WO2008073143A2 - Methods of controlling nanostructure formations and shapes - Google Patents
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- WO2008073143A2 WO2008073143A2 PCT/US2007/014485 US2007014485W WO2008073143A2 WO 2008073143 A2 WO2008073143 A2 WO 2008073143A2 US 2007014485 W US2007014485 W US 2007014485W WO 2008073143 A2 WO2008073143 A2 WO 2008073143A2
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Definitions
- This application is related to methods of controlling the amount, shape and dimension of nanostructures by solution-based synthesis, more specifically, to the controlled formation of metal nanowires.
- Nano-sized materials can differ markedly from their analogous bulk materials.
- the physical and chemical properties of nanomaterials correlate strongly with their size, shape and morphology.
- materials scientists have focused their efforts on developing simple and effective methods for fabricating nanomaterials with controllable shapes, sizes and morphology, hence tailoring their properties.
- a solution-based synthesis (also referred to as the "polyol" process) is reasonably effective in large-scale production of metal nanostructures. See, e.g., Sun, Y. et al., (2002) Science, 298, 2176; Sun, Y. et al., (2002) Nano Lett. 2, 165; Sun, Y. et al., (2002) Adv. Mater.
- the polyol process involves the reduction of a precursor (e.g., a metal salt) of the metal nanostructure by a polyol (e.g., ethylene glycol) in the presence of polyvinyl pyrrolidone) ("PVP"). Typically, the reduction is carried out at a temperature of no more than 200 0 C. Ethylene glycol serves the dual functions as the solvent and the reducing agent.
- a precursor e.g., a metal salt
- PVP polyvinyl pyrrolidone
- the shapes and sizes of the nanostructures formed are affected by parameters including, relative amounts of PVP and the metal salt, concentrations of PVP and the metal salt, reaction time, and reaction temperature.
- metal nanostructures of various morphologies including nanocubes, nanowires, nanopyramides and multiply twinned particles, have been obtained.
- a common problem of the polyol process is that a mixture of nanostructures of several shapes is produced. The problem is compounded by poor reproducibility of the process, which is likely caused by trace amount of contaminants in the constituents of the synthesis. See, e.g., Wiley, B. et al., (2004) Nano Lett. 4(9), 1733-1739.
- the polyol process has been modified in efforts to form nanostructures of uniform shapes and sizes. For example, adding trace amount of chloride to the "polyol" process created single crystal truncated cubes and tetrahedrons. See, e.g., Wiley, B. et al., (2004) Nano Lett. 4(9), 1733-1739. Using a seed material (e.g., platinum or silver nanoparticles) in the "polyol” process generated uniform silver nanowires of high aspect ratio (about 1000). Sun, Y. et al. (2002) Chem. Mater. 14, 4736-4745. However, the problem of producing mixed nanostructures (e.g., the silver nanowires were accompanied by the formation of silver nanoparticles) persists in the existing methods. Additional separation steps are therefore necessary to obtain monodispersed nanostructures.
- a seed material e.g., platinum or silver nanoparticles
- One embodiment describes a modified polyol method for selective formation of metal nanowires, the method comprises: forming a reaction mixture including a metal salt, a capping agent and a quaternary ammonium chloride in a reducing solvent; and forming metal nanowires by reducing the metal salt in the reaction mixture.
- the capping agent is polyvinyl pyrrolidone), polyacrylamide, polyacrylic or a copolymer thereof.
- the reducing solvent comprises at least two hydroxyl groups. More specifically, the reducing solvent can be ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, or glucose.
- compositions comprising: a metal salt; a capping agent selected from polyvinyl pyrrolidone), polyacrylamide, polyacrylic and copolymers thereof; a quaternary ammonium chloride; and a reducing solvent including at least two hydroxyl groups.
- Figures 1A-1C illustrate schematically the nucleation and growth of nanostructures of different morphologies in a polyol process.
- Figure 2 shows the reaction products of mixed nanowires and nanoparticles according to a standard polyol process.
- Figure 3 schematically illustrates a one-dimensional growth of a nanowire with the assistance of a capping agent.
- Figures 4A-4D illustrate various embodiments in which various chloride additives are used in modified polyol processes.
- Figures 5A-5F show a progression of the nanowire formation at different reaction times.
- Figure 6 shows the reaction products of an embodiment in which no ionic additive is present.
- Figure 7 shows an embodiment in which 1 ,2-propylene glycol was used as the reducing solvent.
- Figure 8 shows an embodiment in which 1 ,3-propylene glycol was used as the reducing solvent.
- Nanowires can be used as conductive media in many applications.
- networks of metal nanowires e.g., silver nanowires
- Nanowires formed by the standard polyol process are typically accompanied by varying amounts of nanoparticles. See, e.g. Sun, Y. et al. (2002) Chem. Mater. 14, 4736-4745.
- both “nanoparticles” and “nanowires” refer to nanostructures in which at least one dimension is less than 500nm.
- at least one dimension of the nanostructure may be less than 100nm, less than 50nm, or less than 10nm.
- a nanowire is a one-dimensional nanostructure of high aspect ratio (length/width), i.e., the nanowire has an aspect ratio of greater than 10.
- the nanowire has an aspect ratio of greater than 50, more typically greater than 100, and more typically greater than 1000.
- a nanoparticle has an aspect ratio of no more than 10.
- the nanoparticle typically has an aspect ratio of no more than 5, and more typically no more than 2, more typically no more than 1.
- Figures 1A-1C schematically illustrate the formation of these nanostructures in a standard polyol process.
- the metal salt is reduced to elemental metal atoms by ethylene glycol in a solution phase 10.
- the metal atoms initially form small particulate seeds 14 through a homogeneous nucleation process. These particulate seeds typically have diameters in the range of 1-5nm. Some of these seeds proceed to grow in the solution phase 10 into isotropic nanostructures 20, which result from a growth that progresses indiscriminately in all dimensions. In contrast, some seeds grow into anisotropic nanostructures 24, which result from a preferential growth along a lateral dimension.
- the isotropic nanostructures 20 and anisotropic nanostructures 24 continue to grow into larger structures while maintaining their basic morphologies. Nanoparticles 30 and nanowires 34 are obtained. It is noted that during the growth process, smaller particles are less stable and typically spontaneously dissolve and contribute to the growth of the larger particles. See, e.g., U.S. Published Patent Application No. 2005/0056118,
- Figure 2 is an image of the reaction products of a standard polyol process using silver nitrate as the precursor. As shown, both nanowires and nanoparticles are present.
- One embodiment thus describes a method of forming monodispersed nanostructures (e.g., nanowires) based on a modified polyol process, which is mediated by an ionic additive. It is believed that the ionic additive promotes the formation of a single morphology while discouraging other competing nanostructures. In particular, the method produces predominately nanowires with no or few nanoparticles.
- “monodispersity” refers to at least 85%, more preferably, at least 90%, 95% or 98% by weight of nanowires.
- the method comprises: forming a reaction mixture including a metal salt, an ionic additive and a capping agent in a reducing solvent; and forming metal nanowires by reducing the metal salt in the reaction mixture.
- Metal salt refers to a neutral compound having a positively charged metal ion and a negatively charged counterion.
- the counterion may be inorganic or organic.
- Exemplary metal salts include, without limitation: silver nitrate (AgNO 3 ), silver acetate (CH 3 COO) 2 Ag), silver perchlorate (AgCIO 4 ), gold perchlorate (Au(CIO 4 ) 3 ), palladium chloride (PdCI 2 ), platinum chloride (PtCI 2 ) and the like.
- the metal salt is soluble in the reducing solvent (e.g. ethylene glycol) and dissociates into oppositely charged metal ion and the counterion.
- the solubility of the metal salt in the reducing solvent is at least 0.001 g/ml, at least 0.05g/ml, or at least 0.1g/ml.
- Suitable metal nanowires therefore include without limitation, silver, gold, copper, nickel, palladium, platinum and gold-plated silver nanowires.
- Capping agent refers to a chemical agent that preferentially interacts and adheres to a lateral surface of a growth nanowire, such that the capping agent confines the lateral surface from growing and encourages a cross section surface of the nanowire to crystallize.
- Figure 3 schematically illustrates a one-dimensional growth of the growing nanowire 36.
- the growing nanowire 36 includes the lateral surface 37 and the cross section surface 38.
- the capping agent 39 interacts with the lateral surface 36 more strongly than it does with the cross section surface 38.
- the lateral surface 36 is thus passivated while the cross section surface 38 is available for further crystallization to produce the nanowire.
- the capping agent include without limitation, polyvinyl pyrrolidone), polyarylamide, polyacrylic and any of the copolymers thereof.
- Reducing solvent refers to a polar solvent in which the metal salt, the ionic additive and the capping agent are soluble.
- the reducing solvent functions as a reducing agent to transform the metal salt to its corresponding elemental metal.
- the reducing solvent is a chemical reagent comprising at least two hydroxyl groups.
- the reducing solvents include without limitation, diols, polyols, glycols, or mixtures thereof. More specifically, the reducing solvent can be, for example, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, and glucose.
- Ionic additive refers to a salt additive comprising a cation and an anion.
- the cation and anion are associated by ionic interaction and dissociate in polar solvents such as water, alcohol, diols and polyols (including ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, and glucose).
- polar solvents such as water, alcohol, diols and polyols (including ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, and glucose).
- the cation can be organic or inorganic.
- the anions are typically inorganic.
- Exemplary anions include halides (Cl “ , Br “ , I “ , F “ ), phosphate (PO 4 3” ), sulfate (SO 4 2” ), hydrogen sulfate (HSO 4 " ), aryl and alkyl sulfonates (RSO 3 " ), and the like.
- the ionic additive may further include their corresponding acids, i.e., the cation is a proton.
- the ionic additive is a quaternary ammonium chloride.
- quaternary ammonium chloride refers to ammonium chloride (NH 4 + CI " ) in which, all four hydrogens have been replaced by an organic group.
- the quaternary ammonium chloride can be typically represented by formula NR 4 + CI ' , wherein each R is the same or different and independently an alkyl, alkenyl, alkynyl, aryl, or aralkyl.
- Alkyl refers to monovalent saturated hydrocarbon structure of between 1 and 20 carbons, in which the carbons are arranged in either a linear or branched manner.
- Lower alkyl refers to alkyl groups of 1 to 5 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s- and t-butyl and the like. Examples of alkyl groups of longer chains include octyl (Ce), decyl (C10), dodecyl (C12), cetyl (Ci 6 ), and the like.
- butyl is meant to include n-butyl, sec-butyl, isobutyl and t-butyl; propyl includes n-propyl and isopropyl.
- alkyl can be optionally substituted with a halogen (F, Br, Cl or I), alkoxy, amine and the like.
- halogen F, Br, Cl or I
- alkoxy amine and the like.
- alkenyl refers to a monovalent hydrocarbon structure of between
- alkyl can be optionally substituted with a halogen (F, Br, Cl or I), alkoxy, amine or the like.
- halogen F, Br, Cl or I
- Alkynyl refers to a monovalent hydrocarbon structure of between
- 2 and 20 carbon atoms with at least one triple bond.
- Examples include without limitation: ethynyl, propynyl, butynyl, pentynyl, hexynyl, methylpropynyl, 4- methyl-1-butynyl, 4-propyl-2-pentynyl and the like.
- Alkoxy refers to a radical of the formula -O-alkyl. Examples include methoxy, ethoxy, propoxy, isopropoxy, and the like. Lower-alkoxy refers to groups containing one to five carbons.
- Aryl refers to optionally substituted phenyl or naphthyl.
- exemplary substituents for aryl include one or more of halogen, hydroxy, alkoxy, amino, mercapto or the like.
- Alkyl refers to an alkyl residue substituted with at least an aryl group.
- the aralkyl can be typically represented by the formula aryl-alkyl-.
- Exemplary aralkyls include without limitation phenylmethyl ⁇ i.e., benzyl) or phenylethyl group.
- Exemplary ionic additives therefore include without limitation: tetramethylammonium chloride (TMAC), tetrabutylammonium chloride (TBAC), cetyl trimethylammonium chloride (CTAC), Cs-Ci ⁇ alkyl dimethyl benzyl ammonium chloride, methyl trioctylammonium chloride ⁇ i.e., Aliquat 336 ® ) and the like.
- TMAC tetramethylammonium chloride
- TBAC tetrabutylammonium chloride
- CAC cetyl trimethylammonium chloride
- Cs-Ci ⁇ alkyl dimethyl benzyl ammonium chloride methyl trioctylammonium chloride ⁇ i.e., Aliquat 336 ®
- TMAC tetramethylammonium chloride
- TBAC tetrabutylammonium chloride
- CAC cetyl trimethylammonium chloride
- Quaternary ammonium ions are permanently charged cations that typically are not influenced by the pH of their environment. They are soluble in the reducing solvent, as defined herein. Moreover, they are compatible with the capping agent (e.g., PVP and its copolymers) due to the organic moieties present.
- the capping agent e.g., PVP and its copolymers
- the quaternary ammonium ions differ from inorganic cations in their effects on the formation of silver nanowires in the modified polyol process. More specifically, the presence of a quaternary ammonium based ionic additive encourages a predominately anisotropic growth of nanostructures to produce nanowires in relatively high yield and relatively high monodispersity.
- Figures 4A-4D show images of silver nanowire formations using various chloride-based ionic additives, including HCI, ZnCI 2 , MgCI 2 and TBAC, respectively. All the reactions were carried out by initially mixing 0.1 M AgNU 3 , 0.15M PVP and 0.001 M of the chlorides at room temperature (25 0 C) to 40 0 C. The reaction mixture was then heated to about 160 0 C. Typically, nanostructures (nanowires and/or nanoparticles) were formed rapidly after a brief induction period (10-30 minutes). The products were collected after about 30 minutes.
- Figures 4A-4C show that silver nanowires were formed accompanied by varying degrees of other nanostructures (e.g., nanoparticles).
- Figure 4D shows uniform silver nanowires of between 3 and 100 ⁇ m long with little or no nanoparticle formation. The yield of the silver nanowires is therefore particularly optimized using TBAC as the additive, with high overall yield and high monodispersity.
- the anion (i.e., chloride) in the ionic additive also plays an important role in controlling the nanowire formation. It is found that ionic additives based on other halides (e.g., bromide), do not have the same effect as the chloride-based ionic additive. For example, using cetyl trimethylammonium bromide in the place of cetyl trimethylammonium chloride produces only nanoparticles.
- halides e.g., bromide
- the concentrations of the constituents in the reaction mixture have certain impact on the formation of the nanostructures and their yields.
- the metal salt in the reaction mixture is typically in the range of about 0.01 M to 0.2M, more preferably 0.05M to 0.1 M, for an optimal yield of nanowires.
- the concentration of PVP is typically in the range of 0.01 M to 0.2M, more preferably, 0.05M to 0.15M.
- the concentration of the quaternary ammonium chloride in the reaction mixture is in the range of 0.001 M - 0.5 M. Preferably, the concentration is less than 0.1 M to avoid precipitation.
- the relative molar ratio between the quaternary ammonium chloride and the metal salt is about 0.1% to 10%, more preferably, about 0.5% to 1%.
- the reaction temperature influences the yields and length of the metal nanowires formed.
- the metal salt, PVP and the ionic additive are mixed in ethylene glycol at a first temperature to provide a reaction mixture.
- the first temperature can be in the range of about 20 0 C to 4O 0 C.
- the reaction mixture is thoroughly mixed before it is heated to a second temperature.
- the second temperature is typically maintained in a range of about 5O 0 C to about 200 0 C 1 more typically, at about 150-160 0 C. At temperatures higher than 170 0 C, shorter nanowires were formed as compared to the nanowires formed at lower temperatures.
- Figures 5A- 5F illustrate a progression of the nanowire formation visualized at x100DF. Samples were taken from the reaction mixture at the reaction times indicated. Each sample was cooled in an ice bath to halt the growth of the nanostructures. Figure 5A shows that within an initial induction period (about 7 minutes), minute particles 40 (e.g., seeds) were formed. As shown in Figures 5B-5D, in the next 3 minutes, nanowires 44 rapidly took shape. At 15 minutes into the reaction, longer nanowires 48 populated the reaction mixture ( Figure 5E). Thereafter, an additional 5 minutes yielded more nanowires (Figure 5F). The reaction was completed within 30 minutes, whereby no more nanowires were formed even with prolonged reaction time.
- minute particles 40 e.g., seeds
- reaction times are greatly influenced by the choice of solvent, e.g. 1 ,2-propylene glycol leads to faster nanowire growth than ethylene glycol while glycerol shows slower reaction rates.
- the modified polyol process is described in more detail by the following non-limiting examples.
- reaction products were allowed to settle to the bottom of the vial and the ethylene glycol was removed.
- the reaction products were dried, and the reaction products were then re-suspended in 5ml deionized water.
- the suspension was filtered through a glass frit (Fine, 4-6 ⁇ m, Kontes).
- the retentate (containing nanowires which could not filter through the frit) were dried and weighed. Further analysis of the reaction products indicated that they were substantially nanowires, with no or very few nanoparticles.
- the silver nanowires produced had a mean diameter of 75 ⁇ 8 nm, and an average length of 9.7 ⁇ 2.6 ⁇ m.
- microscale reaction described herein was highly reproducible which consistently yielded at a high percentage of silver nanowires.
- Example 1 As a comparison, the reaction of Example 1 was carried out without the tetrabutylammonium chloride additive. As shown in Figure 6, only nanoparticles were obtained.
- the silver nanowires produced had a mean diameter of 62 ⁇ 7 nm, and an average length of 8.5 ⁇ 1.9 ⁇ m. There was no precipitate or nanoparticles formed (See, e.g., Figure 4D).
- the large-scale reaction described herein was highly reproducible.
- silver nanowires were also prepared according to the method described in U.S. Published Patent Application No. 2005/0056118. More specifically, 5ml ethylene glycol was preheated at 160 0 C. 3ml of AgNO3 solution in ethylene glycol (0.085M) and 3ml of PVP solution in ethylene glycol (0.13M) were simultaneously added to the preheated ethylene glycol. The reaction mixture was heated and maintained at 160 0 C for 40 minutes. The resulting products were observed as a mixture of nanowires and nanoparticles, shown in Figure 2.
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Abstract
A method of forming monodispersed metal nanowires comprising: forming a reaction mixture including a metal salt, a capping agent and a quaternary ammonium chloride in a reducing solvent at a first temperature; and forming metal nanowires by reducing the metal salt in the reaction mixture.
Description
METHODS OF CONTROLLING NANOSTRUCTURE FORMATIONS AND SHAPES
BACKGROUND OF THE INVENTION
Field of the Invention This application is related to methods of controlling the amount, shape and dimension of nanostructures by solution-based synthesis, more specifically, to the controlled formation of metal nanowires.
Description of the Related Art
Nano-sized materials (or nanomaterials) can differ markedly from their analogous bulk materials. In particular, the physical and chemical properties of nanomaterials correlate strongly with their size, shape and morphology. As a result, materials scientists have focused their efforts on developing simple and effective methods for fabricating nanomaterials with controllable shapes, sizes and morphology, hence tailoring their properties. A solution-based synthesis (also referred to as the "polyol" process) is reasonably effective in large-scale production of metal nanostructures. See, e.g., Sun, Y. et al., (2002) Science, 298, 2176; Sun, Y. et al., (2002) Nano Lett. 2, 165; Sun, Y. et al., (2002) Adv. Mater. 14, 833; Kim, F. et al., (2004) Angew. Chem. Int. Ed. 116, 3759; and U.S. Published Application 2005/0056118. The polyol process involves the reduction of a precursor (e.g., a metal salt) of the metal nanostructure by a polyol (e.g., ethylene glycol) in the presence of polyvinyl pyrrolidone) ("PVP"). Typically, the reduction is carried out at a temperature of no more than 2000C. Ethylene glycol serves the dual functions as the solvent and the reducing agent. Typically, the shapes and sizes of the nanostructures formed are affected by parameters including, relative amounts of PVP and the metal salt, concentrations of PVP and the metal salt, reaction time, and reaction temperature.
According to this method, metal nanostructures of various morphologies, including nanocubes, nanowires, nanopyramides and multiply twinned particles, have been obtained. However, a common problem of the polyol process is that a mixture of nanostructures of several shapes is produced. The problem is compounded by poor reproducibility of the process, which is likely caused by trace amount of contaminants in the constituents of the synthesis. See, e.g., Wiley, B. et al., (2004) Nano Lett. 4(9), 1733-1739.
The polyol process has been modified in efforts to form nanostructures of uniform shapes and sizes. For example, adding trace amount of chloride to the "polyol" process created single crystal truncated cubes and tetrahedrons. See, e.g., Wiley, B. et al., (2004) Nano Lett. 4(9), 1733-1739. Using a seed material (e.g., platinum or silver nanoparticles) in the "polyol" process generated uniform silver nanowires of high aspect ratio (about 1000). Sun, Y. et al. (2002) Chem. Mater. 14, 4736-4745. However, the problem of producing mixed nanostructures (e.g., the silver nanowires were accompanied by the formation of silver nanoparticles) persists in the existing methods. Additional separation steps are therefore necessary to obtain monodispersed nanostructures.
There remains a need in the art to fabricate nanostructures with controllable shapes and sizes in an effective and reproducible fashion.
BRIEF SUMMARY OF THE INVENTION
One embodiment describes a modified polyol method for selective formation of metal nanowires, the method comprises: forming a reaction mixture including a metal salt, a capping agent and a quaternary ammonium chloride in a reducing solvent; and forming metal nanowires by reducing the metal salt in the reaction mixture.
In various embodiments, the capping agent is polyvinyl pyrrolidone), polyacrylamide, polyacrylic or a copolymer thereof.
In various embodiments, the reducing solvent comprises at least two hydroxyl groups. More specifically, the reducing solvent can be ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, or glucose.
Another embodiment describes a composition comprising: a metal salt; a capping agent selected from polyvinyl pyrrolidone), polyacrylamide, polyacrylic and copolymers thereof; a quaternary ammonium chloride; and a reducing solvent including at least two hydroxyl groups.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS In the drawings, identical reference numbers identify similar elements or acts. The sizes and relative positions of elements in the drawings are not necessarily drawn to scale. For example, the shapes of various elements and angles are not drawn to scale, and some of these elements are arbitrarily enlarged and positioned to improve drawing legibility. Further, the particular shapes of the elements as drawn are not intended to convey any information regarding the actual shape of the particular elements, and have been selected solely for ease of recognition in the drawings.
Figures 1A-1C illustrate schematically the nucleation and growth of nanostructures of different morphologies in a polyol process.
Figure 2 shows the reaction products of mixed nanowires and nanoparticles according to a standard polyol process.
Figure 3 schematically illustrates a one-dimensional growth of a nanowire with the assistance of a capping agent.
Figures 4A-4D illustrate various embodiments in which various chloride additives are used in modified polyol processes. Figures 5A-5F show a progression of the nanowire formation at different reaction times.
Figure 6 shows the reaction products of an embodiment in which no ionic additive is present.
Figure 7 shows an embodiment in which 1 ,2-propylene glycol was used as the reducing solvent.
Figure 8 shows an embodiment in which 1 ,3-propylene glycol was used as the reducing solvent.
DETAILED DESCRIPTION OF THE INVENTION
Nanowires, especially metal nanowires, can be used as conductive media in many applications. In particular, networks of metal nanowires (e.g., silver nanowires) impart both electrical conductivity and high optical transmission, which makes them a suitable material for fabricating transparent conductors.
Nanowires formed by the standard polyol process are typically accompanied by varying amounts of nanoparticles. See, e.g. Sun, Y. et al. (2002) Chem. Mater. 14, 4736-4745. As used herein, both "nanoparticles" and "nanowires" refer to nanostructures in which at least one dimension is less than 500nm. For example, at least one dimension of the nanostructure may be less than 100nm, less than 50nm, or less than 10nm. A nanowire is a one-dimensional nanostructure of high aspect ratio (length/width), i.e., the nanowire has an aspect ratio of greater than 10. Typically, the nanowire has an aspect ratio of greater than 50, more typically greater than 100, and more typically greater than 1000. In contrast, a nanoparticle has an aspect ratio of no more than 10. For example, the nanoparticle typically has an aspect ratio of no more than 5, and more typically no more than 2, more typically no more than 1.
Figures 1A-1C schematically illustrate the formation of these nanostructures in a standard polyol process. At an initial stage (Figure 1A), the metal salt is reduced to elemental metal atoms by ethylene glycol in a solution phase 10. In general, the metal atoms initially form small particulate seeds 14 through a homogeneous nucleation process. These particulate seeds typically have diameters in the range of 1-5nm. Some of these seeds proceed to grow in the solution phase 10 into isotropic nanostructures 20, which result from a growth that progresses indiscriminately in all dimensions. In contrast, some seeds grow into anisotropic nanostructures 24, which result from a preferential
growth along a lateral dimension. As shown in Figure 1C, the isotropic nanostructures 20 and anisotropic nanostructures 24 continue to grow into larger structures while maintaining their basic morphologies. Nanoparticles 30 and nanowires 34 are obtained. It is noted that during the growth process, smaller particles are less stable and typically spontaneously dissolve and contribute to the growth of the larger particles. See, e.g., U.S. Published Patent Application No. 2005/0056118,
Although reaction conditions such as the reaction time and temperature can be adjusted to bias the formation of the nanowires, the standard polyol process fails to produce uniform nanowires in satisfactory yields. Figure 2 is an image of the reaction products of a standard polyol process using silver nitrate as the precursor. As shown, both nanowires and nanoparticles are present.
One embodiment thus describes a method of forming monodispersed nanostructures (e.g., nanowires) based on a modified polyol process, which is mediated by an ionic additive. It is believed that the ionic additive promotes the formation of a single morphology while discouraging other competing nanostructures. In particular, the method produces predominately nanowires with no or few nanoparticles. As used herein, "monodispersity" refers to at least 85%, more preferably, at least 90%, 95% or 98% by weight of nanowires.
More specifically, the method comprises: forming a reaction mixture including a metal salt, an ionic additive and a capping agent in a reducing solvent; and forming metal nanowires by reducing the metal salt in the reaction mixture.
"Metal salt" refers to a neutral compound having a positively charged metal ion and a negatively charged counterion. The counterion may be inorganic or organic. Exemplary metal salts include, without limitation: silver nitrate (AgNO3), silver acetate (CH3COO)2Ag), silver perchlorate (AgCIO4), gold perchlorate (Au(CIO4)3), palladium chloride (PdCI2), platinum chloride (PtCI2) and the like. Typically, the metal salt is soluble in the reducing solvent (e.g.
ethylene glycol) and dissociates into oppositely charged metal ion and the counterion. Typically, the solubility of the metal salt in the reducing solvent is at least 0.001 g/ml, at least 0.05g/ml, or at least 0.1g/ml.
Reduction of the metal salt in the above reaction mixture produces corresponding elemental metal. The elemental metal crystallizes or grows into a one-dimensional nanostructure (i.e. nanowires). Suitable metal nanowires therefore include without limitation, silver, gold, copper, nickel, palladium, platinum and gold-plated silver nanowires.
"Capping agent" refers to a chemical agent that preferentially interacts and adheres to a lateral surface of a growth nanowire, such that the capping agent confines the lateral surface from growing and encourages a cross section surface of the nanowire to crystallize. Figure 3 schematically illustrates a one-dimensional growth of the growing nanowire 36. The growing nanowire 36 includes the lateral surface 37 and the cross section surface 38. The capping agent 39 interacts with the lateral surface 36 more strongly than it does with the cross section surface 38. The lateral surface 36 is thus passivated while the cross section surface 38 is available for further crystallization to produce the nanowire. Examples of the capping agent include without limitation, polyvinyl pyrrolidone), polyarylamide, polyacrylic and any of the copolymers thereof.
"Reducing solvent" refers to a polar solvent in which the metal salt, the ionic additive and the capping agent are soluble. In addition, the reducing solvent functions as a reducing agent to transform the metal salt to its corresponding elemental metal. Typically, the reducing solvent is a chemical reagent comprising at least two hydroxyl groups. Examples of the reducing solvents include without limitation, diols, polyols, glycols, or mixtures thereof. More specifically, the reducing solvent can be, for example, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, and glucose.
"Ionic additive" refers to a salt additive comprising a cation and an anion. The cation and anion are associated by ionic interaction and dissociate in polar solvents such as water, alcohol, diols and polyols (including ethylene
glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, and glucose). The cation can be organic or inorganic. The anions are typically inorganic. Exemplary anions include halides (Cl", Br", I", F"), phosphate (PO4 3"), sulfate (SO4 2"), hydrogen sulfate (HSO4 "), aryl and alkyl sulfonates (RSO3 "), and the like. The ionic additive may further include their corresponding acids, i.e., the cation is a proton.
In certain embodiments, the ionic additive is a quaternary ammonium chloride. As used herein, "quaternary ammonium chloride" refers to ammonium chloride (NH4 +CI") in which, all four hydrogens have been replaced by an organic group. Thus, the quaternary ammonium chloride can be typically represented by formula NR4 +CI', wherein each R is the same or different and independently an alkyl, alkenyl, alkynyl, aryl, or aralkyl.
"Alkyl" refers to monovalent saturated hydrocarbon structure of between 1 and 20 carbons, in which the carbons are arranged in either a linear or branched manner. Lower alkyl refers to alkyl groups of 1 to 5 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s- and t-butyl and the like. Examples of alkyl groups of longer chains include octyl (Ce), decyl (C10), dodecyl (C12), cetyl (Ci6), and the like. When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are contemplated; thus, for example, "butyl" is meant to include n-butyl, sec-butyl, isobutyl and t-butyl; propyl includes n-propyl and isopropyl.
Unless specified otherwise, the alkyl can be optionally substituted with a halogen (F, Br, Cl or I), alkoxy, amine and the like. "Alkenyl" refers to a monovalent hydrocarbon structure of between
2 and 20 carbon atoms with at least one double bond. Examples include without limitation: ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl and the like. Unless specified otherwise, the alkyl can be optionally substituted with a halogen (F, Br, Cl or I), alkoxy, amine or the like. "Alkynyl" refers to a monovalent hydrocarbon structure of between
2 and 20 carbon atoms with at least one triple bond. Examples include without
limitation: ethynyl, propynyl, butynyl, pentynyl, hexynyl, methylpropynyl, 4- methyl-1-butynyl, 4-propyl-2-pentynyl and the like.
"Alkoxy" refers to a radical of the formula -O-alkyl. Examples include methoxy, ethoxy, propoxy, isopropoxy, and the like. Lower-alkoxy refers to groups containing one to five carbons.
"Aryl" refers to optionally substituted phenyl or naphthyl. Exemplary substituents for aryl include one or more of halogen, hydroxy, alkoxy, amino, mercapto or the like.
"Aralkyl" refers to an alkyl residue substituted with at least an aryl group. The aralkyl can be typically represented by the formula aryl-alkyl-. Exemplary aralkyls include without limitation phenylmethyl {i.e., benzyl) or phenylethyl group.
Exemplary ionic additives therefore include without limitation: tetramethylammonium chloride (TMAC), tetrabutylammonium chloride (TBAC), cetyl trimethylammonium chloride (CTAC), Cs-Ciβ alkyl dimethyl benzyl ammonium chloride, methyl trioctylammonium chloride {i.e., Aliquat 336®) and the like.
Quaternary ammonium ions (NR4 +) are permanently charged cations that typically are not influenced by the pH of their environment. They are soluble in the reducing solvent, as defined herein. Moreover, they are compatible with the capping agent (e.g., PVP and its copolymers) due to the organic moieties present.
The quaternary ammonium ions differ from inorganic cations in their effects on the formation of silver nanowires in the modified polyol process. More specifically, the presence of a quaternary ammonium based ionic additive encourages a predominately anisotropic growth of nanostructures to produce nanowires in relatively high yield and relatively high monodispersity.
Figures 4A-4D show images of silver nanowire formations using various chloride-based ionic additives, including HCI, ZnCI2, MgCI2 and TBAC, respectively. All the reactions were carried out by initially mixing 0.1 M AgNU3, 0.15M PVP and 0.001 M of the chlorides at room temperature (250C) to 400C.
The reaction mixture was then heated to about 1600C. Typically, nanostructures (nanowires and/or nanoparticles) were formed rapidly after a brief induction period (10-30 minutes). The products were collected after about 30 minutes. Figures 4A-4C show that silver nanowires were formed accompanied by varying degrees of other nanostructures (e.g., nanoparticles). Figure 4D, by comparison, shows uniform silver nanowires of between 3 and 100 μm long with little or no nanoparticle formation. The yield of the silver nanowires is therefore particularly optimized using TBAC as the additive, with high overall yield and high monodispersity.
The anion (i.e., chloride) in the ionic additive also plays an important role in controlling the nanowire formation. It is found that ionic additives based on other halides (e.g., bromide), do not have the same effect as the chloride-based ionic additive. For example, using cetyl trimethylammonium bromide in the place of cetyl trimethylammonium chloride produces only nanoparticles.
It has been further observed that the concentrations of the constituents in the reaction mixture have certain impact on the formation of the nanostructures and their yields. For example, the metal salt in the reaction mixture is typically in the range of about 0.01 M to 0.2M, more preferably 0.05M to 0.1 M, for an optimal yield of nanowires. In addition, the concentration of PVP is typically in the range of 0.01 M to 0.2M, more preferably, 0.05M to 0.15M. In various embodiments, the concentration of the quaternary ammonium chloride in the reaction mixture is in the range of 0.001 M - 0.5 M. Preferably, the concentration is less than 0.1 M to avoid precipitation. Typically, the relative molar ratio between the quaternary ammonium chloride and the metal salt is about 0.1% to 10%, more preferably, about 0.5% to 1%.
The reaction temperature influences the yields and length of the metal nanowires formed. Typically, the metal salt, PVP and the ionic additive are mixed in ethylene glycol at a first temperature to provide a reaction mixture. The first temperature can be in the range of about 200C to 4O0C. The reaction
mixture is thoroughly mixed before it is heated to a second temperature. The second temperature is typically maintained in a range of about 5O0C to about 2000C1 more typically, at about 150-1600C. At temperatures higher than 1700C, shorter nanowires were formed as compared to the nanowires formed at lower temperatures.
The yield and length of the metal nanowires produced by the modified polyol process are further controlled by the reaction time. Figures 5A- 5F illustrate a progression of the nanowire formation visualized at x100DF. Samples were taken from the reaction mixture at the reaction times indicated. Each sample was cooled in an ice bath to halt the growth of the nanostructures. Figure 5A shows that within an initial induction period (about 7 minutes), minute particles 40 (e.g., seeds) were formed. As shown in Figures 5B-5D, in the next 3 minutes, nanowires 44 rapidly took shape. At 15 minutes into the reaction, longer nanowires 48 populated the reaction mixture (Figure 5E). Thereafter, an additional 5 minutes yielded more nanowires (Figure 5F). The reaction was completed within 30 minutes, whereby no more nanowires were formed even with prolonged reaction time.
The reaction times are greatly influenced by the choice of solvent, e.g. 1 ,2-propylene glycol leads to faster nanowire growth than ethylene glycol while glycerol shows slower reaction rates.
The modified polyol process is described in more detail by the following non-limiting examples.
EXAMPLES
EXAMPLE 1
MODIFIED POLYOL PROCESS - MICROSCALE
In a 10ml vial, 0.5 ml solution of AgNU3 in ethylene glycol (0.1M) was combined with 0.5 ml solution of PVP in ethylene glycol (0.15M) and 0.5ml solution of tetrabutylammonium chloride in ethylene glycol (0.001 M) at room temperature (25°C). The vial was dipped into an oil bath (1900C) for 20-30
minutes for the reaction to complete. Grey and iridescent reaction products were obtained. Visualization under a microscope (x1 OODF) indicated uniform nanowires were formed.
The reaction products were allowed to settle to the bottom of the vial and the ethylene glycol was removed. The reaction products were dried, and the reaction products were then re-suspended in 5ml deionized water. The suspension was filtered through a glass frit (Fine, 4-6μm, Kontes). The retentate (containing nanowires which could not filter through the frit) were dried and weighed. Further analysis of the reaction products indicated that they were substantially nanowires, with no or very few nanoparticles.
The silver nanowires produced had a mean diameter of 75 ± 8 nm, and an average length of 9.7 ± 2.6 μm.
The microscale reaction described herein was highly reproducible which consistently yielded at a high percentage of silver nanowires.
EXAMPLE 2
WITHOUT IONIC ADDITIVE
As a comparison, the reaction of Example 1 was carried out without the tetrabutylammonium chloride additive. As shown in Figure 6, only nanoparticles were obtained.
EXAMPLE 3
MODIFIED POLYOL PROCESS - LARGE-SCALE In a 1000 ml flask, 4.171 g PVP (MW=50,000, 37.6 mmol), 70mg tetrabutylammonium chloride (0.25 mmol), and 4.254 g AgNO3 (25 mmol) were mixed in 500 ml ethylene glycol). The reaction mixture was stirred at room temperature (25°C) for 15 minutes before the flask was heated with a heating mantle set to 2000C. The internal temperature of the reaction mixture was controlled at about 1500C. Within 30 minutes, the reaction mixture has turned
into a grey and iridescent suspension of silver nanowires. The silver nanowires produced had a mean diameter of 62 ± 7 nm, and an average length of 8.5 ± 1.9 μm. There was no precipitate or nanoparticles formed (See, e.g., Figure 4D). The large-scale reaction described herein was highly reproducible.
EXAMPLE 4
COMPARATIVE RESULT - STANDARD POLYOL PROCESS
For comparison purpose, silver nanowires were also prepared according to the method described in U.S. Published Patent Application No. 2005/0056118. More specifically, 5ml ethylene glycol was preheated at 1600C. 3ml of AgNO3 solution in ethylene glycol (0.085M) and 3ml of PVP solution in ethylene glycol (0.13M) were simultaneously added to the preheated ethylene glycol. The reaction mixture was heated and maintained at 1600C for 40 minutes. The resulting products were observed as a mixture of nanowires and nanoparticles, shown in Figure 2.
EXAMPLE 5
MODIFIED POLYOL PROCESS - LARGE-SCALE
In a 5000 ml flask, 49.98 g PVP (MW=50,000, 450 mmol), 0.84 g tetrabutylammonium chloride (3 mmol), and 51.02 g AgNOβ (300 mmol) were mixed in 3000 ml ethylene glycol). The PVP was thoroughly dispersed in about 1/3 of the ethylene glycol with a high shear mixer before being added into the reaction flask. The reaction mixture was stirred at room temperature (25°C) for 15 minutes before the flask was heated with a heating mantle set to 2000C. The internal temperature of the reaction mixture was controlled at about 1400C. Within 30 minutes, the reaction mixture has turned into a grey and iridescent suspension of silver nanowires. The silver nanowires produced had a mean diameter of 82.6 ± 22.3 nm, and an average length of 14.1 ± 8.1 μm. There were few nanoparticles formed.
The large-scale reaction described herein was highly reproducible.
EXAMPLE 6
MODIFIED POLYOL PROCESS - LOWER TEMPERATURE
In a 100 ml flask, 0.42 g PVP (MW=50,000, 3.76 mmol), 0.07 ml tetrabutylammonium chloride (0.25 mmol), and 0.43 g AgNO3 (2.5 mmol) were mixed in 50 ml ethylene glycol). The reaction mixture was stirred at room temperature (250C) for 15 minutes before the flask was heated in an oven set to 8O0C without stirring. Within 2 weeks, the reaction mixture turned into a grey and iridescent suspension of silver nanowires. The silver nanowires produced had a mean diameter of 62 ± 18 nm, and an average length of 43 ± 20 μm. The reaction products were predominantly long, thin nanowires.
EXAMPLE 7
MODIFIED POLYOL PROCESS - 1 ,3-PROPYLENE GLYCOL SOLVENT
In a 1000 ml flask, 4.17 g PVP (MW=50,000, 37.6 mmol), 72 mg tetrabutylammonium chloride (0.25 mmol), and 4.25 g AgNO3 (25 mmol) were mixed in 500 ml 1 ,2-propylene glycol). The reaction mixture was stirred at room temperature (250C) for 15 minutes before the flask was heated with a heating mantle set to 2000C. The internal temperature of the reaction mixture was controlled at about 16O0C. Within 30 minutes, the reaction mixture turned into a grey and iridescent suspension of silver nanowires. The reaction products were predominantly nanowires.
EXAMPLE 8
MODIFIED POLYOL PROCESS - 1 ,2-PROPYLENE GLYCOL SOLVENT
In a 1000 ml flask, 0.417 g PVP (MW=50,000, 3.76 mmol), 7.2 mg tetrabutylammonium chloride (0.025 mmol), and 0.425 g AgNO3 (2.5 mmol) were mixed in 50 ml 1 ,2-propylene glycol). The reaction mixture was stirred at
room temperature (25°C) for 15 minutes before the flask was heated with a heating mantle set to 810C. Within 2 days, the reaction mixture turned into a grey and iridescent suspension of silver nanowires. The reaction products were predominantly nanowires as shown in Figure 7.
EXAMPLE 9 MODIFIED POLYOL PROCESS - 1 ,3-PROPYLENE GLYCOL SOLVENT
In a 100 ml flask, 0.42 g PVP (MW=50,000, 3.76 mmol), 0.07 ml tetrabutylammonium chloride (0.25 mmol), and 0.43 g AgNO3 (2.5 mmol) were mixed in 50 ml 1 ,3-propylene glycol). The reaction mixture was stirred at room temperature (250C) for 15 minutes before the flask was heated in an oven set to 1000C without stirring. Within 12 hours, the reaction mixture turned into a grey and iridescent suspension of silver nanowires. The reaction products were predominantly nanowires as shown in Figure 8.
All of the above U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non- patent publications referred to in this specification and/or listed in the Application Data Sheet, are incorporated herein by reference, in their entirety. From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims.
Claims
1. A method of forming monodispersed metal nanowires comprising: forming a reaction mixture including a metal salt, a capping agent and a quaternary ammonium chloride in a reducing solvent; and forming metal nanowires by reducing the metal salt in the reaction mixture.
2. The method of claim 1 wherein the metal salt is silver nitrate, silver acetate, silver perchlorate, gold perchlorate, palladium chloride, or platinum chloride.
3. The method of claim 1 wherein the quaternary ammonium chloride is represented by formula NR4 +CI", each R being the same or different and independently an alkyl, alkenyl, alkynyl, aryl, or aralkyl.
4. The method of claim 3 wherein each R is the same or different and independently methyl, butyl, octyl, decyl or cetyl.
5. The method of claim 4 wherein the quaternary ammonium chloride is tetramethylammonium chloride, tetrabutylammonium chloride , cetyl trimethylammonium chloride, C8-C-Ie alkyl dimethyl benzyl ammonium chloride, or methyl trioctylammonium chloride.
6. The method of claim 1 wherein the capping agent is polyvinyl pyrrolidone), polyacrylamide, polyacrylic or a copolymer thereof.
7. The method of claim 1 wherein the reducing solvent includes at least two hydroxyl groups.
8. The method of claim 7 wherein the reducing solvent is ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, glycerol, or glucose.
9. The method of claim 1 wherein the reaction mixture is formed at a first temperature of about 2O0C to about 40°C.
10. The method of claim 1 wherein the reducing is carried out at a second temperature of about 500C to about 17O0C.
11. The method of claim 1 wherein the metal salt is silver nitrate and silver nanowires are formed.
12. The method of claim 11 wherein the silver nanowires have a mean diameter of 75±8nm, and an average length of 9.7±2.6μm.
13. The method of claim 1 wherein the reaction mixture includes silver nitrate, polyvinyl pyrrolidone), tetrabutylammonium chloride and ethylene glycol.
14. The method of claim 1 wherein a molar ratio of the quaternary ammonium chloride and the metal salt is between about 0.001 and 0.1.
15. A composition comprising: a metal salt; a capping agent selected from polyvinyl pyrrolidone), polyacrylamide, polyacrylic and copolymers thereof; a quaternary ammonium chloride; and a reducing solvent including at least two hydroxyl groups.
16. The composition of claim 15 wherein the metal salt is silver nitrate, silver acetate, silver perchlorate, gold perchlorate, palladium chloride, or platinum chloride
17. The composition of claim 15 wherein the quaternary ammonium chloride is represented by formula NR4 +CI", each R being the same or different and independently an alkyl, alkenyl, alkynyl, aryl, or aralkyl.
18. The composition of claim 15 wherein each R is the same or different and independently methyl, butyl, octyl, decyl or cetyl.
19. The composition of claim 15 wherein the quaternary ammonium chloride is tetramethylammonium chloride, tetrabutylammonium chloride , cetyl trimethylammonium chloride, Cβ-C-iβ alkyl dimethyl benzyl ammonium chloride, or methyl trioctylammonium chloride.
20. The composition of claim 15 wherein a molar ratio of the quaternary ammonium chloride and the metal salt is between about 0.001 and 0.1.
21. The composition of claim 15 wherein the reducing solvent is ethylene glycol, 1 ,2-propylene glycol, 1,3-propylene glycol, glycerin, glycerol, or glucose.
22. The composition of claim 15 wherein the capping agent is polyvinyl pyrrolidone) having a molecular weight of 50,000.
23. The composition of claim 15 comprising silver nitrate, polyvinyl pyrrolidone), tetrabutylammonium chloride and ethylene glycol.
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US10960343B2 (en) | 2016-12-19 | 2021-03-30 | Lummus Technology Llc | Methods and systems for performing chemical separations |
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US11186529B2 (en) | 2015-04-01 | 2021-11-30 | Lummus Technology Llc | Advanced oxidative coupling of methane |
WO2022044448A1 (en) | 2020-08-26 | 2022-03-03 | 昭和電工株式会社 | Transparent conductive substrate |
US11370724B2 (en) | 2012-05-24 | 2022-06-28 | Lummus Technology Llc | Catalytic forms and formulations |
WO2022138882A1 (en) | 2020-12-24 | 2022-06-30 | 昭和電工株式会社 | Transparent electroconductive film laminate |
Families Citing this family (87)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US9095837B2 (en) * | 2008-06-18 | 2015-08-04 | Broad of Trustees of the University of Arkansas | Renewable resource-based metal oxide-containing materials and applications of the same |
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EP2632850B1 (en) * | 2010-12-14 | 2015-12-09 | LG Innotek Co., Ltd. | Nano wire and method for manufacturing the same |
KR101305892B1 (en) | 2010-12-14 | 2013-09-06 | 주식회사 나노픽시스 | Nanowire and method for manufacturing the same by using low temperature polyol process |
KR101360688B1 (en) * | 2010-12-14 | 2014-02-11 | 주식회사 나노픽시스 | Nanowire and method for manufacturing 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 |
US8551211B2 (en) | 2011-02-15 | 2013-10-08 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
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US10494720B2 (en) | 2011-02-28 | 2019-12-03 | Nthdegree Technologies Worldwide Inc | Metallic nanofiber ink, substantially transparent conductor, and fabrication method |
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WO2012161857A1 (en) | 2011-05-23 | 2012-11-29 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US8741026B2 (en) * | 2011-05-23 | 2014-06-03 | Carestream Health, Inc. | Branched nanowire preparation methods, compositions, and articles |
CN102259190A (en) * | 2011-06-16 | 2011-11-30 | 浙江科创新材料科技有限公司 | Method for quickly preparing nano silver wires with high length-diameter ratio in large batch |
US9205493B1 (en) | 2011-06-28 | 2015-12-08 | Innova Dynamics, Inc. | Production of nanostructures |
CN103889595B (en) | 2011-07-01 | 2016-06-22 | 凯博瑞奥斯技术公司 | Anisotropic reduction in the coating of conducting film |
TWI462791B (en) * | 2011-07-08 | 2014-12-01 | Benq Materials Corp | Method for forming nano sliver particles |
US9956616B2 (en) | 2011-07-29 | 2018-05-01 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
KR101334601B1 (en) | 2011-10-11 | 2013-11-29 | 한국과학기술연구원 | Metal nanowire with high linearity, fabrication method of the same and transparent conducting film comprising the same |
KR20190092492A (en) | 2011-10-13 | 2019-08-07 | 캄브리오스 필름 솔루션스 코포레이션 | Opto-electrical devices with electrode incorporating metal nanowires |
CN104067351B (en) | 2011-11-04 | 2018-07-06 | 凯姆控股有限公司 | Optical stack based on nanostructured and the display with the optical stack |
US9568646B2 (en) | 2011-11-04 | 2017-02-14 | Cam Holding Corporation | Methods for reducing diffuse reflection of nanostructure-based transparent conductive films and touch panels made of the same |
TWI476160B (en) | 2011-12-19 | 2015-03-11 | Ind Tech Res Inst | Method for preparing silver nanowire |
US20130192423A1 (en) * | 2012-01-27 | 2013-08-01 | Blue Nano Inc. | Method of producing silver nanowires |
US9490048B2 (en) | 2012-03-29 | 2016-11-08 | Cam Holding Corporation | Electrical contacts in layered structures |
US10029916B2 (en) | 2012-06-22 | 2018-07-24 | C3Nano Inc. | Metal nanowire networks and transparent conductive material |
US9920207B2 (en) | 2012-06-22 | 2018-03-20 | C3Nano Inc. | Metal nanostructured networks and transparent conductive material |
EP2900409B1 (en) * | 2012-09-27 | 2019-05-22 | Rhodia Operations | Process for making silver nanostructures and copolymer useful in such process |
TW201416327A (en) * | 2012-10-16 | 2014-05-01 | Niching Ind Corp | Method of preparing silver nanowire |
US20140123808A1 (en) * | 2012-11-08 | 2014-05-08 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US8957322B2 (en) | 2012-12-07 | 2015-02-17 | Cambrios Technologies Corporation | Conductive films having low-visibility patterns and methods of producing the same |
WO2014116738A1 (en) | 2013-01-22 | 2014-07-31 | Cambrios Technologies Corporation | Nanostructure transparent conductors having high thermal stability for esd protection |
SG11201506221SA (en) | 2013-02-15 | 2015-09-29 | Cambrios Technologies Corp | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10720257B2 (en) | 2013-02-15 | 2020-07-21 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10971277B2 (en) | 2013-02-15 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10020807B2 (en) | 2013-02-26 | 2018-07-10 | C3Nano Inc. | Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks |
US20140251087A1 (en) | 2013-03-08 | 2014-09-11 | Innova Dynamics, Inc. | Production of nanostructures |
KR20140144807A (en) * | 2013-06-11 | 2014-12-22 | 삼성디스플레이 주식회사 | Fabricating method for metal nanowire and fabricating method for transparent conductor using the same |
US9759846B2 (en) | 2013-09-27 | 2017-09-12 | Cam Holding Corporation | Silver nanostructure-based optical stacks and touch sensors with UV protection |
TWI520911B (en) | 2013-10-21 | 2016-02-11 | 財團法人紡織產業綜合研究所 | Preparation method of silver nanowires |
US11274223B2 (en) | 2013-11-22 | 2022-03-15 | C3 Nano, Inc. | Transparent conductive coatings based on metal nanowires and polymer binders, solution processing thereof, and patterning approaches |
EP3131694B1 (en) * | 2013-12-31 | 2019-12-11 | Rhodia Operations | Processes for making silver nanostructures |
US11343911B1 (en) | 2014-04-11 | 2022-05-24 | C3 Nano, Inc. | Formable transparent conductive films with metal nanowires |
US20160001370A1 (en) * | 2014-07-03 | 2016-01-07 | Carestream Health, Inc. | Reducing agents for silver morphology control |
US9801287B2 (en) | 2014-07-09 | 2017-10-24 | Cam Holding Corporation | Electrical contacts in layered structures |
KR101554927B1 (en) | 2014-07-21 | 2015-09-22 | 주식회사 에이든 | Preparing method of silver nanowire and transparent electrode using it |
US9183968B1 (en) | 2014-07-31 | 2015-11-10 | C3Nano Inc. | Metal nanowire inks for the formation of transparent conductive films with fused networks |
DE102015013220A1 (en) * | 2014-10-28 | 2016-04-28 | Dow Global Technologies Llc | Process for the preparation of silver nanowires |
WO2016073717A1 (en) | 2014-11-05 | 2016-05-12 | Champ Great Int'l Corporation | Short-chain fluorosurfactants with iodide additives for forming silver nanowire-based transparent conductive films |
KR102271520B1 (en) * | 2014-12-29 | 2021-07-01 | 솔브레인 주식회사 | Silver nanowire complex and method for preparing the same |
TWI695848B (en) | 2015-03-03 | 2020-06-11 | 德商巴斯夫歐洲公司 | Silver nanowire synthesis with (meth) acrylate based capping agents |
DE102015105831A1 (en) | 2015-04-16 | 2016-10-20 | Rent-A-Scientist Gmbh | Metal nanoparticle-containing, disperse formulation |
CN106466714A (en) * | 2015-08-20 | 2017-03-01 | 南昌来捷尔新材料技术有限公司 | A kind of preparation method of nano silver wire aqueous dispersions |
US10564780B2 (en) | 2015-08-21 | 2020-02-18 | 3M Innovative Properties Company | Transparent conductors including metal traces and methods of making same |
JP6653973B2 (en) | 2015-09-30 | 2020-02-26 | 昭和電工株式会社 | Manufacturing method of metal nanowire |
WO2017174539A1 (en) | 2016-04-06 | 2017-10-12 | Basf Se | Method of preparing a product comprising surface modified silver nanowires, and use of the product |
CN106623966B (en) * | 2016-10-10 | 2019-04-30 | 中国科学院深圳先进技术研究院 | The silver nanowires for preparing the method for silver nanowires based on ionic liquid and being prepared |
WO2019034623A1 (en) | 2017-08-16 | 2019-02-21 | Rhodia Operations | Process for the manufacture of metal 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 |
US11446738B2 (en) | 2018-05-25 | 2022-09-20 | Seiko Pmc Corporation | Method for manufacturing silver nanowire |
CN108436105B (en) * | 2018-06-07 | 2023-06-20 | 乐凯华光印刷科技有限公司 | Ultra-long nano silver wire dispersion liquid and preparation method thereof |
US11819922B2 (en) | 2019-03-01 | 2023-11-21 | Seiko Pmc Corporation | Silver nanowire manufacturing method |
CN110640163B (en) * | 2019-10-18 | 2021-11-30 | 上海交通大学 | Method for preparing superfine silver nanowires with ultrahigh length-diameter ratio |
CN112705721B (en) * | 2019-10-25 | 2022-08-19 | 深圳市善柔科技有限公司 | Preparation method of silver nanowires |
KR20230066423A (en) * | 2020-12-24 | 2023-05-15 | 가부시끼가이샤 레조낙 | Manufacturing method of silver nanowire |
WO2023118954A1 (en) | 2021-12-22 | 2023-06-29 | Bosch Car Multimedia Portugal, S.A. | Method for producing silver nanowires and device for carrying out the method |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3167429A (en) | 1961-05-26 | 1965-01-26 | Levy Marilyn | Monobaths containing sodium polyacrylate and polyvinyl-pyrrolidone |
US3552969A (en) | 1967-09-25 | 1971-01-05 | Eastman Kodak Co | Photographic compositions and processes |
DE3216125A1 (en) * | 1982-04-30 | 1983-11-10 | Cassella Ag, 6000 Frankfurt | METHOD FOR PRODUCING SULFUR DYES OF THE PHTHALOCYANIN SERIES |
FR2537898A1 (en) | 1982-12-21 | 1984-06-22 | Univ Paris | METHOD FOR REDUCING METAL COMPOUNDS BY THE POLYOLS, AND METAL POWDERS OBTAINED BY THIS PROCESS |
US5565143A (en) | 1995-05-05 | 1996-10-15 | E. I. Du Pont De Nemours And Company | Water-based silver-silver chloride compositions |
US6221222B1 (en) * | 1998-12-03 | 2001-04-24 | Baxter International Inc. | Reference electrode solution containing organic ammonium and phosphonium salts for potentiometric measurement of pH |
WO2000061220A1 (en) | 1999-04-13 | 2000-10-19 | Hisamitsu Pharmaceutical Co., Inc. | Iontophoresis device |
US7585349B2 (en) * | 2002-12-09 | 2009-09-08 | The University Of Washington | Methods of nanostructure formation and shape selection |
JP4636454B2 (en) * | 2003-05-13 | 2011-02-23 | 三菱マテリアル株式会社 | Manufacturing method and use of metal nanorods |
US7048806B2 (en) * | 2003-12-16 | 2006-05-23 | The Clorox Company | Cleaning substrates having low soil redeposition |
US20050220882A1 (en) | 2004-03-04 | 2005-10-06 | Wilson Pritchard | Materials for medical implants and occlusive devices |
US7785922B2 (en) * | 2004-04-30 | 2010-08-31 | Nanosys, Inc. | Methods for oriented growth of nanowires on patterned substrates |
US20060083694A1 (en) * | 2004-08-07 | 2006-04-20 | Cabot Corporation | Multi-component particles comprising inorganic nanoparticles distributed in an organic matrix and processes for making and using same |
WO2006076611A2 (en) | 2005-01-14 | 2006-07-20 | Cabot Corporation | Production of metal nanoparticles |
EP2922099B1 (en) | 2005-08-12 | 2019-01-02 | Cambrios Film Solutions Corporation | Nanowires-based transparent conductors |
US20080003130A1 (en) | 2006-02-01 | 2008-01-03 | University Of Washington | Methods for production of silver nanostructures |
US8454721B2 (en) | 2006-06-21 | 2013-06-04 | Cambrios Technologies Corporation | Methods of controlling nanostructure formations and shapes |
WO2008046011A2 (en) | 2006-10-12 | 2008-04-17 | Cambrios Technologies Corporation | Systems, devices, and methods for controlling electrical and optical properties of transparent conductors based on nanowires |
KR101545219B1 (en) | 2006-10-12 | 2015-08-18 | 캄브리오스 테크놀로지즈 코포레이션 | Nanowire-based transparent conductors and applications thereof |
US20090052029A1 (en) | 2006-10-12 | 2009-02-26 | Cambrios Technologies Corporation | Functional films formed by highly oriented deposition of nanowires |
JP2008190006A (en) | 2007-02-06 | 2008-08-21 | Achilles Corp | Wire-shaped silver particle, and method for synthesizing the same |
US20080229612A1 (en) | 2007-03-22 | 2008-09-25 | Poshpeds Incorporated | Human wearable laminar structure, insole made therefrom and methods for their manufacture |
KR101456838B1 (en) | 2007-04-20 | 2014-11-04 | 캄브리오스 테크놀로지즈 코포레이션 | Composite transparent conductors and methods of forming the same |
CN101971354B (en) | 2007-04-20 | 2012-12-26 | 凯博瑞奥斯技术公司 | High contrast transparent conductors and methods of forming the same |
JP2009108407A (en) | 2007-10-12 | 2009-05-21 | Fujifilm Corp | Bent rod-shaped metal particle, manufacturing method for the same, composition containing the same, and conductive material |
JPWO2009063744A1 (en) | 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 | Method for producing metal nanowire, metal nanowire and transparent conductor |
US7922787B2 (en) | 2008-02-02 | 2011-04-12 | Seashell Technology, Llc | Methods for the production of silver nanowires |
JP5203769B2 (en) | 2008-03-31 | 2013-06-05 | 富士フイルム株式会社 | Silver nanowire and method for producing the same, aqueous dispersion and transparent conductor |
US8382878B2 (en) | 2008-08-07 | 2013-02-26 | Xerox Corporation | Silver nanoparticle process |
US20110024159A1 (en) | 2009-05-05 | 2011-02-03 | Cambrios Technologies Corporation | Reliable and durable conductive films comprising metal nanostructures |
JP2012526359A (en) | 2009-05-05 | 2012-10-25 | カンブリオス テクノロジーズ コーポレイション | Reliable and durable conductive film containing metal nanostructures |
US8269214B2 (en) | 2010-07-29 | 2012-09-18 | General Electric Company | Organic light emitting device with outcoupling layer for improved light extraction |
-
2007
- 2007-06-21 US US11/766,552 patent/US8454721B2/en active Active
- 2007-06-21 WO PCT/US2007/014485 patent/WO2008073143A2/en active Application Filing
- 2007-06-21 TW TW096122329A patent/TWI397446B/en active
-
2011
- 2011-03-04 US US13/040,549 patent/US8709125B2/en active Active
-
2014
- 2014-04-08 US US14/247,689 patent/US9440291B2/en active Active
-
2016
- 2016-08-11 US US15/234,272 patent/US10195670B2/en active Active
-
2018
- 2018-12-19 US US16/226,613 patent/US10875098B2/en active Active
-
2019
- 2019-05-20 US US16/416,569 patent/US11020802B2/en active Active
Non-Patent Citations (5)
Title |
---|
FILANKEMBO A ET AL: "Is the anion the major parameter in the shape control of nanocrystals?" JOURNAL OF PHYSICAL CHEMISTRY B ACS USA, vol. 107, no. 30, 31 July 2003 (2003-07-31), pages 7492-7500, XP002487040 ISSN: 1089-5647 * |
NIKOOBAKHT B ET AL: "Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method" CHEMISTRY OF MATERIALS AMERICAN CHEM. SOC USA, vol. 15, no. 10, 20 May 2003 (2003-05-20), pages 1957-1962, XP002487039 ISSN: 0897-4756 * |
SUN Y ET AL: "LARGE-SCALE SYNTHESIS OF UNIFORM SILVER NANOWIRES THROUGH A SOFT, SELF-SEEDING, POLYOL PROCESS" ADVANCED MATERIALS, WILEY VCH, WEINHEIM, DE, vol. 14, no. 11, 5 June 2002 (2002-06-05), pages 833-837, XP001130211 ISSN: 0935-9648 cited in the application * |
WILEY B ET AL: "Polyol synthesis of silver nanoparticles: use of chloride and oxygen to promote the formation of single-crystal, truncated cubes and tetrahedrons" NANO LETTERS AMERICAN CHEM. SOC USA, vol. 4, no. 9, September 2004 (2004-09), pages 1733-1739, XP002487041 ISSN: 1530-6984 cited in the application * |
ZUSING YANG ET AL: "Anisotropic syntheses of boat-shaped core-shell Au-Ag nanocrystals and nanowires" NANOTECHNOLOGY, IOP, BRISTOL, GB, vol. 17, no. 9, 14 May 2006 (2006-05-14), pages 2304-2310, XP020104726 ISSN: 0957-4484 * |
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US9233421B2 (en) | 2008-11-18 | 2016-01-12 | Kwang Suck Suh | Method for manufacturing metallic nanowires using ionic liquids |
US8323744B2 (en) | 2009-01-09 | 2012-12-04 | The Board Of Trustees Of The Leland Stanford Junior University | Systems, methods, devices and arrangements for nanowire meshes |
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US10195603B2 (en) | 2010-05-24 | 2019-02-05 | Siluria Technologies, Inc. | Production of ethylene with nanowire catalysts |
US8980170B2 (en) | 2011-01-14 | 2015-03-17 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
WO2012096754A1 (en) * | 2011-01-14 | 2012-07-19 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US8613887B2 (en) | 2011-01-14 | 2013-12-24 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
US8815150B2 (en) | 2011-01-14 | 2014-08-26 | Carestream Health, Inc. | Nanowire preparation methods, compositions, and articles |
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US9963402B2 (en) | 2011-05-24 | 2018-05-08 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US9446387B2 (en) | 2011-05-24 | 2016-09-20 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US11795123B2 (en) | 2011-05-24 | 2023-10-24 | Lummus Technology Llc | Catalysts for petrochemical catalysis |
US8921256B2 (en) | 2011-05-24 | 2014-12-30 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US10654769B2 (en) | 2011-05-24 | 2020-05-19 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US9751818B2 (en) | 2011-11-29 | 2017-09-05 | Siluria Technologies, Inc. | Nanowire catalysts and methods for their use and preparation |
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US8962517B2 (en) | 2011-11-29 | 2015-02-24 | Siluria Technologies, Inc. | Nanowire catalysts and methods for their use and preparation |
CN104039451A (en) * | 2011-11-29 | 2014-09-10 | 希路瑞亚技术公司 | Nanowire catalysts and methods for their use and preparation |
WO2013082318A3 (en) * | 2011-11-29 | 2014-01-30 | Siluria Technologies, Inc. | Nanowire catalysts and methods for their use and preparation |
US11078132B2 (en) | 2011-11-29 | 2021-08-03 | Lummus Technology Llc | Nanowire catalysts and methods for their use and preparation |
US9133079B2 (en) | 2012-01-13 | 2015-09-15 | Siluria Technologies, Inc. | Process for separating hydrocarbon compounds |
US9527784B2 (en) | 2012-01-13 | 2016-12-27 | Siluria Technologies, Inc. | Process for separating hydrocarbon compounds |
US11254626B2 (en) | 2012-01-13 | 2022-02-22 | Lummus Technology Llc | Process for separating hydrocarbon compounds |
US9446397B2 (en) | 2012-02-03 | 2016-09-20 | Siluria Technologies, Inc. | Method for isolation of nanomaterials |
WO2013161996A2 (en) | 2012-04-26 | 2013-10-31 | 国立大学法人大阪大学 | Transparent conductive ink, and method for producing transparent conductive pattern |
US9556086B2 (en) | 2012-05-24 | 2017-01-31 | Siluria Technologies, Inc. | Oxidative coupling of methane systems and methods |
US9469577B2 (en) | 2012-05-24 | 2016-10-18 | Siluria Technologies, Inc. | Oxidative coupling of methane systems and methods |
US11370724B2 (en) | 2012-05-24 | 2022-06-28 | Lummus Technology Llc | Catalytic forms and formulations |
CN102689018A (en) * | 2012-06-11 | 2012-09-26 | 清华大学深圳研究生院 | Production method of nanometer silver wire material |
US9670113B2 (en) | 2012-07-09 | 2017-06-06 | Siluria Technologies, Inc. | Natural gas processing and systems |
US11242298B2 (en) | 2012-07-09 | 2022-02-08 | Lummus Technology Llc | Natural gas processing and systems |
US9969660B2 (en) | 2012-07-09 | 2018-05-15 | Siluria Technologies, Inc. | Natural gas processing and systems |
US10787398B2 (en) | 2012-12-07 | 2020-09-29 | Lummus Technology Llc | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US11168038B2 (en) | 2012-12-07 | 2021-11-09 | Lummus Technology Llc | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US9598328B2 (en) | 2012-12-07 | 2017-03-21 | Siluria Technologies, Inc. | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US10183900B2 (en) | 2012-12-07 | 2019-01-22 | Siluria Technologies, Inc. | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
DE102013002855A1 (en) | 2013-02-20 | 2014-08-21 | Heraeus Precious Metals Gmbh & Co. Kg | Formulations of washed silver wires and PEDOT |
WO2014127909A1 (en) | 2013-02-20 | 2014-08-28 | Heraeus Precious Metals Gmbh & Co. Kg | Formulations comprising washed silver nanowires and pedot |
US10865166B2 (en) | 2013-03-15 | 2020-12-15 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US10308565B2 (en) | 2013-03-15 | 2019-06-04 | Silura Technologies, Inc. | Catalysts for petrochemical catalysis |
US9738571B2 (en) | 2013-03-15 | 2017-08-22 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
WO2014209235A1 (en) * | 2013-06-26 | 2014-12-31 | Agency For Science, Technology And Research | Metal-containing particles, processes for their preparation, and uses thereof |
EP2830110A1 (en) | 2013-07-22 | 2015-01-28 | Heraeus Precious Metals GmbH & Co. KG | Patterning of a composition comprising silver nanowires |
US10927056B2 (en) | 2013-11-27 | 2021-02-23 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US11407695B2 (en) | 2013-11-27 | 2022-08-09 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US10047020B2 (en) | 2013-11-27 | 2018-08-14 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US9321702B2 (en) | 2014-01-08 | 2016-04-26 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US9512047B2 (en) | 2014-01-08 | 2016-12-06 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US9321703B2 (en) | 2014-01-08 | 2016-04-26 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US10894751B2 (en) | 2014-01-08 | 2021-01-19 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US11254627B2 (en) | 2014-01-08 | 2022-02-22 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10829424B2 (en) | 2014-01-09 | 2020-11-10 | Lummus Technology Llc | Oxidative coupling of methane implementations for olefin production |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US11208364B2 (en) | 2014-01-09 | 2021-12-28 | Lummus Technology Llc | Oxidative coupling of methane implementations for olefin production |
US11008265B2 (en) | 2014-01-09 | 2021-05-18 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US9352295B2 (en) | 2014-01-09 | 2016-05-31 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US10081058B2 (en) | 2014-04-11 | 2018-09-25 | Cam Holding Corporation | Methods of controlling nanowire morphology |
US10967432B2 (en) * | 2014-04-11 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods of controlling nanowire morphology |
WO2015157741A3 (en) * | 2014-04-11 | 2016-05-12 | Champ Great Int'l Corporation | Methods of controlling nanowire morphology |
US10780420B2 (en) | 2014-05-02 | 2020-09-22 | Lummus Technology Llc | Heterogeneous catalysts |
US9956544B2 (en) | 2014-05-02 | 2018-05-01 | Siluria Technologies, Inc. | Heterogeneous catalysts |
EP2977993A1 (en) | 2014-07-25 | 2016-01-27 | Heraeus Deutschland GmbH & Co. KG | Formulations comprising metal nanowires and pedot |
US9751079B2 (en) | 2014-09-17 | 2017-09-05 | Silura Technologies, Inc. | Catalysts for natural gas processes |
US10300465B2 (en) | 2014-09-17 | 2019-05-28 | Siluria Technologies, Inc. | Catalysts for natural gas processes |
US11000835B2 (en) | 2014-09-17 | 2021-05-11 | Lummus Technology Llc | Catalysts for natural gas processes |
EP3249708A1 (en) | 2014-11-21 | 2017-11-29 | Heraeus Deutschland GmbH & Co. KG | Pedot in perovskite solar cells |
EP3024042A1 (en) | 2014-11-21 | 2016-05-25 | Heraeus Deutschland GmbH & Co. KG | Pedot in perovskite solar cells |
CN104607656A (en) * | 2015-03-06 | 2015-05-13 | 中国科学院上海硅酸盐研究所 | Super-long silver nanowire and preparation method thereof |
US11542214B2 (en) | 2015-03-17 | 2023-01-03 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US9334204B1 (en) | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US9567269B2 (en) | 2015-03-17 | 2017-02-14 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US10787400B2 (en) | 2015-03-17 | 2020-09-29 | Lummus Technology Llc | Efficient oxidative coupling of methane processes and systems |
US9790144B2 (en) | 2015-03-17 | 2017-10-17 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US11186529B2 (en) | 2015-04-01 | 2021-11-30 | Lummus Technology Llc | Advanced oxidative coupling of methane |
US10865165B2 (en) | 2015-06-16 | 2020-12-15 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US9328297B1 (en) | 2015-06-16 | 2016-05-03 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US11001543B2 (en) | 2015-10-16 | 2021-05-11 | Lummus Technology Llc | Separation methods and systems for oxidative coupling of methane |
US9944573B2 (en) | 2016-04-13 | 2018-04-17 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
US10407361B2 (en) | 2016-04-13 | 2019-09-10 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
US11505514B2 (en) | 2016-04-13 | 2022-11-22 | Lummus Technology Llc | Oxidative coupling of methane for olefin production |
US10870611B2 (en) | 2016-04-13 | 2020-12-22 | Lummus Technology Llc | Oxidative coupling of methane for olefin production |
US10960343B2 (en) | 2016-12-19 | 2021-03-30 | Lummus Technology Llc | Methods and systems for performing chemical separations |
US11001542B2 (en) | 2017-05-23 | 2021-05-11 | Lummus Technology Llc | Integration of oxidative coupling of methane processes |
US10836689B2 (en) | 2017-07-07 | 2020-11-17 | Lummus Technology Llc | Systems and methods for the oxidative coupling of methane |
WO2020255458A1 (en) | 2019-06-20 | 2020-12-24 | 昭和電工株式会社 | Transparent electroconductive film laminate and method for processing same |
WO2021075424A1 (en) | 2019-10-18 | 2021-04-22 | 昭和電工株式会社 | Transparent electroconductive film laminate and method for processing same |
WO2022044448A1 (en) | 2020-08-26 | 2022-03-03 | 昭和電工株式会社 | Transparent conductive substrate |
WO2022138882A1 (en) | 2020-12-24 | 2022-06-30 | 昭和電工株式会社 | Transparent electroconductive film laminate |
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US11020802B2 (en) | 2021-06-01 |
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US20190275590A1 (en) | 2019-09-12 |
US10195670B2 (en) | 2019-02-05 |
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US20160346843A1 (en) | 2016-12-01 |
US10875098B2 (en) | 2020-12-29 |
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