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  • 专利说明
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    • 专利摘要:
    The present invention relates to a method of manufacturing silver nanowires having a high aspect ratio wherein the produced silver solids comprise silver nanowires having a high aspect ratio and are depleted of silver particles having a high aspect ratio. a low aspect ratio.
    公开号:FR3037265A1
    申请号:FR1655241
    申请日:2016-06-08
    公开日:2016-12-16
    发明作者:Raymond M Collins；Patrick T Mcgough；William R Bauer
    申请人:Dow Global Technologies LLC；
    IPC主号:
    专利说明:

    [0001] This invention relates generally to the field of manufacturing silver nanowires. In particular, the present invention relates to a method for producing silver nanowires having a high aspect ratio, wherein the silver solids provided comprise silver nanowires having a high aspect ratio and are depleted of particles. money with a low aspect ratio. [0002] High conductivity films with high transparency are of great value for use as electrodes or coatings in a wide range of electronic applications, including, for example, touchscreen displays and cells. PV. Current technology for these applications involves the use of films containing tin-doped indium oxide (ITO) that are deposited by physical vapor deposition processes. The high capital cost of physical vapor deposition processes has led to the desire to find other transparent conductive materials and other coating approaches. The use of dispersed silver nanowires in the form of a percolation network has emerged as a promising alternative to films containing ITO. The use of silver nanowires has the potential advantage that they can be implemented using roll-to-roll techniques. Thus, silver nanowires have the advantage of low cost manufacturing with the potential to provide higher transparency and conductivity than conventional ITO containing films. Various methods have been proposed for the manufacture of silver nanowires for use in transparent conductive materials. Unfortunately, conventional methods of manufacturing silver nanowires invariably produce polydispersed silver solids, where the solids include a mixture of structures including different shapes and sizes. For use in transparent conductive materials, however, it is desirable to provide a uniform suspension of silver nanowires having a high aspect ratio. The low aspect ratio particles provide a negligible contribution to the desired conductive properties for the transparent conductive materials, while having a significant negative impact on optical properties, such as haze and transmission, of transparent conductive materials. [0004] Conventional methods employed in an effort to separate the low aspect ratio particles from the desired high aspect ratio silver nanowires have been found to be inadequate. [0005] An approach to this problem constituting an alternative has been described by Spaid, et al. in the US patent application published under no. 20090321364. Spaid, et al. describe a method for separating contaminating particles from a solution containing nanowires; wherein, to filter the solution containing nanowires, a stream of the solution is formed and directed through a passage defining an opening having a small width or above a microstructured surface configured to filter the solution. [0006] Nevertheless, there remains a need to effectively separate silver particles having a low aspect ratio from silver nanowires having a high aspect ratio without appreciable loss of silver nanowires having a high aspect ratio. high aspect ratio or significant reduction in the average length of silver nanowires recovered in the product. [: 77] The present invention provides a method of manufacturing silver nanowires having a high aspect ratio, comprising: providing a raw feed, comprising: mother liquor and silver solids; where the silver solids in the raw feed include silver nanowires having a high aspect ratio and silver particles having a low aspect ratio; providing a dynamic filtration device, wherein the dynamic filtration device 3037265 3 comprises: a housing, comprising: a cavity having a first side and a second side; wherein there is at least one inlet in the first side of the cavity, at least one product outlet from the first side of the cavity and at least one permeate outlet from the second side of the cavity; and a porous member disposed in the cavity; a turbulence inducing element disposed in the cavity; and a source of pressure; wherein the porous member is interposed between the first side of the cavity and the second side of the cavity; wherein the porous member has a plurality of passages therethrough from the first side of the cavity to the second side of the cavity; wherein the passages of this plurality of passages are sufficiently large to allow transfer of the mother liquor and silver particles having a low aspect ratio and sufficiently small to block the transfer of silver nanowires having an aspect ratio. Student ; wherein the porous element and the turbulence-inducing element cooperate to form a filtration gap, FG; and wherein at least one of the porous element and the turbulence inducing element is movable; transferring the raw feed to the dynamic filtration device through the at least one inlet in the first side of the cavity; where the filtration interval, FG, is filled by the mother liquor; wherein the porous element and the turbulence inducing element disposed in the cavity are both in contact with the mother liquor; pressurizing the first side of the cavity by means of the pressure source which leads to a first-side pressure, FSp, in the first side of the cavity; where the first side pressure, FSp, is higher than a second side pressure, SSp, in the second side of the cavity, so that a pressure drop, PEA, is created through the porous element from the first side of the cavity to the second side of the cavity; wherein the source of pressure provides a primary driving force for inducing a current from the first side of the cavity through the porous member to the second side of the cavity, thereby producing a permeate; initiating at least one of the porous element and the turbulence-inducing element such that a shear stress is produced in the mother liquor in the filtration range, FG; wherein the shear stress produced in the mother liquor in the filtration range, FG, acts to reduce fouling of the porous member; removing the permeate from the at least one permeate outlet from the second side of the cavity, wherein the permeate comprises a second portion of the mother liquor and a second portion of the silver solids; where the second portion of the silver solids is rich in silver particles having a low aspect ratio; and removing a product from the at least one product outlet from the first side of the cavity, wherein the product comprises a first portion of the mother liquor and a first portion of the silver solids; where the first portion of the silver solids is depleted of silver particles having a low aspect ratio; and where the shear stress produced in the mother liquor in the filtration range, FG, and the pressure drop, PEA, through the porous element from the first side of the cavity to the second side of the cavity are decoupled. [0008] According to alternative embodiments of the process of the invention, to be considered independently or in combination: the method of the invention further comprises: the supply of a transport fluid; and transferring a volume of the transport fluid to the dynamic filtration device through the at least one inlet in the first side of the cavity; the method of the invention further comprises: continuously moving the turbulence-inducing element with respect to the porous element; The turbulence-inducing element provided is an agitator with an impeller, and the impeller is rotated continuously in a plane disposed in the first side of the cavity; the porous element is a porous membrane; said porous membrane is flat and has an upper surface and a lower surface; said upper surface and the lower surface are parallel; said porous membrane has a thickness, T, measured from the upper surface to the lower surface along a straight line (A) perpendicular to the upper surface; and the upper surface is close to the turbulence-inducing element; each passage of the plurality of passages has a cross-sectional area, Zire, parallel to the upper surface; where the cross-sectional area, Zire, is uniform across the thickness, T, of the porous membrane; The filtration interval, FG, is defined by the plane in which the impeller is rotated continuously and the upper surface of the porous member near the impeller; the filtration interval, FG, measures from 1 to 100 mm; the volumetric flow of permeate through the porous element is from 280 to 360 L / m2.hour; the pressure drop across the porous element is 20 to 35 kPa. BRIEF DESCRIPTION OF THE DRAWINGS [0009] Figure 1 shows a dynamic filtration device of the present invention. Figure 2 shows a cross-sectional view along the line A-A in Figure 1.
    [0002] Figure 3 shows a perspective view of a porous member disposed in a dynamic filtration device of the present invention. Fig. 4 shows a dynamic filtration device 5 of the present invention with an associated permeate container. Figure 5 illustrates a dynamic filtration device of the present invention with an associated permeate container and transport fluid components.
    [0003] DETAILED DESCRIPTION [0014] A method has been found for making silver nanowires having a high aspect ratio which surprisingly allows the efficient separation of silver particles having a low aspect ratio from the silver solids present in a raw feed without substantial loss of silver nanowires having a desired high aspect ratio or substantial reduction in the average length of the silver nanowires recovered in the product. [7:15] The term "high aspect ratio silver nanowires" as used herein refers to silver solids having an aspect ratio of> 3. The term "particles of silver having a high aspect ratio" as used herein refers to silver solids having an aspect ratio of> 3. silver having a low aspect ratio "as used herein means silver solids having an aspect ratio of 3. The term" fraction by gross weight "or" Weave as it is " used herein means the weight of silver nanowires having a high aspect ratio in the raw feed divided by the total weight of the silver solids contained in the raw feed. [The term "weight fraction of permeate" or "Faermeat" as used herein means the weight of high aspect ratio silver nanowires in the permeate divided by the total weight of the silver solids contained in the permeate. [0019] The term "product weight fraction" or "product" as used herein means the weight of silver nanowires having a high aspect ratio in the product divided by the total weight of the products. solid silver contained in the product. The term "first side pressure" or 1, -P "as used herein means the pressure measured in the first side (35) of the cavity (30) relative to the atmospheric pressure on the outer side 10 of the housing (20) The term "second side pressure" or "SSp" as used herein means the pressure measured in the second side (45) of the cavity (30) by relative to the atmospheric pressure on the outside of the housing (20). The term "pressure drop across the porous element" or "PEA" as used herein means the difference between first side, F, Sp, and the second side pressure, SSp, i.e. PEA = FSp-SSp The term "substantially constant" as used herein with reference to the area of cross-section, Xire, of a passage (55) through a porous element (50) means that the largest cross-sectional area, X- L- presented by the passage Given perpendicularly to the permeate stream through the thickness, T, of the porous element (55) may be up to 20% greater than the smallest cross-sectional area, s) Gire, presented by the passage . The term "substantially perpendicular" as used herein with reference to an axis of symmetry, Lsym, of a passageway (55) through a porous member (50) means that the axis of symmetry, axesym, meets the upper surface (52) of the porous member (50) at an angle, y, of 85 to 95 °. Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention comprises: providing a raw feed (5), comprising: a mother liquor; and silver solids; where the silver solids in the raw feed 5 (5) include silver nanowires having a high aspect ratio and silver particles having a low aspect ratio (preferably, where the raw feed a fraction by gross weight, WF.rute) the supply of a dynamic filtration device (10), wherein the dynamic filtration device (10) comprises: a housing (20), comprising: a cavity (30) having a first side (35) and a second side (45); wherein there is at least one inlet (32) in the first side (15) of the cavity (30), at least one outlet (37) from the first side (35) of the cavity (30) and at least one outlet (47) from the second side (-5) of the cavity (30); and a porous member (50) disposed in the cavity (30); a turbulence-inducing element (60) disposed in the cavity (30); and a pressure source (70); wherein the porous member (50) is interposed between the first side (35) of the cavity (30) and the second side (45) of the cavity (30); wherein the porous member (E)) has a plurality of passages (55) extending therethrough from the first side (35) of the cavity (30) to the second side (45) of the cavity (a; (55) of this plurality of passages (55) are sufficiently large to allow transfer of the mother liquor and silver particles having a low aspect ratio and sufficiently small to block transfer of the silver nanowires having a ratio the porous element (50) and the turbulence-inducing element (60) cooperate to form a filtration gap (FG), and wherein at least one of the porous element (50) and the turbulence inducing element (60) is movable; transferring the raw supply (L;) to the dynamic filtration device (10) through the at least one inlet (32) in the first side (35) of the cavity (30), where the filtration range (FG) is filled by the mother liquor, where the pore element ux (50) and the turbulence-inducing element (60) disposed in the cavity (30) are both in contact with the mother liquor; pressurizing the first side (35) of the cavity (30) by means of the pressure source (70) which leads to a first side pressure FSp in the first side (35) of the cavity ( 30) ; where the first side pressure, FSp, is higher than a second side pressure, SSp, in the second side (45) of the cavity (30), so that a pressure drop is created (P41) through the porous member (50) from the first side (35) of the cavity (30) to the second side (45) of the cavity (30); wherein the source of pressure (70) provides a primary driving force for inducing a current from the first side (35) of the cavity (30) through the porous member (50) to the second side (45) of the cavity (30), which produces a permeate; initiating (preferably continuously moving) at least one of the porous member (50) and the turbulence inducing member (60) (more preferably, setting the motion in a continuous manner the turbulence inducing element (60) with respect to the porous element (50) so that a shear stress is produced in the mother liquor in the filtration range (FG); wherein the shear stress produced in the mother liquor in the filtration range (FG) acts to reduce fouling of the porous member (50); removing the permeate from the at least one outlet (47) from the second side (45) of the cavity (30), wherein the permeate comprises a second portion of the mother liquor and a second portion of the silver solids; wherein the second portion of the silver solids is rich in silver particles having a low aspect ratio (preferably, where the permeate has a fraction by weight of permeate, preferably FPermeat, where Un.-rute WFPermeatest still, where WFermeat 0.05, more preferably, where WFBrute> WFPermeat 0.01, particularly preferably, where WFBrute> WFPermeat 5.001); and removing a product from the at least one outlet (37) from the first side (35) of the cavity (30), wherein the product comprises a first portion of the mother liquor and a first portion of the solids 'money ; wherein the first portion of the silver solids is depleted of silver particles having a low aspect ratio (preferably, wherein the product has a fraction by weight of product, WFProduct, preferably, where WFBrute - .rute <WFProduct; more preferably, where WFBrute <WFProduct 0.8; more preferably, where WFBrute <W-product 0.85; particularly preferably, where WFBrute <WFProduct 0.9); where the shear stress produced in the mother liquor in the filtration gap (FG) and the pressure drop (PEA) through the porous element (50) from the first side (35) of the cavity (30) to the second side (45) of the cavity (30) are decoupled (i.e. they can be controlled independently).  (See Figure 1)  Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the gross feed (5) supplied comprises: a mother liquor; and silver solids; where the silver solids are suspended in the mother liquor.  Preferably, the raw feed contains 5% by weight of silver solids.  More preferably, the raw feed contains 0.01 to 1% by weight (more preferably 0.05 to 0.75% by weight, particularly preferably 0.1 to 0.5% by weight). ) silver solids.  [0027] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the mother liquor in the raw feed is a liquid.  More preferably, the mother liquor in the raw feed is a liquid selected from the group consisting of water and a polyol.  More preferably, the mother liquor in the raw feed is a liquid selected from the group consisting of water, diethylene glycol and ethylene glycol.  Particularly preferably, the mother liquor in the raw feed is water.  Preferably, the mother liquor in the raw feed is water, where the water is at least one of deionized water and distilled water to limit accidental impurities.  More preferably, the mother liquor in the raw feed is water, where the water is deionized and distilled.  Particularly preferably, the mother liquor in the raw feed is water, where the water is ultrapure water that meets or exceeds the requirements for Type 1 water according to ASTM D1193-99e1 ("Standard Specification for Reagent Water ").  [0028] Preferably, in the process for manufacturing high aspect ratio silver nanowires of the present invention, the silver solids contained in the raw feed include silver nanowires having a ratio of high aspect and silver particles having a low aspect ratio.  Preferably, the raw feed has a fraction by gross weight, wF.  . convert silver nanowires having a high aspect ratio to silver particles having a low aspect ratio.  Preferably, the fraction by gross weight, WFR - -ruter is maximized by the method used to synthesize the silver nanowires having a high aspect ratio.  Nevertheless, the synthesis of silver nanowires having a high aspect ratio invariably gives a certain amount of silver particles having a low undesirable aspect ratio which are desirably removed so that the fraction by weight of product, Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the raw feed supplied further comprises: at least one of a polyvinylpyrrolidone , a reducing sugar, a reducing agent, a copper (II) ion source and a halide ion source.  More preferably, in the high aspect ratio silver nanowire manufacturing method of the present invention, the gross feed supplied with the September 2016 unevenness notification without apparent modifications further comprises: polyvinylpyrrolidone and a reducing sugar.  Particularly preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the raw feed supplied further comprises: polyvinylpyrrolidone, reducing sugar, reducing agent, source of copper (II) ions and a source of halide ions.  [0030] Preferably, the polyvinylpyrrolidone (PVP) incorporated in the raw feed supplied in the process for manufacturing silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, from 20000 to 300000 u.  More preferably, the polyvinylpyrrolidone (PVP) has a weight average molecular weight, Mw, of 30000 to 200000 u.  Particularly preferably, the polyvinylpyrrolidone (PVP) has a weight average molecular weight, Mw, of 40000 to 60000 u.  [0031] Preferably, the reducing sugar, incorporated into the raw feed supplied in the high aspect ratio silver nanowire manufacturing process of the present invention, is selected from the group consisting of at least one of the aldoses (for example glucose, glyceraldehyde, galactose, mannose); disaccharides with a free hemiacetal unit (eg lactose and maltose); and sugars carrying a ketone (eg fructose).  More preferably, the reducing sugar is selected from the group consisting of at least one of an aldose, lactose, maltose and fructose.  More preferably, the reducing sugar is selected from the group consisting of at least one of glucose, glyceraldehyde, galactose, mannose, lactose, fructose and maltose.  Most preferably, the reducing sugar is D-glucose.  [0032] Preferably, the reducing agent incorporated in the raw feed provided in the silver nanowire manufacturing process having a high aspect ratio of the present invention is selected from the group consisting of ascorbic acid; borohydride salts (for example NaBH4, KBH4, LiBH4, Ca (BH4) 2); hydrazine; salts of hydrazine; hydroquinone; C1-5 alkylaldehyde and benzaldehyde.  More preferably, the reducing agent is selected from the group consisting of ascorbic acid, sodium borohydride (NaBH4), potassium borohydride (KBH4), lithium borohydride (LiBH4), calcium borohydride ( Ca (BH4) 2), hydrazine, hydrazine salts, hydroquinone, acetaldehyde, propionaldehyde and benzaldehyde.  Most preferably, the reducing agent is at least one of ascorbic acid and sodium borohydride.  Preferably, the source of copper (II) ions, incorporated in the raw feed supplied in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, is chosen from the group consisting of at least one of CuCl2 and Cu (NO3) 2.  More preferably, the copper (II) ion source is selected from the group consisting of CuCl 2 and Cu (NO 3) 2.  Particularly preferably, the copper (II) ion source is CuCl 2, where CuCl 2 is a copper (II) chloride dihydrate.  [0034] Preferably, the halide ion source incorporated in the raw feed provided in the silver nanowire manufacturing process having a high aspect ratio of the present invention is selected from the group consisting of at least one of a chloride ion source, a fluoride ion source, a bromide ion source and an iodide ion source.  More preferably, the halide ion source is selected from the group consisting of at least one of a chloride ion source and a fluoride ion source.  More preferably, the halide ion source is a source of chloride ions.  Most preferably, the halide ion source is a source of chloride ions, where the source of chloride ions is an alkali metal chloride.  Preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride, potassium chloride and lithium chloride.  More preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride and potassium chloride.  Most preferably, the alkali metal chloride is sodium chloride.  [0035] Preferably, the process for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing a transport fluid; and transferring a volume of the transport fluid to the dynamic filtration device through the at least one inlet into the first side of the cavity (incidentally, it will be noted here that, obviously, the raw feed and the fluid volume of The transport in question is not necessarily transferred to the dynamic filtration device by the same inlet in the first side of the cavity (the advantageous variant of the transfers by the same inlet being shown in FIG. 5)).  Preferably, the volume of transport fluid can be transferred to the dynamic filtration device in a manner selected from at least one of the transfer of a single charge, the transfer of a plurality of charges (where the charges may contain the same amount of transport fluid or different amounts of transport fluid) and transfer continuously.  More preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing a transport fluid; and transferring a volume of transport fluid to the dynamic filtration device through the at least one inlet in the first side of the cavity; wherein the concentration of the silver solids in the first side of the cavity is controlled by adjusting the volume of the transport fluid transferred to the first side of the cavity.  Most preferably, the high aspect ratio silver nanowire manufacturing method of the present invention further comprises: providing a transport fluid; and transferring a volume of transport fluid to the dynamic filtration device through the at least one inlet in the first side of the cavity; where the concentration of the silver solids in the first side of the cavity is maintained at 25% by weight.  More preferably, the volume of transport fluid transferred to the dynamic filtration device is controlled so that the concentration of the silver solids in the first side of the cavity is maintained from 0.01 to 1% by weight (preferably more preferably from 0.05 to 0.75% by weight, particularly preferably from 0.1 to 0.5% by weight).  [0036] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the transport fluid comprises a liquid.  More preferably, the transport fluid comprises a liquid selected from the group consisting of water and a polyol.  More preferably, the transport fluid comprises a liquid selected from the group consisting of water, diethylene glycol and ethylene glycol.  Particularly preferably, the transport fluid comprises water.  [0037] Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the transport fluid provided further comprises: at least one of polyvinylpyrrolidone, a reducing sugar , a reducing agent, a source of copper (II) ions and a source of halide ions.  More preferably, in the method for manufacturing high aspect ratio silver nanowires of the present invention, the transport fluid provided further comprises: polyvinylpyrrolidone.  More preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the transport fluid provided further comprises: polyvinylpyrrolidone and reducing sugar.  Particularly preferably, in the process of manufacturing 3037265 16 silver nanowires having a high aspect ratio of the present invention, the transport fluid provided further comprises: polyvinylpyrrolidone, reducing sugar, reducing agent, a source of copper (II) ions and a source of halide ions.  [0038] Preferably, in the high aspect ratio silver nanowire manufacturing method of the present invention, the raw feed (5) is transferred to the dynamic filter apparatus by means of a filtering device. moving fluid (80).  Those skilled in the art will be able to select a fluid setting device (80) suitable for use with the raw feed.  Preferably, in the high aspect ratio silver nanowire manufacturing method of the present invention, the fluid moving device () used to transfer the raw feed (5) to the dynamic filtration device (10) is decoupled from the driving force used to induce a pressure drop (PEA) through the porous member (50) from the first side (35) of the cavity (30) in the dynamic filtration device (10). ) to the second side (45) of the cavity (30).  More preferably, the raw feed is transferred to the dynamic filtration device (10) by means of a low shear fluid setting device (80), such as a peristaltic pump or a system head pressure ( for example, the gravity or the pressure of an inert gas).  Preferably, when system head pressure is used as a fluid moving device (80) to facilitate the transfer of the raw feed (5) to the dynamic filtration device (10), the delivery device fluid movement (80) further comprises a fluid valve (85) (preferably a fluid control valve) for regulating the rate at which the raw feed (5) is transferred to the dynamic filtration device (10).  (See Figure 1)  Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: providing a liquid level detector (90) and a circuit control (95), wherein the liquid level detector (90) and the control circuit (95) are integrated with the dynamic filtration device (10) and the fluid movement device (C) (from preferably, a peristaltic pump or system head pressure coupled with a control valve (85) for maintaining a stable liquid level (100) in the housing (20) such that the filtration interval (FG ) remains filled by the mother liquor.  (See Figure 1)  Preferably, in the method for manufacturing silver nanowires having a high aspect ratio of the present invention, the volume (150) of transport fluid is transferred to the dynamic filtration device (10) by means of a liquid moving device (140).  Those skilled in the art will be able to select a liquid moving device (140) suitable for use with the transport fluid.  Preferably, in the method of manufacturing silver nanowires having a high aspect ratio of the present invention, the liquid moving device (1, -) used to transfer the volume (150) of transport to the dynamic filtration device (10) is decoupled from the driving force used to induce a pressure drop (PEA) through the porous member (50) from the first side (35) of the cavity (30) into the device dynamic filtration system (10) to the second side (45) of the cavity (30).  More preferably, the volume of transport fluid is transferred to the dynamic filtration device (10) by means of a pump or pressure at the top of the system (for example, the gravity or pressure of an inert gas ).  Preferably, the dynamic filtration device (10) further comprises a liquid valve (145) (preferably a liquid control valve (145)) for regulating the transfer of transport fluid to the dynamic filtration device ( 10).  (See Figure 5)  Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing a liquid level detector (90) and a control circuit (95). ), where the liquid level detector (90) and the control circuit (95) (preferably, where the control circuit includes a programmable logic controller) are integrated with the dynamic filter device (10), the fluid moving device (80) (preferably a peristaltic pump or system head pressure coupled with a fluid control valve (85)), and a liquid control valve (145) for maintaining a stable liquid level (100) in the housing (20) such that the filtration gap (FG) remains filled by the mother liquor.  (See Figure 5)  Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the porous element (50) used in the dynamic filtration device (10) has several passes (55). ) passing therethrough from the first side (35) of the cavity (37) to the second side (45) of the cavity (30); wherein the plurality of passages (55) are large enough to allow the transfer of mother liquor and silver particles having a low aspect ratio and sufficiently small to block the transfer of silver nanowires having a high aspect ratio.  More preferably, each passageway (55) in the plurality of passages (55) has a cross-sectional area, Xire, perpendicular to the permeate flow through the thickness, T, of the porous member (50). that is to say, parallel to its upper surface; wherein the cross-sectional area, Xire, is substantially constant over the thickness, T, of the porous member (50).  Preferably, the porous member (50) has a pore size dimensioned to September 2016 unevenness notification with apparent changes at 10 μm (more preferably, from 2 to 8 μm, more preferably, from 2 to 5 μm, particularly preferably from 2.5 to 3.5 μm).  Preferably, the porous element is chosen from curved porous elements and flat porous elements.  More preferably, the porous member is a flat porous member.  Preferably, in the method of manufacturing silver nanowires having a high aspect ratio of the present invention, the porous member (50) used in the dynamic filtration device (10) is a porous membrane.  More preferably, the porous element (50) is a polycarbonate membrane 10 rendered porous by Etch track technology (PCTE).  (See Figures 1-3).  [0043] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, a shear stress is produced in the mother liquor present in the filtration range, FG; wherein the shear stress induces sufficient movement in the mother liquor tangentially to the upper surface (52) of the porous member (50) to reduce or prevent clogging or fouling of the porous member.  The shear stress is produced by a relative clearance between the porous member (50) and the turbulence inducing member (60) adjacent to the filtration gap. With the high aspect ratio silver nanowires of the present invention, the porous member (50) is stationary with respect to the cavity (30) and the turbulence-inducing member (60) moves relative to the porous element (50).  Preferably, when the porous member (50) is a stationary and flat porous member, the turbulence-inducing member (60) rotates in a plane near the top surface (52) of the porous member (50).  More preferably, when the porous member (50) is a flat porous membrane, the turbulence-inducing member (60) is a stirrer.  Preferably, the agitator is selected from the group consisting of a stirring bar, a stirring bar suspended and attached to (or in a piece with) a shaft, and an impeller mounted on a tree.  Preferably, the porous membrane is flat and has an upper surface (52) and a lower surface (5 "), where the upper surface (52) and the lower surface) are parallel, wherein the porous membrane has a thickness, T measured from the upper surface (52) to the lower surface (54) along a straight line (A) perpendicular to the upper surface (52), and wherein the upper surface (52) faces the turbulence-inducing element ( 60).  Preferably, the turbulence-inducing element (60) provided with the flat porous membrane is a stirrer with an impeller; wherein the impeller is rotated continuously in a plane disposed in the first side (35) of the cavity (30).  Preferably, the filtration interval is defined by the plane in which the impeller is rotated continuously and the upper surface (52) of the porous member (50) near the impeller (preferably , where the plane is parallel to the upper surface of the porous element).  Preferably, the filtration range, FG, is 1 to 100 mm.  (See Figures 1-3) [(75] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the turbulence-inducing element has a permeable surface.  More preferably, when the turbulence inducing member has a permeable surface, the permeable surface is interposed between the first side of the cavity and the second side of the cavity and at least a certain fraction of the permeate removed from the dynamic filtration device. passes through the permeable surface of the turbulence-inducing element from the first side of the cavity to the second side of the cavity.  Preferably, when the turbulence inducing member has a permeable surface, the permeable surface of the turbulence inducing member faces the plurality of passages of the porous member.  Preferably, when the turbulence inducing member has a permeable surface, the permeable surface is curved and disposed about a central axis of rotation; where the turbulence inducing element rotates about the central axis.  More preferably, when the turbulence-inducing element has a curved permeable surface, disposed around a central axis of rotation, where the turbulence-inducing element rotates about the central axis, the porous element also has a surface curved disposed around a central axis of rotation; wherein the curved surface of the porous member has a plurality of passageways therethrough from the first side of the cavity to the second side of the cavity; where the porous element rotates about its central axis; wherein the curved permeable surface of the turbulence inducing member faces the curved surface of the porous member; wherein the space interposed between the curved permeable surface of the turbulence-inducing element and the curved surface of the porous element defines the filtration gap, FG.  Preferably, the central axis of rotation of the turbulence-inducing element and that of the porous element are parallel.  According to one variant, the turbulence-inducing element and the porous element rotate in the same direction.  According to another variant, the turbulence-inducing element and the porous element rotate in opposite directions.  [0046] Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, the filtration gap, FG, is disposed in the filter housing and is interposed between the first side (35) of the cavity (30) and the second side (45) of the cavity (30); where the filtration interval, Fq, is defined by two opposite surfaces; wherein at least one of the opposing surfaces is movable; and wherein the porous member (50) provides at least one of the opposed surfaces.  The filtration gap, FG, is typically formed between opposing, oppositely disposed surfaces which are separated from each other by a distance of from 1 to 25 mm (preferably from 1 to 25 mm). 20 mm, more preferably from 1 to 15 mm, particularly preferably from 1 to 10 mm).  Preferably, the size of the filtration gap, FG, is substantially constant on the opposite surface formed by the porous member (50) (i.e. the largest dimension of the filtration gap, FGSL , and the smallest dimension of the filtration interval, FGSs, between the opposite surfaces are related as follows: 0.9 FGSL FGSs FGSL).  (See Figures 1, 4 and 5).  Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention, at least one of the porous element (50) and the turbulence-inducing element (60). moves relative to the other to produce a shear stress in the mother liquor in a filtration gap, FG, between the opposed surfaces of the porous member (50) and the turbulence-inducing member (60) .  More preferably, at least one of the porous element (50) and the turbulence-inducing element (61) moves continuously with respect to the other 20 to produce shear stress in the mother liquor in a filtration gap, FG, between the opposed surfaces of the porous member (50) and the turbulence inducing member (60).  Preferably, the shear stress produced in the filtration range, FG, induces sufficient movement in the mother liquor tangentially to the surface of the porous member that faces the first side (35) of the cavity (30). to reduce or prevent clogging or fouling of the porous element.  Preferably, the porous member (50) and the turbulence-inducing member (60) move relative to each other at a relative velocity of 0.4 to 1.5 m / s (more preferably from 0.6 to 1.3 m / s, particularly preferably from 0.9 to 1.1 m / s).  Preferably, the shear stress produced in the mother liquor disposed in the filtration range, FG, and the pressure drop across the porous member from the first side of the cavity to the second side. of the cavity are decoupled.  Particularly preferably, the shear stress produced in the mother liquor disposed in the filtration range, FG, and the pressure drop across the porous member from the first side of the cavity to the second side of the cavity can be ordered independently.  [0049] Preferably, in the high aspect ratio silver nanowire manufacturing method of the present invention, the pressure source provides the primary driving force for permeate passage through the porous element to the surface. on the second side of the cavity.  Preferably, the pressure source is a gas pressure exerted on the first side of the cavity.  More preferably, the gas pressure exerted on the first side of the cavity is the pressure of an inert gas.  Particularly preferably, the gas pressure exerted on the first side of the cavity is a nitrogen pressure.  The gas pressure can be applied to the first side of the cavity as a gaseous free space above the liquid level in the cavity.  Alternatively, the first side of the cavity provided may further comprise a pocket; where the bag is pressurized with the gas.  Preferably, the pressure source induces a pressure drop across the porous member of 5 to 70 kPa (more preferably 10 to 55 kPa, more preferably 15 to 40 kPa, particularly preferably from 20 to 35 kPa).  Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: periodically establishing an inverted current through the porous member (50) since the second side (15) of the cavity (30) to the first side (35) of the cavity (30).  Those skilled in the art will be able to choose appropriate means for establishing the reverse current.  More preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: periodically establishing an inverted stream through the porous member (50) since the second side (45) of the cavity (30) to the first side (35) of the cavity (30); wherein the reverse current is set for a period of 1 to 10 seconds (more preferably 2.5 to 7.5 seconds, particularly preferably 3 to 5 seconds) every 10 to 60 seconds (preferably still, 15 to 40 seconds, particularly preferably 20 to 30 seconds).  Preferably, the silver nanowire manufacturing method having a high aspect ratio of the present invention further comprises: providing a conduit (120) for transferring permeate from the at least one outlet (47) from the second side (45) of the cavity (30) to a container (125) (preferably, where there is an intermediate air layer (130) between the conduit (120) and the container (125)).  More preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing a conduit (120) for transferring permeate from the at least one outlet (47); ) from the second side (45) of the cavity (30) to a container (125) (preferably where there is an intermediate air layer (130) between the conduit (120) and the container (125). )); and periodically, reducing the momentary pressure of the first side (35) of the cavity (30) by releasing the pressure source (7r) (e.g., placing the first side of the cavity in the atmosphere); wherein the conduit (120) contains a volume of permeate that is at a height that is higher than that of the liquid level (100) in the dynamic filtration device (10) (preferably, where the volume of permeate that is at a height which is higher than that of the liquid level (100) has a height greater than 20 to 500 mm (more preferably 100 to 375 mm, particularly preferably 150 to 300 mm) such that, periodically, during the momentary pressure reduction of the first side (35) of the cavity (30) there is a current reversal through the porous member (50) from the second side (45) from the cavity (30) to the first side (35) of the cavity (30).  Preferably, the periodic momentary pressure reduction is established for a period of 1 to 10 seconds (more preferably 2.5 to 7.5 seconds, particularly preferably 3 to 5 seconds) every 10 to 60 seconds. 10 seconds (more preferably, every 15 to 40 seconds, particularly preferably every 20 to 30 seconds) pressurizing.  (See Figures 4-5).  [0052] Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing a source of vibratory energy; and periodically applying vibratory energy from the vibratory energy source to the porous member.  [0053] Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention further comprises: providing an ultrasonic energy source; and periodically applying ultrasonic energy from the ultrasonic energy source to the porous member.  [0054] Preferably, the high aspect ratio silver nanowire manufacturing method of the present invention provides a volumetric flow of permeate through the porous element of 20 to 1000 L / m2. hour (more preferably from 140 to 540 L / m2. hour ; particularly preferably from 280 to 360 L / m2. hour).  Preferably, the high aspect ratio silver nanowire manufacturing method of the present invention provides a product wherein the silver solids in the product have a mean diameter. 40 nm (preferably 20 to 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm).  More preferably, the method for producing silver nanowires having a high aspect ratio of the present invention provides a product wherein the silver solids in the product have a mean diameter of 40 nm (preferably 20 to 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) and an average length of 10 to 100 μm.  Preferably, the silver solids in the product have an average aspect ratio of> 500.  [C:] Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention provides a product, wherein the silver solids in the product have a standard deviation of the diameters of 5. 26 nm (preferably 1 to 26 nm, more preferably 5 to 20 nm, particularly preferably 10 to 15 nm).  More preferably, the method for producing silver nanowires having a high aspect ratio of the present invention provides a product, wherein the silver solids in the product have a mean diameter of 40 nm (preferably 20 μm). at 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) with a standard deviation of diameters 26 nm (preferably 1 to 26 nm, more preferably from 5 to 20 nm, particularly preferably from 10 to 15 nm).  Particularly preferably, the high aspect ratio silver nanowire manufacturing method of the present invention provides a product wherein the silver solids in the product have a mean diameter of 40 nm (preferably from 20 to 40 nm, more preferably from 20 to 35 nm, more preferably from 20 to 30 nm) with a standard deviation of diameters 26 nm (preferably from 1 to 26 nm, more preferably from 5 to 20 nm, particularly preferably from 10 to 15 nm) and an average length of 10 to 100 μm.
    [0004] [0057] Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention provides a product where WFBrute <WFprudidt. More preferably, the process for producing high aspect ratio silver nanowires of the present invention provides a product wherein WFB is 0.8 to 0.8 wt. More preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention provides a product where Wekute <WFPruduit k 0.85. Particularly preferably, the high aspect ratio silver nanowire manufacturing method of the present invention provides a product where the product has a ratio of 0.9 to 0.9. Some embodiments of the present invention will now be described in detail in the following examples. The water used in the following examples was obtained by means of a Barnstead NANOPure ThermoScientific purification system with a hollow fiber filter with a pore size of 0.2 pnn positioned downstream of the unit. of water purification. Comparative Example A [0060] A Sterlitech filtration cell with a membrane made porous by the "track etch" technology ("track etch") of 3 μm was used to filter 250 ml of a crude feed solution. where the crude feed solution was a polyol solution containing 0.2% by weight of silver. The raw feed solution was passed through the filtration cell by means of a Masterflex® peristaltic pump at a volumetric flow rate of 400 mL / min. Every five minutes, water was sent through the filtration cell in the other direction. The collected retentate was passed through the filtration cell five more times to form the product solution. Image analysis was used to determine the area of the particles relative to that of the yarns as shown in Table 1 in which the low aspect ratio particles were those classified as having a lower aspect ratio. 3. The diameter data presented in Table 1 were determined from scanning electron microscope (SEM) images obtained from samples prepared by vacuum drying a drop of solution on a wafer. silicon using a FEI Nova NanoSEM Field Emission Scanning Electron Microscope using the FEI Automated Image Acquisition (AIA) program. At least 100 discrete threads on the images were measured in 10 Image.] For their diameter. It was noted that the length of the silver nanowires in the product solution appeared shorter than that of the silver nanowires in the raw feed solution, suggesting that the silver nanowires in the feed solution were deteriorated during the filtration process.
    [0005] TABLE 1 Thread Area Solution (Thread Area Diameter + Particle Area) Medium (nm) Deviation (nm) Gross Feed 0.83 53 16 Product 0.92 60 Example 1 [CT] Aqueous Solutions containing silver solids including silver nanowires with a high aspect ratio and silver particles with a low aspect ratio were filtered using an Advantec stirred cell filter housing / MFS model UHP 150 with a filtration area of 162 cm2 and provided with an impeller ("year 25 impeller") magnetic cylindrical bar type. The filter housing has irregularity notification September 30, with apparent changes been placed on a scale / magnetic stirring device Mettler model SB32001DR. The porous medium used was a 5 μm filter membrane made of hydrophilic polycarbonate made porous by etch track technology (PCTE) supported in the bottom of the filter housing. Nitrogen pressure was used to create the motive force to produce a pressure drop across the porous medium. Nitrogen was introduced into the headspace of the filter housing. Head pressure was measured using a Cole-Parmer model 68075-16 pressure transducer. The nitrogen introduced into the filter housing was passed through a three-way ball valve mounted on the top of the filter housing. The three-way valve allowed for periodic interruption of the nitrogen stream and periodic release of pressure in the headspace of the filter housing to the atmosphere. This allowed for an inverted stream of gravity-induced filtrate material from the exhaust duct and rising into the filter housing through the filter membrane. The three-way valve was controlled by means of a Camille process control computer in such a way that every 25 seconds the nitrogen supply to the filter housing was interrupted and the filter housing was turned off. atmosphere for 5 seconds before the restoration of the nitrogen supply. A weighed amount of raw feed was poured into the filter housing. A transport fluid was introduced into the filter housing by means of a Masterflex Model 77800-16 Easy-Load 3 peristaltic pump with a digital control and a 16-gauge C-Flex hose. The volume of transport fluid transferred to the The filter housing was manually controlled to maintain a constant level in the filter housing throughout the filtration process. The filtrate leaving the bottom of the filter housing was made to mount in a flexible plastic tube of 4.1 mm internal diameter to reach the top of an open container at the top. The fluid column in the filtrate tube created the driving force for the discharge in the filter housing when the free space was periodically vented to the three-way valve. The silver solids in the crude feed and in the product filtrate were analyzed in the same manner as in Comparative Example A. The results are shown in Table 2. It was noted that the length of the nanowires The silver solution in the product solution did not appear to have been compromised during the filtration process, unlike the case of Comparative Example A.
    [0006] 10 TABLE 2 Solution area of wires / (area of wires + Mean Diameter (nm) Median (nm) Particle (nm) area of particles) Gross Feed 0.759 60.1 43.6 45.9 Product 0.998 39.6 38 , 9 9.8 31
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A method of manufacturing silver nanowires having a high aspect ratio, characterized in that it comprises: providing a raw feed (5), comprising: a mother liquor; and silver solids; wherein the silver solids in the raw feed (5) include silver nanowires having a high aspect ratio and silver particles having a low aspect ratio; providing a dynamic filtration device (10), wherein the dynamic filtration device (10) comprises: a housing (20), comprising: a cavity (30) having a first side (35) and a second side (45) ); wherein there is at least one inlet (32) in the first side (35) of the cavity (30), at least one product outlet (37) from the first side (35) of the cavity (30) and at least one a permeate outlet (47) from the second side (45) of the cavity (30); and a porous member (50) disposed in the cavity (30); a turbulence-inducing element (60) disposed in the cavity (30); and a pressure source (70); wherein the porous member (50) is interposed between the first side (35) of the cavity (30) and the second side (45) of the cavity (30); wherein the porous member (50) has a plurality of passages (55) therethrough from the first side (35) of the cavity (30) to the second side (45) of the cavity (30); wherein the passages (55) of this plurality of passages (55) are large enough to allow transfer of mother liquor and silver particles having a low aspect ratio and sufficiently small to block the transfer of nanowires silver having a high aspect ratio; wherein the porous member (50) and the turbulence inducing member (60) cooperate to form a filtration gap (FG); and wherein at least one of the porous element (50) and the turbulence-inducing element (60) is movable; transferring the raw feed (5) to the dynamic filtration device (10) through the at least one inlet (32) in the first side (35) of the cavity (30); where the filtration interval (FG) is filled by the mother liquor; wherein the porous member (50) and the turbulence inducing member (60) disposed in the cavity (30) are both in contact with the mother liquor; pressurizing the first side (35) of the cavity (30) by means of the pressure source (70) which leads to a first side pressure, FS, in the first side (35) of the cavity (30); ); wherein the first side pressure, F.sp, is greater than a second side pressure, 5Sp, in the second side (45) of the cavity (30), so that there is creation of a pressure drop, PEA, through the porous member (50) from the first side (35) of the cavity (30) to the second side (45) of the cavity (30); wherein the pressure source (70) provides a primary driving force for inducing a current from the first side (35) of the cavity (30) through the porous member (50) to the second side (45) of the cavity (30) producing a permeate; moving at least one of the porous member (50) and the turbulence-inducing member (60) such that a shear stress is produced in the mother liquor in the range of filtration (FG); wherein the shear stress produced in the mother liquor in the filtration range (FG) acts to reduce fouling of the porous member (50); removing the permeate from the at least one permeate outlet (47) from the second side (45) of the cavity (30), wherein the permeate comprises a second portion of the mother liquor and a second portion of the silver solids ; where the second portion of the silver solids is rich in silver particles having a low aspect ratio; and removing a product from the at least one product outlet (37) from the first side (35) of the cavity (30), wherein the product comprises a first portion of the mother liquor and a first portion of the solids silver ; where the first portion of the silver solids is depleted of silver particles having a low aspect ratio; and where the shear stress produced in the mother liquor in the filtration gap (FG) and the pressure drop, PE3, through the porous element (50) from the first side (35) of the cavity (30). ) to the second side (45) of the cavity (30) are decoupled.
    [0002]
    2. Method according to claim 1 characterized in that it further comprises: the supply of a transport fluid; and transferring a volume (150) of the transport fluid to the dynamic filtration device (10) through the at least one inlet (32) in the first side (35) of the cavity (30).
    [0003]
    3. The method of claim 1 or 2, further comprising: continuously moving the turbulence inducing member (60) relative to the porous member (50).
    [0004]
    4. A method according to any one of claims 1 to 3, characterized in that the turbulence-inducing element (60) supplied is an agitator with an impeller, and the impeller is rotated 303 726 5 34 continuous in a plane disposed in the first side (35) of the cavity (30).
    [0005]
    5. Method according to any one of claims 1 to 4, characterized in that the porous element (50) is a porous membrane; Wherein the porous membrane is flat and has an upper surface (52) and a lower surface (54); wherein the upper surface (52) and the lower surface (54) are parallel; wherein the porous membrane has a thickness (T) measured from the upper surface (52) to the lower surface (54) along a straight line (A) perpendicular to the upper surface (52); and wherein the upper surface (52) is close to the turbulence-inducing element (60).
    [0006]
    6. A method according to any one of claims 1 to 5, characterized in that each passage (55) in the plurality of passages (55) has a cross-sectional area (Xaire) parallel to the upper surface (52); wherein the cross-sectional area (Xaire) is uniform across the thickness (T) of the porous membrane (50).
    [0007]
    7. A method according to any one of claims 4 to 6, characterized in that the filtration interval (FG) is defined by the plane in which the thruster is continuously rotated and the upper surface (52). the porous element (50) close to the impeller.
    [0008]
    8. Method according to any one of claims 1 to 7, characterized in that the filtration interval, (FG) is from 1 to 100 mm.
    [0009]
    9. A process according to any one of claims 1 to 8, characterized in that the volumetric flow of permeate through the porous element (50) is from 280 to 360 L / m2.hour.
    [0010]
    Process according to one of Claims 1 to 9, characterized in that the pressure drop, PE, through the porous element (50) is 20 to 35 kPa.
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    同族专利:
    公开号 | 公开日
    US10376898B2|2019-08-13|
    US20160361723A1|2016-12-15|
    CN106238742A|2016-12-21|
    DE102016007019A1|2016-12-15|
    CN106238742B|2018-07-20|
    KR20160146543A|2016-12-21|
    TW201710002A|2017-03-16|
    JP2017020103A|2017-01-26|
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