in the form of a dispersion comprising silver nanowires dispersed in liquid medium comprising water, a (C 1 -C 6 )alkanol, or a mixture thereof. Including an alkanol component in the liquid medium of the dispersion is of benefit in reducing oxidation of the silver nanostructure component of the dispersion.
- the nanowire dispersion comprises silver nanowires dispersed in aqueous medium wherein the dispersion comprises less than 100 pbw, or less than 10 pbw, or less than 5 pbw or less than 1 pbw of the copolymer per 1,000,000 pbw of silver nanowires. In one embodiment, the dispersion comprises no detectable amount of the copolymer.
- the silver nanowires made by the process of the present invention are useful in combination with an electrically conductive polymer, as a component of an electrically conductive film.
- Suitable electrically conductive polymers include electrically conductive polythiophene polymers, electrically conductive poly(selenophene)polymers, electrically conductive poly(telurophene) polymers, electrically conductive polypyrrole polymers, electrically conductive polyaniline polymers, electrically conductive fused polycylic heteroaromatic polymers, and blends of any such polymers.
- the electrically conductive polymer comprises a doped electrically conductive polymer known as PEDT:PSS, which comprises poly(3,4-ethylenedioxythiophene or “PEDOT” and a water soluble polymeric acid dopant comprising a poly(styrene sulfonic acid) or “PSS”.
- PEDT:PSS doped electrically conductive polymer
- PEDOT poly(3,4-ethylenedioxythiophene”
- PSS water soluble polymeric acid dopant comprising a poly(styrene sulfonic acid) or “PSS”.
- Such electrically conductive polymer films typically exhibit high conductivity and high optical transparency and are useful as a layer in an electronic device.
- Suitable electronic devices include any device that comprises one or more layers of semiconductor materials and makes use of the controlled motion of electrons through such one or more layers, such as, for example: devices that converts electrical energy into radiation, such as, for example, light-emitting diodes, light emitting diode displays, diode lasers, or lighting panels, devices that detect signals through electronic processes, such as, for example, photodetectors, photoconductive cells, photoresistors, photoswitchs, phototransistors, phototubes, infrared (“IR”) detectors, or biosensors, devices that convert radiation into electrical energy, such as, for example, photovoltaic devices or solar cells, and devices that includes one or more electronic components with one or more semiconductor layers, such as, for example, transistors or diodes.
- devices that converts electrical energy into radiation such as, for example, light-emitting diodes, light emitting diode displays, diode lasers, or lighting panels
- devices that detect signals through electronic processes such as, for example, photodetectors, photo
- the process of the present invention permits the use of a higher concentration of silver compound, for example silver nitrate, in the reaction mixture which enables production of a product mixture having a higher concentration of silver nanostructures, more typically silver nanowires, than an analogous process wherein poly(vinyl(pyrrolidone) homopolymer is used in place of the copolymer component of the process of the present invention.
- a higher concentration of silver compound for example silver nitrate
- the process of the present invention enables production of silver nanowires having a higher aspect ratio than silver nanowires made by an analogous process wherein poly(vinyl(pyrrolidone) homopolymer is used in place of the copolymer component of the process of the present invention.
- silver nanostructures made by the process of the present invention are more easily cleaned than silver nanostructures made by an analogous process wherein poly(vinyl(pyrrolidone) homopolymer is used in place of the copolymer component of the process of the present invention, because residues of the copolymer component of the process of the present invention is more easily removed from silver nanowires structures than are residues of poly(vinyl pyrrolidone) homopolymer.
- poly(VP-co-DADMAN) random copolymers were each made by copolymerizing vinylpyrrolidone monomer with diallyldimethylammonium nitrate monomer (“DADMAN”).
- DADMAN monomer was made by exchanging the chloride counter ion of diallyldimethylammonium chloride monomer (“DADMAC”, shown in structure (b) above) with nitrate counter ions, using silver nitrate, according to reaction:
- DADMAC diallyldimethylammonium chloride monomer
- VP and DADMAN monomers were copolymerized according to the general Scheme A below, using controlled radical polymerization using azobisisobutyronitrile (AIBN) as the polymerization initiator and a thiocarbonylthio transfer agent, to produce a linear poly(VP-co-DADMAN) copolymer.
- AIBN azobisisobutyronitrile
- the poly(vinyl pyrrolidone) homopolymer of Comparative Example C1 was made by a process analogous to that used to make the copolymers of Examples 1A-1E, but using only vinyl pyrrolidone monomer, that is, no DADMAN monomer was included in the reaction mixture.
- the silver nanowires of Examples 2A-2G were made according to the general synthesis process described below, wherein the composition of the copolymer and the amount of silver nitrate added to the reaction mixture were varied. In each case, a respective one of the poly(VP-co-DADMAN) copolymers of Example 1A-1E was used as a protectant.
- an initial amount of silver nitrate (0.05 g, typically in the form of 0.34 mL of a feed solution containing 1 g of silver nitrate in 7.5 g of ethylene glycol) was then fed into the reaction mixture, upon which the reaction mixture turned brown in color. After 6 minutes, the remainder of the silver nitrate feed solution was added to the reaction mixture using a syringe, at a rate of 1.5 ml/min. As the silver nitrate feed was added, the reaction mixture darkened, turned grey in color, and then, typically within about 7 minutes after the beginning of the addition of the silver nitrate feed, nanowires became visible in the reaction mixture. Depending on the total amount of silver nitrate added, the reaction took from about 15 to about 30 minutes reach completion.
- the pH of the ethylene glycol used (high-purity anhydrous ethylene glycol; Sigma-Aldrich Lot SHBB8374V; “Lot A”) in the reaction mixture was determined to be 8.9 by dilution and titration.
- Lot A ethylene glycol was used in the present examples 2A-2G and Comparative Examples C2A-C2C as well as following Examples 3 and 4.
- the silver nanowires of Comparative Examples C2-A to C2-C were made by an analogous process to that used to make the silver nanowires of Examples 2A-2G, except that poly(VP) homopolymer of Comparative Example C1 was substituted for poly(VP-co-DADMAN) copolymer.
- the reaction was left to react until complete reduction of silver nitrate.
- the nanowires of Examples 2A-2G were isolated form the reaction mixture by gravity separation and the poly(VP-co-DADMAN residues were removed from the nanowires by washing with a mixture of water and alkanol.
- the nanowires of Comparative Examples C1-C3 were isolated from the reaction mixture by gravity separation and removal of the poly(VP) residues from the nanowires required multiple (at least 5) iterations of the water/alkanol washing step.
- silver nanowires were separated from isotropic silver nanostructures by agglomerating the silver nanowires in a mixture of acetone and water and collecting the agglomerated silver nanowires.
- the results are also summarized in FIG. 2 as a plot of nanowire diameter as a function of the amount of AgNO 3 used in the nanowire synthesis and amount of DADMAN in the copolymer used in the nanowire synthesis.
- the product nanostructures were classified as “thin nanowires” (nanostructures less than or equal to 150 nm in diameter and greater than 5 ⁇ m in length), “thick nanowires” (nanostructures greater than 150 nm in diameter and greater than 5 ⁇ m in length) and/or “nanoparticles” (nanostructures less than or equal to 5 ⁇ m in length).
- the plot allows the visualization of three regions, that is, a “Nanoparticles” region, wherein the silver nanostructure product was predominately nanoparticles and two nanowire regions, “Nanowires—Zone I”, wherein the silver nanostructure product was predominately thin nanowires, and “Nanowires—Zone II”, wherein the silver nanostructure product was a mixture of thin nanowires and thick nanowires, with a boundary line “C thin ” between the Nanoparticles region and Nanowires Zone I, and a boundary line “C thick ” between Nanowires—Zone I and Nanowires—Zone II.
- the results plotted FIG. 2 indicate that using poly(VP-co-DADMAN) copolymer instead of poly(VP) homopolymer shifts production of thin silver nanowires toward higher concentration of silver nitrate and that synthesis of thin silver nanowires can be achieved at concentrations up to 3 times higher than in pure poly(VP) homopolymer and that this effect increases dramatically as DADMAN content of the poly(VP-co-DADMAN) copolymer increases from 0 to about 2 wt % and continues to increase, although less dramatically as the DADMAN content further increased from 2 wt % to 8%.
- the diameter of the silver nanowires can be determined by transmission electron microscopy (TEM) and/or scanning electron microscopy (SEM). A TEM image of the silver nanowire of Example 2A is shown in FIG. 6 . The diameter of the silver nanowires of Example 2A is 55 nm.
- TEM transmission electron microscopy
- SEM scanning electron microscopy
- the silver nanostructures of Examples 3A-3C were made substantially in accord with the process used to make the nanowires of Examples 2A-2G, as described above, using 0.5 g of the poly(VP-co-DADMAN) copolymer of Example 1E (16 wt % DADMAN content), except that the amount of silver nitrate added to the reaction mixture was varied.
- the length distribution of the as produced nanostructures was determined using the image analysis software “Image)” on picture taken with an optical microscope.
- FIG. 3 shows the size distributions of the nanostructure products of Examples 3A-3C.
- the amount of AgNO 3 used in each synthesis, as well as the symbol used to represent the nanostructure product in FIG. 3 is listed in TABLE III below.
- the silver nanowires of Examples 4A and 4 B were made according the process described above in Examples 2A-2G, using poly(VP-co-DADMAN) having a1 wt % DAMAN content at two different amounts of AgNO 3 .
- FIG. 4 shows the size distributions of the nanostructure products Examples 4A and 4B.
- the amount of AgNO 3 used in each synthesis, as well as the symbol used to represent the nanostructure product in FIG. 4 is listed in TABLE IV below.
- poly(VP-co-DADMAN) The synthesis of poly(VP-co-DADMAN) is composed of two steps:
- the first step was a counter-ion exchange to form DADMAN (Diallydimethylammonium nitrate) from commercially-available DADMAC (Diallydimethylammonium chloride).
- DADMAN Diaallydimethylammonium nitrate
- DADMAC Diaallydimethylammonium chloride
- the white silver solid precipitate of AgCl is washed with 5 mL of water and then centrifuged a second time to extract all the DADMAN monomer from it.
- the combined supernatants were filtered through a 0.20 ⁇ m filter and added to 1452 g of vinylpyrrolidone (VP) and 130 g of molecular sieves.
- the monomers were shaken for an hour after which the sieves were removed.
- the solution was subsequently introduced into a 5-L three-necked round-bottomed flask reactor.
- Initiator solution was prepared separately by adding 2.20 g of AIBN to 20.8 g (about 20 mL) of VP.
- the mixture of monomers was heated up to 60° C. and stirred. 6.66 g of thiocarbonylthio transfer agent and 2.5 g of initiator solution were added to the 5-L flask. Then, 2.5 g of the initiator solution was added every 30 minutes. The reaction temperature was maintained between 57 and 62° C. After 7.5 hours, 500 g of methanol was added to the flask to reduce the viscosity of the reactant and the reaction was allowed to stir for up to 12 hours. A yellow viscous transparent liquid was obtained.
- the copolymer was isolated from remaining monomer by selective precipitation in this solvent. Two volumes of ether were used for 1 volume of copolymer. The ether was removed from the resulting white precipitate, which was subsequently dried in a hood and then in a vacuum oven. The dried copolymer was ground to obtain a white, slightly yellow, fine powder.
- poly(VP-co-DADMAN) The synthesis of poly(VP-co-DADMAN) is composed of two steps:
- the first step was a counter-ion exchange to form DADMAN (Diallydimethylammonium nitrate) from commercially-available DADMAC (Diallydimethylammonium chloride).
- DADMAN Diaallydimethylammonium nitrate
- DADMAC Diaallydimethylammonium chloride
- the white silver solid precipitate of AgCl is washed with 5 mL of water and then centrifuged a second time to extract all the DADMAN monomer from it.
- the combined supernatants were filtered through a 0.20 ⁇ m filter and added to 1452 g of vinylpyrrolidone (VP) and 130 g of molecular sieves.
- the monomers were shaken for an hour after which the sieves were removed.
- the solution was subsequently introduced into a 5-L three-necked round-bottomed flask reactor.
- Initiator solution was prepared separately by adding 2.20 g of AIBN to 20.8 g (about 20 mL) of VP.
- the mixture of monomers was heated up to 60° C. and stirred. 6.66 g of thiocarbonylthio transfer agent and 2.5 g of initiator solution were added to the 5-L flask. Then, 2.5 g of the initiator solution was added every 30 minutes. The reaction temperature was maintained between 57 and 62° C.
- the copolymer suspension is used as is in silver nanowire synthesis without further purification.
- High aspect ratio silver nanowires were achieved using poly(VP-co-DADMAN) in ethylene glycol that required the addition of a base.
- the pH of the ethylene glycol used (high-purity anhydrous ethylene glycol; Sigma-Aldrich Lot SHBC6651V; “Lot B”) in the reaction mixture was determined to be 4.6 by dilution and titration.
- Lot B ethylene glycol was used in the present Example 7 and in the following Examples 8 and 9.
- lithium chloride (LiCl), 2.4 mg lithium hydroxide (LiOH), and 0.5 g poly(VP-co-DADMAN) having a 1 wt % DAMAN content were added to 44 g of ethylene glycol and heated to 175° C. for 30 minutes under nitrogen atmosphere and moderate agitation (100-300 rpm).
- an initial amount of silver nitrate 14 mg AgNO 3 dissolved in 0.45 mL ethylene glycol
- a silver nitrate feed solution (with 0.37 gm of AgNO 3 dissolved in 12 g ethylene glycol) was then fed dropwise to the reaction mixture at a rate of 1.5 mL/minute. The reaction was stopped after 15 minutes from the start of the feed by quenching the solution in ice.
- Example 7 The nanowires of Example 7 were isolated form the reaction mixture by gravity separation and the poly(VP-co-DADMAN residues were removed substantially according to the isolation steps described in the previous Examples.
- FIG. 8 An SEM image of the nanowires of Example 7 is shown in FIG. 8 .
- the average diameter of the nanowires was found to be about 47 nm, and the average length was found to be about 20 ⁇ m.
- FIG. 9 shows an image of the nanowires of Example 7 as seen through optical microscopy.
- the silver nanowires of Example 8 were made by an analogous process to that used to make the silver nanowires of Example 7, except that LiOH was replaced with 5.8 mg of potassium hydroxide (KOH).
- FIG. 10 shows an image of the nanowires of Example 8 as seen through optical microscopy.
- the average diameter of the nanowires of Example 8 was found to be about 65 nm, and the average length was found to be about 25 ⁇ m.
- the silver nanowires of Example 9 were made by an analogous process to that used to make the silver nanowires of Example 7, except that LiOH was replaced with 4.1 mg of sodium hydroxide (NaOH).
- FIG. 11 shows an image of the nanowires of Example 9 as seen through optical microscopy.
- the average diameter of the nanowires of Example 9 was found to be about 57 nm, and the average length was found to be about 22 ⁇ m.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/040,406 US20140178247A1 (en) | 2012-09-27 | 2013-09-27 | Process for making silver nanostructures and copolymer useful in such process |
US15/356,886 US20170066058A1 (en) | 2012-09-27 | 2016-11-21 | Process for making silver nanostructures and copolymer useful in such process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261706280P | 2012-09-27 | 2012-09-27 | |
US14/040,406 US20140178247A1 (en) | 2012-09-27 | 2013-09-27 | Process for making silver nanostructures and copolymer useful in such process |
Publications (1)
Publication Number | Publication Date |
---|---|
US20140178247A1 true US20140178247A1 (en) | 2014-06-26 |
Family
ID=50389153
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/040,365 Active 2034-03-04 US9410007B2 (en) | 2012-09-27 | 2013-09-27 | Process for making silver nanostructures and copolymer useful in such process |
US14/040,406 Abandoned US20140178247A1 (en) | 2012-09-27 | 2013-09-27 | Process for making silver nanostructures and copolymer useful in such process |
US15/194,796 Abandoned US20160303658A1 (en) | 2012-09-27 | 2016-06-28 | Process for making silver nanostructures and copolymer useful in such process |
US15/356,886 Abandoned US20170066058A1 (en) | 2012-09-27 | 2016-11-21 | Process for making silver nanostructures and copolymer useful in such process |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/040,365 Active 2034-03-04 US9410007B2 (en) | 2012-09-27 | 2013-09-27 | Process for making silver nanostructures and copolymer useful in such process |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/194,796 Abandoned US20160303658A1 (en) | 2012-09-27 | 2016-06-28 | Process for making silver nanostructures and copolymer useful in such process |
US15/356,886 Abandoned US20170066058A1 (en) | 2012-09-27 | 2016-11-21 | Process for making silver nanostructures and copolymer useful in such process |
Country Status (9)
Country | Link |
---|---|
US (4) | US9410007B2 (ja) |
EP (1) | EP2900409B1 (ja) |
JP (2) | JP6147860B2 (ja) |
KR (1) | KR102172116B1 (ja) |
CN (1) | CN104797363B (ja) |
AU (1) | AU2013323179B2 (ja) |
BR (1) | BR112015006873A2 (ja) |
CA (1) | CA2886404A1 (ja) |
WO (1) | WO2014052887A2 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10438714B2 (en) | 2017-12-06 | 2019-10-08 | C3Nano Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
US10661348B2 (en) | 2015-03-03 | 2020-05-26 | Basf Se | Silver nanowire synthesis with (meth)acrylate based capping agents |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150155167A1 (en) * | 2012-06-07 | 2015-06-04 | Qunano Ab | Method of manufacturing a structure adapted to be transferred to non-crystalline layer and a structure manufactured using said method |
CN104797363B (zh) * | 2012-09-27 | 2018-09-07 | 罗地亚经营管理公司 | 制造银纳米结构的方法和可用于此方法的共聚物 |
KR101448361B1 (ko) * | 2012-12-14 | 2014-10-14 | 인스콘테크(주) | 공중합물 캡핑제를 이용한 은 나노와이어 제조방법 |
JP6587616B2 (ja) | 2013-12-31 | 2019-10-09 | ローディア オペレーションズ | 銀ナノ構造体の作製方法 |
CN106068166B (zh) * | 2014-03-07 | 2018-10-09 | 同和控股(集团)有限公司 | 银纳米线的制造方法和银纳米线及使用该银纳米线的油墨 |
JP6353671B2 (ja) * | 2014-03-14 | 2018-07-04 | Dowaエレクトロニクス株式会社 | 銀ナノワイヤインクの製造方法および銀ナノワイヤインク並びに透明導電塗膜 |
JP6312090B2 (ja) * | 2015-03-11 | 2018-04-18 | 信越化学工業株式会社 | 導電性材料及び基板 |
JP6526739B2 (ja) * | 2016-06-02 | 2019-06-05 | Dowaエレクトロニクス株式会社 | 銀ナノワイヤおよびその製造法並びに銀ナノワイヤインクおよび透明導電膜 |
US20190352529A1 (en) * | 2016-06-27 | 2019-11-21 | Dowa Electronics Materials Co., Ltd. | Silver nanowire ink, method for producing same, and conductive film |
TWI718002B (zh) * | 2020-02-17 | 2021-02-01 | 中國鋼鐵股份有限公司 | 奈米帶狀銀粉的製造方法 |
CN114933673B (zh) * | 2022-03-30 | 2023-07-21 | 中海石油(中国)有限公司 | 一种基于聚丙烯酰胺-丙烯酸丁酯-两性离子的恒流变流型调节剂及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060116470A1 (en) * | 2002-09-04 | 2006-06-01 | Werner Gauweiler | Production of aqueous dispersions of cationic homo-and copolymers using amphoteric protective colloids |
US7115254B1 (en) * | 2002-10-25 | 2006-10-03 | Nalco Company | Personal care compositions containing N,N-diallyldialkylammonium halide/N-vinylpyrrolidone polymers |
Family Cites Families (231)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3288770A (en) | 1962-12-14 | 1966-11-29 | Peninsular Chem Res Inc | Water soluble quaternary ammonium polymers |
US4347339A (en) | 1981-05-08 | 1982-08-31 | Nalco Chemical Company | Cationic block copolymers |
JP2821754B2 (ja) | 1989-02-16 | 1998-11-05 | 日本ゼオン株式会社 | 磁気記録媒体 |
DE4133621A1 (de) | 1991-10-10 | 1993-04-22 | Inst Neue Mat Gemein Gmbh | Nanoskalige teilchen enthaltende kompositmaterialien, verfahren zu deren herstellung und deren verwendung fuer optische elemente |
DE4235798A1 (de) * | 1992-10-23 | 1994-04-28 | Basf Ag | Verwendung von Vinylpyrrolidon- und Vinylimidazol-Copolymerisaten als Waschmitteladditiv, neue Polymerisate des Vinylpyrrolidons und des Vinylimidazols und Verfahren zu ihrer Herstellung |
DE19501802A1 (de) * | 1994-02-01 | 1995-08-03 | Basf Ag | Verwendung von Zusammensetzungen, enthaltend Metallpartikel im Nanometergrößenbereich |
ES2218560T3 (es) * | 1994-12-28 | 2004-11-16 | Isp Investments Inc. | Procedimiento para preparar copolimeros sustancialmente homogeneos de vinilpirrolidona y n-3,3-dimetilaminopropil metacrilamida para aplicaciones de cuidado personal. |
JPH10511422A (ja) * | 1994-12-28 | 1998-11-04 | アイエスピー インヴェストメンツ インコーポレイテッド | ビニルピロリドンと第四アンモニウム単量体と疎水性単量体との均一な三元共重合体 |
US6011160A (en) | 1997-09-18 | 2000-01-04 | Isp Investments Inc. | Crosslinked polyvinylpyrrolidone (PVPP) copolymer of vinyl pyrrolidone (VP) and monomer derived from 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP) |
ATE502117T1 (de) | 1999-06-25 | 2011-04-15 | Nanosphere Inc | Nanopartikel mit gebundenen oligonukleotiden und deren verwendungen |
US6225429B1 (en) * | 1999-07-01 | 2001-05-01 | Isp Investments Inc. | Process for making vinyl caprolactam-based polymers |
US6539156B1 (en) | 1999-11-02 | 2003-03-25 | Georgia Tech Research Corporation | Apparatus and method of optical transfer and control in plasmon supporting metal nanostructures |
US6716895B1 (en) | 1999-12-15 | 2004-04-06 | C.R. Bard, Inc. | Polymer compositions containing colloids of silver salts |
WO2001051665A2 (en) | 2000-01-13 | 2001-07-19 | Nanosphere Inc. | Nanoparticles having oligonucleotides attached thereto and uses therefor |
AU2001255203A1 (en) | 2000-03-28 | 2001-10-08 | Nanosphere Inc. | Nanoparticles having oligonucleotides attached thereto and uses therefor |
US6720240B2 (en) | 2000-03-29 | 2004-04-13 | Georgia Tech Research Corporation | Silicon based nanospheres and nanowires |
US6440637B1 (en) | 2000-06-28 | 2002-08-27 | The Aerospace Corporation | Electron beam lithography method forming nanocrystal shadowmasks and nanometer etch masks |
US6649138B2 (en) * | 2000-10-13 | 2003-11-18 | Quantum Dot Corporation | Surface-modified semiconductive and metallic nanoparticles having enhanced dispersibility in aqueous media |
WO2003002089A1 (en) | 2001-06-29 | 2003-01-09 | Dow Global Technologies Inc. | Superabsorbent carboxyl-containing polymers with odor control properties and method for preparation |
DE60233176D1 (de) | 2001-11-08 | 2009-09-10 | Seti Inst | Aus chaperonin-polypeptiden gebildete geordnete biologische nanostrukturen |
JP2003191420A (ja) | 2001-12-28 | 2003-07-08 | Mitsubishi Polyester Film Copp | 帯電防止フィルム |
US7547931B2 (en) | 2003-09-05 | 2009-06-16 | Nanomix, Inc. | Nanoelectronic capnometer adaptor including a nanoelectric sensor selectively sensitive to at least one gaseous constituent of exhaled breath |
JP3842177B2 (ja) | 2002-07-03 | 2006-11-08 | 独立行政法人科学技術振興機構 | 貴金属ナノチューブ及びその製造方法 |
US7494704B2 (en) | 2002-08-15 | 2009-02-24 | Eastman Kodak Company | Material, article and method of preparing materials containing oriented anisotropic particles |
US7462298B2 (en) | 2002-09-24 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Water dispersible polyanilines made with polymeric acid colloids for electronics applications |
JP2004114273A (ja) | 2002-09-30 | 2004-04-15 | National Institute For Materials Science | 走査トンネル顕微鏡による銀ナノ構造の作製方法 |
JP3963447B2 (ja) | 2002-10-03 | 2007-08-22 | 竹本油脂株式会社 | ポリエステル系フィルム用帯電防止剤及びポリエステル系フィルムの帯電防止方法 |
US7550611B2 (en) | 2002-11-14 | 2009-06-23 | Catalytic Materials, Llc | Carbon nanochips as catalyst supports for metals and metal oxides |
US7585349B2 (en) | 2002-12-09 | 2009-09-08 | The University Of Washington | Methods of nanostructure formation and shape selection |
US20050008676A1 (en) * | 2002-12-19 | 2005-01-13 | Yongxing Qiu | Medical devices having antimicrobial coatings thereon |
US9422651B2 (en) | 2003-01-13 | 2016-08-23 | Nantero Inc. | Methods for arranging nanoscopic elements within networks, fabrics, and films |
JP4636454B2 (ja) | 2003-05-13 | 2011-02-23 | 三菱マテリアル株式会社 | 金属ナノロッドの製造方法と用途 |
WO2005005687A1 (en) | 2003-07-02 | 2005-01-20 | Seldon Technologies, Llc | Method of coating nanosturctures with metal using metal salts |
US9057705B2 (en) | 2003-07-28 | 2015-06-16 | The Regents Of The University Of California | Surface-enhanced raman spectroscopy substrate for arsenic sensing in groundwater |
US7067341B2 (en) | 2003-10-28 | 2006-06-27 | Stmicroelectronics S.R.L. | Single electron transistor manufacturing method by electro-migration of metallic nanoclusters |
CA2543737A1 (en) | 2003-10-30 | 2005-05-12 | Applied Medical Resources Corporation | Surface treatments and modifications using nanostructure materials |
US7846412B2 (en) | 2003-12-22 | 2010-12-07 | Emory University | Bioconjugated nanostructures, methods of fabrication thereof, and methods of use thereof |
WO2005092286A2 (en) * | 2004-03-29 | 2005-10-06 | The University Of Houston System | Metallic nano-particles and discrete polymer-coated nano-particles |
US7128881B2 (en) | 2004-04-30 | 2006-10-31 | Petrik Viktor I | Configurations and methods for water purification |
US8280214B2 (en) | 2004-05-13 | 2012-10-02 | The Regents Of The University Of California | Nanowires and nanoribbons as subwavelength optical waveguides and their use as components in photonic circuits and devices |
US7718094B2 (en) | 2004-06-18 | 2010-05-18 | The Research Foundation Of State University Of New York | Preparation of metallic nanoparticles |
US7052765B2 (en) | 2004-07-22 | 2006-05-30 | Taiwan Textile Research Institute | Method for manufacturing antibacterial polyester master batches and fibers both containing nano-silver particles |
JP2006038999A (ja) | 2004-07-23 | 2006-02-09 | Sumitomo Electric Ind Ltd | レーザ照射を用いた導電性回路形成方法と導電性回路 |
US8361553B2 (en) | 2004-07-30 | 2013-01-29 | Kimberly-Clark Worldwide, Inc. | Methods and compositions for metal nanoparticle treated surfaces |
US8114187B2 (en) | 2004-08-03 | 2012-02-14 | University Of Washington Through Its Center For Commercialization | Synthesis of platinum nanostructures |
JP2006053270A (ja) | 2004-08-10 | 2006-02-23 | Fuji Photo Film Co Ltd | 熱現像感光材料およびそれを用いた画像形成方法 |
US20060068026A1 (en) | 2004-08-11 | 2006-03-30 | Hu Michael Z | Thermal electrochemical synthesis method for production of stable colloids of "naked" metal nanocrystals |
JP2006053375A (ja) | 2004-08-12 | 2006-02-23 | Fuji Photo Film Co Ltd | 熱現像感光材料およびそれを用いた画像形成方法 |
JP2006089447A (ja) | 2004-09-27 | 2006-04-06 | Fuji Photo Film Co Ltd | 有機銀塩分散物の製造方法および熱現像感光材料 |
US20060068025A1 (en) | 2004-09-29 | 2006-03-30 | Eastman Kodak Company | Silver microribbon composition and method of making |
US7329301B2 (en) | 2004-09-29 | 2008-02-12 | Eastman Kodak Company | Silver nanoparticles made in solvent |
EP1828052A4 (en) | 2004-10-12 | 2011-06-08 | Amroy Europ Oy | NEW HYBRID MATERIALS AND RELATED METHODS AND DEVICES |
WO2006051153A2 (en) | 2004-11-09 | 2006-05-18 | Nanolab Systems Oy | Methods and devices for facile fabrication of nanoparticles and their applications |
US20060115536A1 (en) | 2004-11-12 | 2006-06-01 | Board Of Regents, The University Of Texas System | Glycerin based synthesis of silver nanoparticles and nanowires |
US7582330B2 (en) | 2004-11-24 | 2009-09-01 | 3M Innovative Properties Counsel | Method for making metallic nanostructures |
US8886464B2 (en) | 2005-01-03 | 2014-11-11 | University Of Maryland, Baltimore County | Microwave-accelerated metal-enhanced detection method |
US7824466B2 (en) * | 2005-01-14 | 2010-11-02 | Cabot Corporation | Production of metal nanoparticles |
US8383014B2 (en) | 2010-06-15 | 2013-02-26 | Cabot Corporation | Metal nanoparticle compositions |
TWI283717B (en) | 2005-03-09 | 2007-07-11 | Taiwan Textile Res Inst | Method of fabricating nano-silver fibers |
WO2006113207A2 (en) | 2005-04-13 | 2006-10-26 | Nanosys, Inc. | Nanowire dispersion compositions and uses thereof |
WO2006116424A2 (en) | 2005-04-26 | 2006-11-02 | Nanosys, Inc. | Paintable nanofiber coatings |
US7547347B2 (en) | 2005-05-13 | 2009-06-16 | University Of Rochester | Synthesis of nano-materials in ionic liquids |
JP5546763B2 (ja) | 2005-08-12 | 2014-07-09 | カンブリオス テクノロジーズ コーポレイション | ナノワイヤに基づく透明導電体 |
RU2008112684A (ru) | 2005-09-02 | 2009-10-10 | Тор Гмбх (De) | Синергическая серебросодержащая биоцидная композиция |
KR100716201B1 (ko) | 2005-09-14 | 2007-05-10 | 삼성전기주식회사 | 금속 나노 입자 및 이의 제조방법 |
DE102005060407B3 (de) | 2005-12-15 | 2007-02-08 | Christian-Albrechts-Universität Zu Kiel | Verfahren zur Herstellung von Nanostrukturen auf einem Substrat |
US20080003130A1 (en) | 2006-02-01 | 2008-01-03 | University Of Washington | Methods for production of silver nanostructures |
KR100754326B1 (ko) | 2006-02-15 | 2007-09-03 | 삼성전기주식회사 | 금속 나노입자의 제조방법 |
US7704553B2 (en) | 2006-03-06 | 2010-04-27 | National Institute Of Aerospace Associates | Depositing nanometer-sized particles of metals onto carbon allotropes |
AU2006342738B2 (en) | 2006-04-24 | 2012-06-28 | Ntc S.R.L. | Functional nanomaterials with antibacterial and antiviral activity |
KR100790948B1 (ko) | 2006-05-25 | 2008-01-03 | 삼성전기주식회사 | 금속 나노입자의 제조방법 및 이에 의해 제조되는 금속나노입자 |
US8454721B2 (en) * | 2006-06-21 | 2013-06-04 | Cambrios Technologies Corporation | Methods of controlling nanostructure formations and shapes |
EP2752470A1 (en) | 2006-08-07 | 2014-07-09 | Inktec Co., Ltd. | Process for preparation of silver nanoparticles, and the compositions of silver ink containing the same |
US20080083299A1 (en) | 2006-10-06 | 2008-04-10 | General Electric Company | Composition and associated method |
US7632425B1 (en) | 2006-10-06 | 2009-12-15 | General Electric Company | Composition and associated method |
US20080085962A1 (en) | 2006-10-06 | 2008-04-10 | General Electric Company | Composition and associated method |
JP5309521B2 (ja) | 2006-10-11 | 2013-10-09 | 三菱マテリアル株式会社 | 電極形成用組成物及びその製造方法並びに該組成物を用いた電極の形成方法 |
US20080102122A1 (en) | 2006-10-31 | 2008-05-01 | Shivkumar Mahadevan | Antimicrobial polymeric articles, processes to prepare them and methods of their use |
WO2008127313A2 (en) | 2006-11-17 | 2008-10-23 | The Regents Of The University Of California | Electrically conducting and optically transparent nanowire networks |
US20120141731A1 (en) | 2006-12-18 | 2012-06-07 | Mirkin Chad A | Fabrication of microstructures and nanostructures using etching resist |
EP2109784B2 (en) | 2007-01-31 | 2016-10-05 | Novartis AG | Antimicrobial medical devices including silver nanoparticles |
US9580810B2 (en) | 2007-02-27 | 2017-02-28 | Mitsubishi Materials Corporation | Dispersion of metal nanoparticles, method for producing the same, and method for synthesizing metal nanoparticles |
EP2129513B1 (en) * | 2007-03-22 | 2016-08-03 | Novartis AG | Prepolymers with dangling polysiloxane-containing polymer chains |
JP4890311B2 (ja) | 2007-03-28 | 2012-03-07 | パナソニック株式会社 | 発光素子 |
KR101398821B1 (ko) | 2007-03-30 | 2014-05-30 | 삼성디스플레이 주식회사 | 금속 나노 입자의 제조방법, 이를 포함하는 전도성 잉크조성물 및 이를 이용한 전도성 패턴의 형성방법 |
DE102007018540A1 (de) | 2007-04-19 | 2008-10-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Elektrisch leitfähige und transparente Zusammensetzung |
JP5169389B2 (ja) | 2007-04-19 | 2013-03-27 | 三菱マテリアル株式会社 | 導電性反射膜の製造方法 |
EP2147466B9 (en) | 2007-04-20 | 2014-07-16 | Cambrios Technologies Corporation | Composite transparent conductors |
WO2008143061A1 (ja) | 2007-05-16 | 2008-11-27 | Dic Corporation | 銀含有ナノ構造体の製造方法及び銀含有ナノ構造体 |
KR100887768B1 (ko) | 2007-06-11 | 2009-04-17 | 나노폴리(주) | 항균 및 항곰팡이 기능을 갖는 함수성 티슈의 제조방법 |
US20120164396A1 (en) | 2007-06-20 | 2012-06-28 | Northwestern University | Matrix assisted ink transport |
US8420717B2 (en) | 2007-07-23 | 2013-04-16 | William Marsh Rice University | Polyol functionalized water soluble carbon nanostructures |
US20090074705A1 (en) | 2007-07-26 | 2009-03-19 | Uschi Graham | Process for forming metal nanoparticles in polymers |
US20100258784A1 (en) | 2007-09-18 | 2010-10-14 | Lukin Mikhail D | Method Of Efficient Coupling Of Light From Single-Photon Emitter To Guided Radiation Localized To Sub-Wavelength Dimensions On Conducting Nanowires |
US20090104114A1 (en) | 2007-09-21 | 2009-04-23 | Cytimmune Sciences, Inc. | Nanotherapeutic Colloidal Metal Compositions and Methods |
US20100224026A1 (en) | 2007-10-04 | 2010-09-09 | Margaret Elizabeth Brennan Fournet | A process for synthesising silver nanoparticles |
JPWO2009063744A1 (ja) | 2007-11-16 | 2011-03-31 | コニカミノルタホールディングス株式会社 | 金属ナノワイヤの製造方法、金属ナノワイヤ及び透明導電体 |
US20090148484A1 (en) | 2007-12-07 | 2009-06-11 | National Taiwan University | Stably-dispersing composite of metal nanoparticle and inorganic clay and method for producing the same |
TW200925178A (en) | 2007-12-07 | 2009-06-16 | Univ Nat Taiwan | Polymeric polyamine and method for stabilizing silver nanoparticles using the same |
WO2009078815A1 (en) | 2007-12-14 | 2009-06-25 | Nanyang Technological University | A nanostructured material loaded with noble metal particles |
KR100861399B1 (ko) | 2007-12-17 | 2008-10-02 | 주식회사 잉크테크 | 은 나노입자 분산 수지의 제조 방법 |
KR101234881B1 (ko) | 2007-12-20 | 2013-02-20 | 시마 나노 테크 이스라엘 리미티드 | 나노입자로 형성된 투명한 전극을 갖는 광전지 소자 |
CN101952989B (zh) | 2007-12-28 | 2012-11-28 | 埃克斯-马赛第二大学 | 杂化的纳米复合材料 |
US20110052671A1 (en) | 2008-01-30 | 2011-03-03 | The Regents Of The University Of California | Near infra-red pulsed laser triggered drug release from hollow nanoshell disrupted vesicles and vesosomes |
US7922787B2 (en) | 2008-02-02 | 2011-04-12 | Seashell Technology, Llc | Methods for the production of silver nanowires |
WO2009105662A1 (en) | 2008-02-21 | 2009-08-27 | Immunolight, Llc. | Methods and systems for treating cell proliferation disorders using plasmonics enhanced photospectral therapy (pepst) and exciton-plasmon enhanced phototherapy (epep) |
JP2009205924A (ja) | 2008-02-27 | 2009-09-10 | Kuraray Co Ltd | 透明導電膜、透明導電部材、銀ナノワイヤ分散液および透明導電膜の製造方法 |
JP5507440B2 (ja) | 2008-02-27 | 2014-05-28 | 株式会社クラレ | 金属ナノワイヤの製造方法並びに得られた金属ナノワイヤよりなる分散液および透明導電膜 |
JP5111170B2 (ja) | 2008-03-10 | 2012-12-26 | 富士フイルム株式会社 | 金属ナノワイヤー及びその製造方法、並びに水性分散物及び透明導電体 |
JP5203769B2 (ja) | 2008-03-31 | 2013-06-05 | 富士フイルム株式会社 | 銀ナノワイヤー及びその製造方法、並びに水性分散物及び透明導電体 |
CA2720513C (en) | 2008-04-04 | 2018-09-25 | Immunolight, Llc | Non-invasive systems and methods for in-situ photobiomodulation |
KR101202405B1 (ko) | 2008-05-28 | 2012-11-23 | (주)바이오니아 | 탄소나노튜브 및 금속으로 이루어진 나노복합체 및 이의제조방법 |
JP2009299162A (ja) | 2008-06-16 | 2009-12-24 | Fujifilm Corp | 銀ナノワイヤー及びその製造方法、並びに水性分散物及び透明導電体 |
US8178120B2 (en) | 2008-06-20 | 2012-05-15 | Baxter International Inc. | Methods for processing substrates having an antimicrobial coating |
KR20110044981A (ko) | 2008-06-25 | 2011-05-03 | 나노바이오매터스, 에스. 엘. | 활성 나노복합 재료 및 이의 제조 방법 |
US20110180764A1 (en) | 2008-06-26 | 2011-07-28 | Dic Corporation | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
WO2010005971A2 (en) | 2008-07-09 | 2010-01-14 | The Regents Of The University Of Michigan | Epoxidation catalyst and process |
WO2010009106A1 (en) | 2008-07-14 | 2010-01-21 | Bourke Frederic A Jr | Advanced methods and systems for treating cell proliferation disorders |
EP2310157B1 (de) | 2008-07-23 | 2013-04-10 | Construction Research & Technology GmbH | Verfahren zur herstellung von metallnanopartikeln in polyolen |
IT1391668B1 (it) | 2008-07-23 | 2012-01-17 | Universita' Degli Studi Di Trieste | Materiali nanocompositi basati su nanoparticelle metalliche stabilizzate con polisaccaridi a struttura ramificata. |
WO2010026571A2 (en) | 2008-09-02 | 2010-03-11 | Ramot At Tel-Aviv University Ltd. | Metal nanowire thin-films |
KR102028628B1 (ko) | 2008-09-02 | 2019-10-04 | 나트릭스 세퍼레이션즈, 인코포레이티드 | 크로마토그래피 막, 이를 포함하는 장치 및 이의 이용방법 |
JP5306760B2 (ja) | 2008-09-30 | 2013-10-02 | 富士フイルム株式会社 | 透明導電体、タッチパネル、及び太陽電池パネル |
JP2010087105A (ja) | 2008-09-30 | 2010-04-15 | Fujifilm Corp | 太陽電池 |
JP5189449B2 (ja) | 2008-09-30 | 2013-04-24 | 富士フイルム株式会社 | 金属ナノワイヤー含有組成物、及び透明導電体 |
US20110180133A1 (en) | 2008-10-24 | 2011-07-28 | Applied Materials, Inc. | Enhanced Silicon-TCO Interface in Thin Film Silicon Solar Cells Using Nickel Nanowires |
KR20100045675A (ko) | 2008-10-24 | 2010-05-04 | 삼성전자주식회사 | 표시 장치 |
US20100104652A1 (en) | 2008-10-27 | 2010-04-29 | University Of Arkansas | Use of advanced nanomaterials for increasing sepecific cell functions |
KR101089299B1 (ko) | 2008-11-18 | 2011-12-02 | 광 석 서 | 이온성 액체를 이용한 금속 나노와이어의 제조방법 |
US20100129949A1 (en) | 2008-11-25 | 2010-05-27 | Chang Chen | Increasing solar cell efficiency with silver nanowires |
CN101451270B (zh) | 2008-12-11 | 2011-04-13 | 常振宇 | 一种大批量制备贵金属纳米线的方法 |
DE102009015470A1 (de) | 2008-12-12 | 2010-06-17 | Byk-Chemie Gmbh | Verfahren zur Herstellung von Metallnanopartikeln und auf diese Weise erhaltene Metallnanopartikel und ihre Verwendung |
US8062407B2 (en) | 2008-12-23 | 2011-11-22 | Northwest Missouri State University | Household microwave-mediated carbohydrate-based production of silver nanomaterials |
TWI423930B (zh) | 2008-12-31 | 2014-01-21 | Ind Tech Res Inst | 奈米金屬溶液、奈米金屬複合顆粒以及金屬膜層的製作方法 |
US8273997B2 (en) | 2009-01-16 | 2012-09-25 | The Boeing Company | Antireflective apparatus with anisotropic capacitive circuit analog sheets |
IT1393040B1 (it) | 2009-03-02 | 2012-04-11 | Colorobbia Italiana Spa | Processo per la preparazione di sospensioni stabili di nanoparticelle metalliche e sospensioni colloidali stabili cosi' ottenute |
US20100242679A1 (en) | 2009-03-29 | 2010-09-30 | Yi-Hsiuan Yu | Method for continuously fabricating silver nanowire |
JP5584991B2 (ja) | 2009-04-02 | 2014-09-10 | コニカミノルタ株式会社 | 透明電極、透明電極の製造方法、および有機エレクトロルミネッセンス素子 |
US9536633B2 (en) | 2009-04-10 | 2017-01-03 | Sumitomo Chemical Company, Limited | Metallic composite and composition thereof |
JP2010250110A (ja) | 2009-04-16 | 2010-11-04 | Fujifilm Corp | 感光性組成物、並びに透明導電膜、表示素子及び集積型太陽電池 |
JP2010251611A (ja) | 2009-04-17 | 2010-11-04 | Fujifilm Corp | 太陽電池及びその製造方法 |
EP2421376A4 (en) | 2009-04-21 | 2016-04-27 | Immunolight Llc | NON-INVASIVE ENERGY UPGRADING METHODS AND SYSTEMS FOR IN-SITU PHOTO BODY MODULATION |
WO2010124270A1 (en) | 2009-04-24 | 2010-10-28 | Baker Christina O | Functionalized polymer biosensor |
US8029700B2 (en) | 2009-04-30 | 2011-10-04 | Chung-Shan Institute of Science and Technology Armaments Bureau, Ministry of National Defense | Compound of silver nanowire with polymer and compound of metal nanostructure with polymer |
EP2430639A1 (en) | 2009-05-05 | 2012-03-21 | Cambrios Technologies Corporation | Reliable and durable conductive films comprising metal nanostructures |
US20110024159A1 (en) * | 2009-05-05 | 2011-02-03 | Cambrios Technologies Corporation | Reliable and durable conductive films comprising metal nanostructures |
GB0908300D0 (en) | 2009-05-14 | 2009-06-24 | Dupont Teijin Films Us Ltd | Polyester films |
TWI404753B (zh) | 2009-07-03 | 2013-08-11 | Nat Univ Tsing Hua | 利用團聯共聚物模板製造奈米材料之方法 |
TWI403373B (zh) | 2009-07-16 | 2013-08-01 | Univ Nat Taiwan | 應用乙醇胺以製造奈米銀粒子之方法 |
WO2011008227A1 (en) | 2009-07-17 | 2011-01-20 | Carestream Health, Inc | Transparent conductive film comprising water soluble binders |
US20120107600A1 (en) | 2009-07-17 | 2012-05-03 | Chaofeng Zou | Transparent conductive film comprising cellulose esters |
US20110023658A1 (en) * | 2009-08-03 | 2011-02-03 | Seashell Technology, Llc | Methods For The Production Of Silver Nanocubes |
JP5246096B2 (ja) | 2009-08-10 | 2013-07-24 | 日立電線株式会社 | 複合金属微粒子材料、金属膜及び金属膜の製造方法、並びにプリント配線板及び電線ケーブル |
JP5391932B2 (ja) | 2009-08-31 | 2014-01-15 | コニカミノルタ株式会社 | 透明電極、透明電極の製造方法、および有機エレクトロルミネッセンス素子 |
US20120175585A1 (en) | 2009-09-17 | 2012-07-12 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd., | Cage nanostructures and prepartion thereof |
US8636823B2 (en) | 2009-09-26 | 2014-01-28 | Ames Advanced Materials Corporation | Silver ribbons, methods of their making and applications thereof |
CN102574206B (zh) | 2009-10-20 | 2014-06-04 | Dic株式会社 | 含有金属纳米粒子的复合物、其分散液以及它们的制造方法 |
CN102666879B (zh) | 2009-10-30 | 2016-02-24 | 西北大学 | 模板化的纳米缀合物 |
KR101130698B1 (ko) | 2009-11-03 | 2012-04-02 | 삼성전자주식회사 | 밸브 유닛과 이를 구비한 미세유동장치 및 밸브 유닛의 구동방법 |
KR101125191B1 (ko) | 2009-11-09 | 2012-03-19 | 한국과학기술원 | 콜로이드 입자로 안정화된 액적을 이용한 표면구조를 갖는 미세입자의 제조방법 |
CN107149689A (zh) | 2009-11-10 | 2017-09-12 | 免疫之光有限责任公司 | 对可辐射固化介质进行固化的系统和产生光的方法 |
CA2783788C (en) | 2009-12-11 | 2015-02-10 | Korea Research Institute Of Chemical Technology | Dimeric core-shell nanostructure labeled with raman active molecule localized at interparticle junction, use thereof, and method for preparing the same |
DE102009058832A1 (de) | 2009-12-18 | 2011-06-30 | Bayer Technology Services GmbH, 51373 | Verfahren zur elektrochemischen Sauerstoffreduktion im Alkalischen |
WO2011078170A1 (ja) | 2009-12-25 | 2011-06-30 | 富士フイルム株式会社 | 導電性組成物、並びに、それを用いた透明導電体、タッチパネル及び太陽電池 |
EP2524380B1 (en) | 2010-01-15 | 2021-06-23 | Cambrios Film Solutions Corporation | Low-haze transparent conductors |
CN102781816A (zh) | 2010-01-25 | 2012-11-14 | 小利兰·斯坦福大学托管委员会 | 富勒烯掺杂的纳米结构及其方法 |
WO2011101837A1 (en) | 2010-02-16 | 2011-08-25 | The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin | Substrate for surface enhanced raman spectroscopy |
US9362390B2 (en) | 2010-02-22 | 2016-06-07 | Nantero, Inc. | Logic elements comprising carbon nanotube field effect transistor (CNTFET) devices and methods of making same |
US8591624B2 (en) | 2010-02-25 | 2013-11-26 | National Tsing Hua University | Methods for preparing hydrophobic metal nanoparticles and precursors used therein |
US8765862B2 (en) | 2010-03-01 | 2014-07-01 | Nippon Steel & Sumikin Chemical Co., Ltd. | Metal nanoparticle composite and production method thereof |
EP2543098B1 (en) | 2010-03-03 | 2019-07-31 | Amprius, Inc. | Template electrode structures for depositing active materials |
US20110218304A1 (en) | 2010-03-03 | 2011-09-08 | Tecona Technologies, Inc. | Low cost and high yield method of making large quantity and homogenous metal nanoparticles and controlling their solubility |
US8518472B2 (en) | 2010-03-04 | 2013-08-27 | Guardian Industries Corp. | Large-area transparent conductive coatings including doped carbon nanotubes and nanowire composites, and methods of making the same |
EP2547370A4 (en) | 2010-03-17 | 2014-06-25 | Univ Texas | UNIVERSAL THERANOSTICS MANAGED BY CELLS |
EP2547735B1 (en) | 2010-03-19 | 2016-03-16 | Carestream Health, Inc. | Anti-corrosion agents for transparent conductive film |
WO2011149991A1 (en) | 2010-05-24 | 2011-12-01 | The Regents Of The University Of California | Inorganic nanostructure-organic polymer heterostructures useful for thermoelectric devices |
US20110291032A1 (en) | 2010-05-27 | 2011-12-01 | Industrial Technology Research Institute | Electromagnetic shielding composition, electromagnetic shielding device, anti-electrostatic device and method of manufacturing electromagnetic shielding structure |
DE102010017706B4 (de) * | 2010-07-02 | 2012-05-24 | Rent-A-Scientist Gmbh | Verfahren zur Herstellung von Silber-Nanodrähten |
WO2012011774A2 (ko) | 2010-07-22 | 2012-01-26 | 공주대학교산학협력단 | 은 나노와이어의 제조방법 |
KR101119269B1 (ko) | 2010-07-26 | 2012-03-16 | 삼성전기주식회사 | 터치패널용 투명도전막 및 그 제조방법 |
US20110088511A1 (en) | 2010-08-28 | 2011-04-21 | Ghanavi Jalaledin | Method for producing rod-shaped and branched metallic nano-structures by polyol compounds |
US8729233B2 (en) | 2010-08-30 | 2014-05-20 | Board Of Trustees Of Michigan State University | Microbial nanowires and products related thereto |
US20120061625A1 (en) | 2010-09-09 | 2012-03-15 | Eckert Karissa L | Transparent conductive films, compositions, articles, and methods |
US9321108B2 (en) | 2010-09-09 | 2016-04-26 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
WO2012040637A2 (en) | 2010-09-24 | 2012-03-29 | The Regents Of The University Of California | Nanowire-polymer composite electrodes |
DK2627713T3 (da) | 2010-10-11 | 2019-10-07 | Novomer Inc | Polymerblandinger |
US8603574B2 (en) | 2010-11-05 | 2013-12-10 | Apple Inc. | Curved touch sensor |
US9680160B2 (en) | 2010-11-08 | 2017-06-13 | The Regents Of The University Of California | Extended two dimensional metal nanotubes and nanowires useful as fuel cell catalysts and fuel cells containing the same |
GB201019212D0 (en) | 2010-11-12 | 2010-12-29 | Dupont Teijin Films Us Ltd | Polyester film |
US20120126181A1 (en) | 2010-11-22 | 2012-05-24 | Whitcomb David R | Nanowire preparation methods, compositions, and articles |
JP2014505963A (ja) | 2010-12-07 | 2014-03-06 | ロディア オペレーションズ | 導電性ナノ構造、そのようなナノ構造を作製するための方法、そのようなナノ構造を含有する導電性ポリマーフィルム、およびそのようなフィルムを含有する電子デバイス |
US9017450B2 (en) | 2010-12-09 | 2015-04-28 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US9101983B2 (en) | 2010-12-09 | 2015-08-11 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US20120148443A1 (en) | 2010-12-09 | 2012-06-14 | Whitcomb David R | Nanowire preparation methods, compositions, and articles |
US9278390B2 (en) | 2010-12-09 | 2016-03-08 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US20120148823A1 (en) | 2010-12-13 | 2012-06-14 | Innovation & Infinity Global Corp. | Transparent conductive structure and method of making the same |
WO2012081904A2 (en) | 2010-12-14 | 2012-06-21 | Lg Innotek Co., Ltd. | Nano wire and method for manufacturing the same |
WO2012083082A1 (en) | 2010-12-15 | 2012-06-21 | Sun Chemical Corporation | Printable etchant compositions for etching silver nanoware-based transparent, conductive film |
US20120156458A1 (en) | 2010-12-16 | 2012-06-21 | Innovation & Infinity Global Corp. | Diffusion barrier structure, transparent conductive structure and method for making the same |
US9630250B2 (en) | 2010-12-17 | 2017-04-25 | Seiko Pmc Corporation | Process for producing silver nanowires and agent for controlling growth of silver nanowires |
US20120164470A1 (en) | 2010-12-28 | 2012-06-28 | Applied Materials, Inc. | Silver-nickel core-sheath nanostructures and methods to fabricate |
TWI429598B (zh) | 2010-12-28 | 2014-03-11 | Benq Materials Corp | 奈米銀線及其製造方法 |
WO2012090034A1 (en) | 2010-12-30 | 2012-07-05 | Indian Institute Of Technology Madras | Gold and silver quantum clusters and methods for their preparation and use |
US9184319B2 (en) | 2011-01-14 | 2015-11-10 | The Board Of Trustees Of The Leland Stanford Junior University | Multi-terminal multi-junction photovoltaic cells |
JP5861480B2 (ja) * | 2011-02-07 | 2016-02-16 | 住友化学株式会社 | 金属ナノワイヤーの製造方法 |
US8551211B2 (en) | 2011-02-15 | 2013-10-08 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
EP2666190A4 (en) | 2011-02-28 | 2017-07-26 | University of Florida Research Foundation, Inc. | Up-conversion devices with a broad band absorber |
KR101853695B1 (ko) * | 2011-03-08 | 2018-05-02 | 디아이씨 가부시끼가이샤 | 잉크젯 기록용 도전성 수성 잉크 |
WO2012123435A1 (en) | 2011-03-14 | 2012-09-20 | Fundació Privada Institut Català De Nanotecnologia | Platinium/silver noble metal single wall hollow nanoparticles and their preparation process |
US9080255B2 (en) | 2011-03-31 | 2015-07-14 | The Hong Kong University Of Science And Technology | Method of producing silver nanowires in large quantities |
KR101970022B1 (ko) | 2011-04-05 | 2019-08-13 | 유니버시티 오브 플로리다 리서치 파운데이션, 아이엔씨. | 적어도 부분적으로 투명한 일면 발광 oled 조명 및 ir 감지 광전지 패널을 갖는 창을 제공하기 위한 방법 및 장치 |
KR20140048110A (ko) | 2011-04-05 | 2014-04-23 | 유니버시티 오브 플로리다 리서치 파운데이션, 아이엔씨. | 적어도 부분적으로 투명한 일면 발광 oled에 의한 고상 조명 창을 위한 방법 및 장치 |
BR112013025596A2 (pt) | 2011-04-05 | 2016-12-27 | Nanoholdings Llc | método e aparelho para integrar uma célula fotovoltaica infravermelha (ir) em uma célula fotovoltaica de película fina |
WO2013022499A2 (en) | 2011-04-22 | 2013-02-14 | Emory University | Polymer coated metal particles and uses related thereto |
US20120280168A1 (en) | 2011-05-03 | 2012-11-08 | Chung-Shan Institute of Science and Technology, Armaments, Bureau, Ministry of National Defense | Silver-nanowire thermo-interface material composite |
US9175183B2 (en) | 2011-05-23 | 2015-11-03 | Carestream Health, Inc. | Transparent conductive films, methods, and articles |
US8741025B2 (en) | 2011-05-23 | 2014-06-03 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US8956439B2 (en) | 2011-05-23 | 2015-02-17 | Carestream Health, Inc. | Zero-valent catalysis of metal ion reduction methods, compositions, and articles |
US20120298930A1 (en) | 2011-05-23 | 2012-11-29 | Chaofeng Zou | Nanostructure compositions, coatings, and films |
US20120298931A1 (en) | 2011-05-23 | 2012-11-29 | Carestream Health Inc. | Viscosity modifier compositions and methods |
AU2012268322A1 (en) | 2011-06-06 | 2014-01-16 | Nanoholdings, Llc | Infrared imaging device integrating an IR up-conversion device with a CMOS image sensor |
US9324508B2 (en) | 2011-06-15 | 2016-04-26 | Nokia Technologies Oy | Substrate for electrode capable of undergoing reversible deformation |
CN102259190A (zh) | 2011-06-16 | 2011-11-30 | 浙江科创新材料科技有限公司 | 一种快速大批量制备高长径比纳米银线的方法 |
KR20130000504A (ko) | 2011-06-23 | 2013-01-03 | 엘지이노텍 주식회사 | 나노 와이어 제조방법 및 나노 와이어 복합체 |
WO2012177223A1 (en) | 2011-06-24 | 2012-12-27 | Nanyang Technological University | A nanocomposite, a filtration membrane comprising the nanocomposite, and methods to form the nanocomposite and the filtration membrane |
MX2013015214A (es) | 2011-06-30 | 2014-03-21 | Nanoholdings Llc | Metodo y aparato para detectar radiacion infrarroja con ganancia. |
WO2013010398A1 (en) | 2011-07-21 | 2013-01-24 | Tsinghua University | Flexible and transparent acoustic apparatus |
WO2013019020A2 (en) | 2011-07-29 | 2013-02-07 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
KR101902927B1 (ko) | 2011-08-10 | 2018-10-02 | 삼성전자주식회사 | 신축가능한 전도성 나노섬유, 이를 포함하는 신축가능한 전극 및 그 제조방법 |
EP3358050A1 (en) | 2011-08-30 | 2018-08-08 | Cornell University | Metal and ceramic nanofibers |
CN104797363B (zh) * | 2012-09-27 | 2018-09-07 | 罗地亚经营管理公司 | 制造银纳米结构的方法和可用于此方法的共聚物 |
-
2013
- 2013-09-27 CN CN201380061858.2A patent/CN104797363B/zh active Active
- 2013-09-27 AU AU2013323179A patent/AU2013323179B2/en not_active Ceased
- 2013-09-27 EP EP13842613.5A patent/EP2900409B1/en active Active
- 2013-09-27 US US14/040,365 patent/US9410007B2/en active Active
- 2013-09-27 KR KR1020157009969A patent/KR102172116B1/ko active IP Right Grant
- 2013-09-27 US US14/040,406 patent/US20140178247A1/en not_active Abandoned
- 2013-09-27 JP JP2015534769A patent/JP6147860B2/ja active Active
- 2013-09-27 CA CA2886404A patent/CA2886404A1/en not_active Abandoned
- 2013-09-27 BR BR112015006873A patent/BR112015006873A2/pt not_active IP Right Cessation
- 2013-09-27 WO PCT/US2013/062399 patent/WO2014052887A2/en active Application Filing
-
2016
- 2016-06-28 US US15/194,796 patent/US20160303658A1/en not_active Abandoned
- 2016-10-11 JP JP2016199713A patent/JP6352358B2/ja active Active
- 2016-11-21 US US15/356,886 patent/US20170066058A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060116470A1 (en) * | 2002-09-04 | 2006-06-01 | Werner Gauweiler | Production of aqueous dispersions of cationic homo-and copolymers using amphoteric protective colloids |
US7115254B1 (en) * | 2002-10-25 | 2006-10-03 | Nalco Company | Personal care compositions containing N,N-diallyldialkylammonium halide/N-vinylpyrrolidone polymers |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10661348B2 (en) | 2015-03-03 | 2020-05-26 | Basf Se | Silver nanowire synthesis with (meth)acrylate based capping agents |
US10438714B2 (en) | 2017-12-06 | 2019-10-08 | C3Nano Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
US10714230B2 (en) | 2017-12-06 | 2020-07-14 | C3Nano Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
US11037694B2 (en) | 2017-12-06 | 2021-06-15 | C3 Nano, Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
US11848117B2 (en) | 2017-12-06 | 2023-12-19 | C3 Nano, Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
Also Published As
Publication number | Publication date |
---|---|
US20140178246A1 (en) | 2014-06-26 |
US20160303658A1 (en) | 2016-10-20 |
JP2017063036A (ja) | 2017-03-30 |
BR112015006873A2 (pt) | 2017-07-04 |
KR20150082220A (ko) | 2015-07-15 |
JP6352358B2 (ja) | 2018-07-04 |
JP6147860B2 (ja) | 2017-06-14 |
CN104797363B (zh) | 2018-09-07 |
CN104797363A (zh) | 2015-07-22 |
US20170066058A1 (en) | 2017-03-09 |
JP2016500897A (ja) | 2016-01-14 |
AU2013323179A1 (en) | 2015-04-09 |
WO2014052887A2 (en) | 2014-04-03 |
EP2900409A4 (en) | 2016-05-25 |
EP2900409A2 (en) | 2015-08-05 |
CA2886404A1 (en) | 2014-04-03 |
WO2014052887A3 (en) | 2014-06-26 |
KR102172116B1 (ko) | 2020-10-30 |
US9410007B2 (en) | 2016-08-09 |
AU2013323179B2 (en) | 2018-02-15 |
EP2900409B1 (en) | 2019-05-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9410007B2 (en) | Process for making silver nanostructures and copolymer useful in such process | |
US10130992B2 (en) | Processes for making silver nanostructures | |
AU2011338991B2 (en) | Electrically conductive nanostructures, method for making such nanostructures, electrically conductive polymer films containing such nanostructures, and electronic devices containing such films | |
WO2009038544A1 (en) | Amphiphilic polymer and processes of forming the same | |
CA2554331A1 (en) | Nanoparticles | |
HOSSEINI et al. | Chemical and electrochemical grafting of polyaniline onto chitosan | |
CN107828032B (zh) | 一种超支化星状聚离子液体及其制备方法和应用 | |
KR100666146B1 (ko) | 신규한 폴리에틸렌다이옥시싸이오펜 그래프트 공중합체 | |
CN108384000A (zh) | 一种具有生物相容性的水溶性聚苯胺的制备方法 | |
Mahalakshmi et al. | Synthesis and characterization of water soluble nanosize polyaniline using benzalkonium chloride cationic surfactant | |
Mincheva et al. | Polyelectrolyte complex nanoparticles from N‐carboxyethylchitosan and polycationic double hydrophilic diblock copolymers | |
CN111715888B (zh) | 铜基纳米结构体、其制备方法、透明导电膜及电子装置 | |
Riaz et al. | Template polymerization of nano-scale poly (1-naphthylamine): effect of oxidant on the spectral, thermal and morphological characteristics | |
JP2022114670A (ja) | 導電性高分子水溶液、及び導電性高分子膜 | |
JP2023031073A (ja) | 導電性高分子溶液の製造方法、及び導電性高分子 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: RHODIA OPERATIONS, FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALSAYED, AHMED;HOUGH, LAWRENCE;BADRE, CHANTAL;REEL/FRAME:031628/0075 Effective date: 20131107 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |