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    • 专利摘要:
    STABLE DISPERSIONS OF MONOCRYSTALLINE SILVER NANOMETRIC PARTICLES AND METHOD FOR PRODUCING SUCH DISPERSIONS. A concentrated dispersion of nanometric silver particles, and a method for producing the dispersion, which includes a first solvent; a plurality of nanometer silver particles, the majority of which are single-crystal silver particles, the plurality of nanometer silver particles having an average secondary particle size (d50) within a range of 30 to 300 nanometers, the particles arranged in the solvent, and at least one dispersant, where a concentration of silver particles within the dispersion is within a range of 30% to 75%, by weight, and where a concentration of the dispersant is within a range variation of 0.2% to 30% of the concentration of silver particles by weight.
    公开号:BR112013013885B1
    申请号:R112013013885-8
    申请日:2011-12-06
    公开日:2020-12-22
    发明作者:Fernando De La Vega；Ganit Shter Bar Joshua；Semyon Melamed；Reuven Geva；Moshe Link
    申请人:P.V. Nano Cell Ltd.；
    IPC主号:
    专利说明:

    FIELD AND FUNDAMENTALS OF THE INVENTION
    [001] The present invention relates to stable and concentrated dispersions of nanometric silver particles and a method of producing such dispersions.
    [002] Nanometer silver particles are finding increasing use in the pharmaceutical industry, especially in the field of wound care. Fine silver particle dispersions are widely used in the manufacture of conductive inks and electrically conductive films for applications such as internal electrodes in multilayer capacitors, interconnections in multichip components, conductive lines in defrosters and defrosters, photovoltaic modules, resistors, inductors , antennas, membrane switches, electromagnetic shield, thermally conductive films, light reflecting films, and conductive adhesives. In many existing and emerging technologies, the demand for ultrafine silver particles with specific properties is increasing.
    [003] In some applications, the required characteristics of such particles can be related to at least one of: average particle size, small particle size distribution, particle density, and crystalline grain structure.
    [004] Nanometric silver particles have found commercial use as dispersions in organic solvents. The stability of such dispersions can generally be guaranteed for up to six months.
    [005] The production of fine silver particles by precipitation of particles from a liquid medium is well known. However, as taught by US Patent No. 6,277,169 to Hampden-Smith, et al., Such liquid precipitation techniques are often difficult to control to produce particles with the desired characteristics. Specifically, US Patent No. 6,277,169 discloses that it is especially difficult to obtain, through the liquid precipitation route, particles that have a dense and spherical morphology and good crystallinity.
    [006] The production of small silver particles by reducing silver oxide (for example, using hydrogen peroxide) in aqueous liquid media is known. Poorly soluble silver oxide can be dissolved in the reaction medium prior to the reduction reaction through the formation of silver ion complexes with ammonia, as disclosed by WO Patent Publication No. 2003/080231.
    [007] Various liquid precipitation techniques may promote the agglomeration or aggregation of silver particles, as well as the sedimentation of particles. This agglomeration can be undesirable for several reasons, among them: the particle size distribution and the average particle size can be adversely affected, and contaminants in the mother liquor can be occluded between particles, reducing the purity of the product. We have found that the specific electrical resistance of thin films formed from such contaminated silver particles can be adversely increased. In addition, agglomerated particles and / or sedimentation can clog the nozzles on the inkjet printer head, decreasing the robustness of the printing process.
    [008] Various liquid precipitation techniques may promote the formation of polycrystalline silver particles. We found that such polycrystalline silver particles can adversely exhibit greater specific electrical resistance. In addition, they may be significantly more prone to agglomeration and sedimentation.
    [009] Notwithstanding advances in the production of silver nanoparticles, the present inventors recognized the need for improved silver nanoparticles and dispersions of silver nanoparticles, and methods of producing such nanoparticles and dispersions thereof. SUMMARY OF THE INVENTION
    [0010] We have found that chemical reduction in an aqueous medium, according to the present invention, can have enormous potential for the industrial scale production of concentrated nanometric silver particle dispersions (up to 75% by weight) that can exhibit superior stability (24 months or more) and may also enable the production of thin silver films with extremely low specific electrical resistance (eg 2.5 x 10-6ohmxm or less). However, several additional processing steps may be necessary to ensure that the nanometric silver particles produced, usually as diluted dispersions, do not suffer from disadvantageous agglomeration and other transformations with increasing dispersion concentration and as the washing and solvent displacement are made.
    [0011] In accordance with the teachings of the present invention, a concentrated dispersion of nanometric silver particles, including a first solvent, is provided; a plurality of nanometer silver particles, most of which are monocrystalline silver particles, the plurality of nanometer silver particles having an average secondary particle size (d50) within a range of 30 to 300 nanometers, such particles arranged in the said solvent; and at least one dispersant, where a concentration of silver particles within the dispersion is within a range of 30 to 75% by weight, and where the concentration of the dispersant dispersion is within a range of 0.2% to 30% concentration of silver particles, by weight.
    [0012] According to additional resources in the described preferential modalities, the dispersant concentration is a maximum of 20%, 15%, 10%, 7%, 5%, 3% or 2%.
    [0013] According to other additional resources in the preferred modes described, the dispersion viscosity at 25 ° C is less than 2000 cP, 1000 cP, 600 cP, 300 cP or 120cP, and in many cases, less than 80 cP , 60 cP, 45 cP, 35 cP, 25 cP or 20 cP.
    [0014] According to other additional resources in the preferred modalities described, the average size of secondary particles is at least 40 nanometers, at least 50 nanometers, at least 60 nanometers or at least 75 nanometers.
    [0015] According to other additional resources in the described preferential modalities, at least 60%, at least 70%, at least 75%, at least 80%, at least 85% or at least 90% of the nanometric silver particles are monocrystal silver particles.
    [0016] According to other additional resources in the preferred modalities described, the average size of secondary particles is a maximum of 250 nanometers, a maximum of 200 nanometers, a maximum of 150 nanometers, a maximum of 120 nanometers, a maximum of 100 nanometers, or a maximum 80 nanometers.
    [0017] According to other additional resources in the preferred modalities described, at least one dispersant is selected from the group of dispersants that consists of polyvinylpyrrolidone (PVP), gum arabic, polyvinyl alcohol (APV), polyacrylic acid (APA) , polyalylamine (PAAm), polystyrene sodium sulfonate (PSS), 3-aminopropyl trimethoxysilane (APS), a fatty acid, lauryl amine, cetyl trimethyl ammonium bromide (BCTA) and tetraoctylammonium bromide (BTOA).
    [0018] According to other additional resources in the described preferential modalities, the dispersant includes PVP. The average molecular weight of PVP is at least 8,000 g / mol, at least 10,000 g / mol, within the range of 10,000 g / mol to 1,600,000 g / mol, or within the range of 10,000 g / mol to 200,000 g / mol.
    [0019] According to other additional resources in the preferred embodiments described, the first solvent includes, consists substantially of, or consists of water.
    [0020] According to other additional resources in the preferred modalities described, the first solvent includes an alcohol.
    [0021] According to other additional resources in the described preferential modalities, the water concentration within the dispersion is less than 25%, less than 15%, less than 10%, less than 7%, less than 5%, unless 3%, or less than 2%, by weight.
    [0022] According to other additional resources in the preferred embodiments described, the first solvent includes at least one volatile organic solvent.
    [0023] According to other additional resources in the described preferred modalities, the first solvent includes at least one non-volatile organic solvent.
    [0024] According to other additional resources in the preferred embodiments described, the first solvent includes at least one volatile organic solvent and at least one non-volatile organic solvent.
    [0025] According to other additional resources in the preferred embodiments described, the first solvent includes water and at least one volatile organic solvent, and in which the volatile organic solvent forms at least 80%, at least 85% or at least 90% of the first solvent, by weight.
    [0026] According to other additional resources in the preferred modalities described, the specific electrical resistance of silver particles, after standard sintering, is a maximum of 4 x 10-5 ohmxm, 6 x 10-6 ohmxm, a maximum of 5 x 10 -6 ohmxm, maximum 4 x 10-6 maximum, 3.5 x 10-6 ohmxm, maximum 3 x 10-6 ohmcm or maximum 2.5 x 10-6 ohm ^ cm.
    [0027] According to other additional resources in the described preferential modalities, the dispersion contains at least 35%, at least 40%, at least 45%, at least 50%, or at least 55%, by weight, of nanometric particles silver.
    [0028] According to other additional resources in the described preferential modalities, the average size of secondary particles of at least 90% of the particles, per volume (d90), is a maximum of 500 nanometers, a maximum of 300 nanometers, a maximum of 200 nanometers , maximum 150 nanometers, maximum 120 nanometers, maximum 100 nanometers, maximum 80 nanometers, or maximum 70 nanometers.
    [0029] According to other additional resources in the preferred embodiments described, the average molecular weight of the dispersant is at least 8,000 g / mol, within a range of 10,000 g / mol to 1,600,000 g / mol, or within a range from 10,000 g / mol to 200,000 g / mol.
    [0030] According to other additional resources in the preferred embodiments described, the first solvent includes at least one solvent selected from the group of solvents consisting of an alcohol, dimethylsulfoxide (DMSO), an alkylamine; ethylene diamine, dimethyl acetamide, 1,4-butanediol, formic acid, acetic acid, a glycol or glycol derivative, N-methyl-2-pyrrolidone (NMP), butyl carbitol acetate and an epoxy resin.
    [0031] According to other additional resources in the preferred embodiments described, the glycol includes at least one of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol.
    [0032] According to other additional resources in the preferred embodiments described, the glycol derivative includes at least one of dipropylene glycol monomethyl ether (DPM), tripropylene glycol monomethyl ether (TP) and diethylene glycol monomethyl ether (DGME).
    [0033] According to other additional resources in the described preferential modalities, alcohol includes at least one of ethanol, isopropanol, benzyl alcohol and terpineol.
    [0034] According to other additional resources in the preferred embodiments described, the alkyl amine includes butylamine.
    [0035] According to other additional resources in the described preferential modalities, the dispersion contains less than 70%, by weight, of nanometric silver particles.
    [0036] According to other additional resources in the described preferential modalities, the inventive dispersion is produced according to a process, including the steps of: (a) reacting at least one soluble silver compound with an alkali metal hydroxide in a aqueous medium, in the presence of a first dispersant, to produce solid silver oxides with an average secondary particle size below 1200 nanometers; (b) reaction of solid silver oxides with at least one reducing agent in an aqueous medium, in the presence of a second dispersant, to produce silver particles, which have an average secondary particle size below 1000 nanometers; and (c) supply of silver particles in the concentrated dispersion, with the concentration of the nanometric silver particles within a range of 30% to 75%, by weight.
    [0037] According to other additional resources in the preferred modalities described, the reducing agent includes, or substantially consists of, a reducing agent selected from the group consisting of peroxides and sodium borohydride.
    [0038] According to other additional resources in the preferred embodiments described, the reducing agent includes, or substantially consists of, hydrogen peroxide.
    [0039] According to other additional resources in the described preferential modalities, at least one of the first and the second dispersant includes PVP.
    [0040] According to other additional resources in the preferred modalities described, the second dispersant is added in sufficient quantity, whereby the silver particles have an average secondary particle size of a maximum of 250 nanometers, a maximum of 200 nanometers, a maximum of 150 nanometers, maximum 100 nanometers or maximum 80 nanometers.
    [0041] According to other additional resources in the preferred modalities described, the first dispersant is added in sufficient quantity by which the solid silver oxides have an average secondary particle size of a maximum of 200 nanometers.
    [0042] According to other additional resources in the preferred modalities described, the alkali metal hydroxide and the soluble silver compound react in a stoichiometric relationship between the hydroxide and the soluble silver compound, and in what amounts of the alkali metal hydroxide and of the soluble silver compound are added in a specific proportion that is, at most, 1.2 times, 0.98 times or 0.95 times such stoichiometric relationship.
    [0043] According to other additional resources in the preferred modalities described, after step (b), the silver particles are washed and concentrated, so that the aqueous medium is only partially removed from the particles (up to 90%, up to 80% , up to 75% or up to 70%) to form a concentrate.
    [0044] In accordance with another aspect of the present invention, a method is provided for producing a dispersion of nanometric silver particles which includes: (a) reacting at least one soluble silver compound with an alkali metal hydroxide in an aqueous medium , in the presence of a first dispersant, to produce solid silver oxides with an average secondary particle size below 1200 nanometers; (b) reaction of solid silver oxides with at least one reducing agent in an aqueous medium, in the presence of a second dispersant, to produce a first dispersion of silver particles, which have an average secondary particle size below 300 nanometers; and (c) removing at least a part of the aqueous medium from the particles to produce the dispersion.
    [0045] According to other resources in the described preferential modalities, the method also includes the concentration of the particles to form a second dispersion, concentrated in relation to the first dispersion.
    [0046] According to other additional resources in the described preferential modalities, the second dispersion has a concentration of at least 10% and less than 75% by weight.
    [0047] According to other additional resources in the preferred modalities described, step (c) includes washing and concentration of silver particles, so that the aqueous medium is partially removed from the particles, forming a concentrate containing most of the silver particles .
    [0048] According to other additional resources in the described preferential modalities, the method also includes the replacement of most of such aqueous medium with at least one volatile organic solvent.
    [0049] According to other additional resources in the preferred modalities described, the method also includes the replacement of the volatile organic solvent by at least one additional organic solvent.
    [0050] According to other additional resources in the described preferred modalities, the concentration of nanometric silver particles within the dispersion is within a range of 30% to 75%, by weight.
    [0051] According to other additional resources in the described preferential modalities, the dispersion that has any of the characteristics described above has been aged for at least 6 months, at least 9 months, at least 12 months, at least 18 months, or at least 24 months.
    [0052] According to other additional resources in the preferred modalities described, the reaction of solid silver oxides is carried out in the presence of a second dispersant, the excess of which is removed in step (c). BRIEF DESCRIPTION OF THE FIGURES
    [0053] The foregoing discussion will be more easily understood from the following detailed description of the invention, when analyzed together with the attached Figures (1-6), in which:
    [0054] Figure 1 is a schematic block diagram of a process for producing a nanometer silver product, in accordance with an aspect of the present invention;
    [0055] Figure 2 is a High Resolution Scanning Electron Microscopy (HRSEM) image showing a typical field containing nanometric silver particles produced according to one embodiment of the present invention, described in Example 7;
    [0056] Figure 3 is a Backscattered Electron Diffraction (EBSD) pattern of nanometric silver particles produced according to the modality described in Example 7;
    [0057] Figure 4 is an image of High Resolution Scanning Electron Microscopy (HRSEM) showing a typical field containing nanometric silver particles produced according to an embodiment of the present invention, described in Example 10;
    [0058] Figure 5 is a SEM image of a sample containing nanometric silver particles, produced in accordance with the present invention, showing six selected sites for EBSD scanning; and
    [0059] Figure 6 provides five illustrations of the 3D crystal orientation for the five locations in Figure 5 where monocrystalline particles were identified. DESCRIPTION OF PREFERENTIAL MODALITIES
    [0060] The principles of stable dispersions of inventive silver nanometric particles, and the inventive methods of producing such dispersions, can be better understood with reference to the drawings and accompanying description.
    [0061] Before explaining in detail at least one embodiment of the invention, it should be understood that the application of the invention is not limited to the details of construction and the organization of the components set out in the following description or illustrated in the drawings. The invention is capable of other modalities or of being practiced or carried out in several ways. In addition, it should be understood that the wording and terminology used in this document are for description purposes and should not be considered as representing limitations.
    [0062] We have discovered a method of producing nanometric silver particles, in which a large fraction of the particles is monocrystalline. However, we have found that producing stable dispersions of these silver nanometer particles is an extremely complex and, at times, confusing subject. The production of stable dispersions can be especially problematic when producing such dispersions directly in various organic solvents that can be used in the final product dispersions. In addition, it has also been found that the production of stable dispersions of prefabricated nanometric silver particles (eg, commercially available) is extremely difficult and unpredictable.
    [0063] Notwithstanding these challenges, surprisingly we have discovered a method of purifying such nanometer silver particles while a stable dispersion is maintained, whereby nanocrystal silver nanometer particles retain their monocrystalline nature, even during displacement or contact with organic solvents problematic and during the formulation of concentrated dispersions, having at least 30% silver by weight and, more commonly, at least 35%, at least 40%, at least 45%, at least 50% or at least 55% silver by weight.
    [0064] Furthermore, the inventive method can advantageously produce concentrated dispersions containing, mainly or predominantly, monocrystalline silver particles, having an average particle size of at least 30 nanometers and, more commonly, at least 40 nanometers, at least 50 nanometers , at least 60 nanometers or at least 75 nanometers. We believe that the monocrystallinity of the silver particles is a decisive factor in obtaining, after sintering, low values of specific electrical resistance. We also believe that the monocrystallinity of the silver particles allows the formulation of concentrated dispersions of silver nanoparticles, without going through remarkable agglomeration.
    [0065] Normally, the concentrated dispersions produced contain a maximum of 10% ultrafine particles, by weight. Thus, the concentrated dispersions of the present invention can have a d10 of at least 20 nanometers or at least 25 nanometers and, more commonly, at least 30 nanometers, at least 35 nanometers, or at least 40 nanometers.
    [0066] Although it is possible to produce silver single crystals according to other methods, the dispersions of the present invention can be distinguished in at least one of several ways, including: 1. average particle size 2. fine fractions (d10) 3. concentration of silver particles within the dispersion 4. percentage of single crystals within the silver particles, by weight. 5. Average Particle Size
    [0067] In the concentrated dispersions of the present invention, nanometric silver particles with an average secondary particle size (d50) within a range of 30 to 300 nanometers. These dispersions contain, mainly or predominantly, single crystal silver particles.
    [0068] It should be noted that the production of a monocrystal with 60 nanometers in diameter is more than 200 times the size of a monocrystal with a diameter of 10 nanometers [(60/10) A3 = 216]. The growth of a 10 nanometer diameter monocrystal to 60 nanometers in a solvent requires more than 200 times the deposition of supersaturated silver in a 10 nanometer monocrystal than was necessary to initially form the 10 nanometer monocrystal.
    [0069] In crystallization processes, competing mechanisms, including nucleation and agglomeration, can interfere, or even predominate, in relation to crystal growth. In the case of reactive precipitation processes, in which moderately soluble and similar materials are precipitated out of solution in a reactive process, these competing processes can be highly favored, taking into account the extremely high levels of global supersaturation and even higher levels of local supersaturation. These competing processes can also be favored due to the presence of particles of solid reagent, around which local supersaturation can be even greater, favoring nucleation and agglomeration in relation to crystal growth. In the methods of the present invention, silver particles are precipitated out of solution in this reactive process. Hence, the production of silver particles that are mostly or predominantly monocrystalline silver particles would seem, at the very least, unexpected. The production of a monocrystalline silver product having a d50 of 30 nanometers and, normally more, is surprising. 6. Fine Fractions (d10)
    [0070] The silver particles in dispersions of the present invention can be further characterized by a shortage of fine silver particles. Using a Brookhaven 90Plus particle size analyzer, the dispersions of the present invention exhibited a d10 of at least 25 nanometers and, more commonly, at least 30 nanometers, at least 35 nanometers and, in some cases, at least 40 nanometers. The data from the Brookhaven particle size analyzer was subsequently confirmed through measurements based on High Resolution Scanning Electron Microscopy (HRSEM) images.
    [0071] Thus, at least 90%, by weight, of silver particles in the dispersions of the present invention has a diameter of at least 25-40 nanometers. 7. Concentration of silver particles within the dispersion
    [0072] The concentration of nanometric silver particles within the concentrated dispersions of the present invention is typically within a range of 30 to 75% by weight. The production of the nanoparticles is generally carried out, whereby a relatively diluted dispersion is obtained. The process of obtaining diluted dispersion, which may include washing, adding and / or replacing solvent, etc., may be a major contributor to the agglomeration of silver nanoparticles. During the inventive process, described below, silver nanoparticle agglomeration is largely avoided. 8. Percentage of single crystals within the silver particles, by weight.
    [0073] In the concentrated dispersions of the present invention, the nanometer silver particles can be, mainly or predominantly, monocrystalline silver particles, in relation to weight. The presence of single crystals was demonstrated qualitatively by means of Backscattered Electron Diffraction (EBSD). The quantification of the results was achieved by conducting a plurality of scans at randomly chosen points, as described in more detail below. We found that, in our inventive dispersions, at least 50% or at least 70% of the nanometer silver particles are monocrystalline and, more commonly, at least 80% or at least 90% are monocrystalline.
    [0074] Referring now to the drawings, Figure 1 is a schematic block diagram of a method of producing a nanometer silver product, in accordance with an aspect of the present invention. The method can include the following steps:
    [0075] Step 1: reaction of at least one soluble silver compound with an alkali metal hydroxide in aqueous medium, in the presence of a first dispersant, to produce solid silver oxides with an average secondary particle size below 1200 nanometers;
    [0076] Step 2: reaction of solid silver oxides with at least one reducing agent in an aqueous medium, in the presence of a second dispersant, to produce silver particles, with such silver particles having an average secondary particle size below 500 nanometers and, more commonly, below 300 nanometers;
    [0077] Step 3: purification of the silver particles from Step 2 by washing with water; the aqueous medium can also be partially removed from the particles, forming a concentrate containing most of the silver particles;
    [0078] Step 4: introduction, in the purified silver particles, of at least one volatile organic solvent and replacement of most of the aqueous medium with this; and
    [0079] Step 5: replacement of most of the volatile organic solvent with at least one organic solvent, normally non-volatile.
    [0080] Various modalities of the inventive method of producing a nanometer silver product will now be described in more detail. Step 1
    [0081] At least one soluble silver compound is dissolved in an aqueous solvent to form a first solution. The alkaline hydroxide (eg, sodium or potassium hydroxide) can then be added, under vigorous stirring, to this first solution. However, it may be advantageous to prepare a second solution of the alkali hydroxide. The second solution can then be introduced into the first solution, under vigorous stirring, and in the presence of a dispersant, to form a fine silver oxide precipitate. The resulting dispersion is preferably agitated, and a defoaming agent can be added to prevent or reduce foaming.
    [0082] The vigorous mixing can be done in an ultrasonic bath, normally maintained at a temperature ranging from 10 ° C to 35 ° C.
    [0083] Several and varied dispersants can be used to contribute to the quality of the inventive nanometric silver product, including polyvinylpyrrolidone (PVP), gum arabic, polyvinyl alcohol (APV), polyacrylic acid (APA), polyalylamine (PAAm), polystyrene sodium sulfonate (PSS), 3-aminopropyl-trimethoxysilane (APS), a fatty acid such as stearic and palmitic, lauryl amine, cetyl trimethyl ammonium bromide (BCTA) and tetraoctylammonium bromide (BTOA).
    [0084] The use of PVP has been found to be particularly advantageous. While PVP with an average molecular weight of up to about 2,000,000 gram / mol can be used, we have found that, in most cases, PVP molecules with an average molecular weight greater than about 8,000 g / mol and, more commonly, average molecular weight within the 10,000 / mol range with 200,000 g / mol are particularly effective. The weight ratio of PVP to the silver particles in Step 1 is normally within the range of 0.01 to 10 and, more commonly, within the range of 0.1 to 5.
    [0085] An antifoam agent can be introduced, at any of the process steps, for foam control, as needed. Step 2
    [0086] A reducing agent can be added, under vigorous mixing, to a dispersion containing fine silver oxide particles, by which the oxide particles are reduced, producing a second dispersion containing nanometric silver particles. The presence of a dispersant in Step 2 can significantly reduce or inhibit agglomeration. The dispersant can be the previously added Step 1 dispersant, or it can be a mixture of the previously added Step 1 dispersant and a newly added dispersant. The newly added dispersant can be identical to the dispersant used in Step 1, or it can be a different kind of chemistry.
    [0087] The vigorous mixing can be done in an ultrasonic bath, normally maintained at a temperature ranging from 10 ° C to 35 ° C.
    [0088] We found that, in producing the dispersion of nanometric silver particles of the present invention, it is essential to reduce precipitated solid silver oxides, which have been precipitated in the presence of a suitable dispersant, as described in Step 1. In our attempts to get around Step 1 Using commercially available solid silver oxides as the raw material for Step 2, the nanometer silver particle dispersions had different physical properties and were generally disadvantageous compared to those obtained by the methods of the present invention. We found this to be the case, even when a suitable dispersant is pre-introduced to the reaction mixture (containing the commercially available solid silver oxides) from Step 2.
    [0089] Preferably, the reduction reaction is carried out within an ambient temperature range (generally between 10 ° C and 35 ° C) to obtain the desired dispersion of nanometric silver particles. However, the reduction reaction temperature can rise to about 60 ° C, without adversely affecting the properties of the resulting product. We note that, within this temperature range, an alcohol (such as ethanol or ethylene glycol) is unable to convert silver ions into silver (0), so that the reduction is carried out exclusively by the reducing agent or agents.
    [0090] These reducing agents may include a peroxide, ascorbic acid, sugars such as glucose, metal hydrides such as sodium borohydride, hydrazine hydrate, formaldehyde and a saccharide or reducing agents, belonging to the chemical families of these reducing agents. Hydrogen peroxide, which can be considered a "green" reagent, as its decomposition ends up leading to the formation of water and oxygen, can be a preferred peroxide.
    [0091] In order to simplify the method of the invention, the dispersant used in Step 1 can be reused as the dispersant for Step 2. Additional dispersants can be introduced in Step 2, including the dispersants mentioned above with respect to Step 1.
    [0092] Yield and economic considerations seem to dictate a stoichiometric ratio of at least 1 to 1 between the alkali hydroxide and the soluble silver salt (such as silver nitrate) of the reaction in Step 1. Thus, the yield of the intermediate product of silver oxide would be higher. Surprisingly, however, we found that using a stoichiometric excess of alkaline hydroxide can ultimately result in large clumps of silver particles. In the laboratory, an excess of 50% of an alkaline hydroxide (such as potassium hydroxide), with respect to the stoichiometric relationship between the hydroxide and soluble silver compounds, resulted in disadvantageous agglomeration of silver particles.
    [0093] Similar results were obtained for approximately a 20% excess of alkaline hydroxide with respect to the stoichiometric relationship between alkaline hydroxide and silver nitrate.
    [0094] We consider it advantageous, after long experimentation, to operate Step 1 in a stoichiometric relationship between the hydroxide and a soluble silver compound within a small range of 0.8 to 1.0 and, more typically, 0.8 to 0.98 or 0.8 to 0.96. Within that range, the silver yield is actually lower, but the yield of the high quality product can be much higher.
    [0095] In Step 2, the concentration of silver particles within the reaction mixture is normally 0.5% to 5%, by weight, and more commonly 1% to 3%, by weight.
    [0096] In addition to water, an additional solvent can be introduced in Step 1 and / or Step 2. Typically, the additional solvent includes a polar solvent as a polar organic solvent. It is generally advantageous for the additional solvent to be relatively volatile, soluble in water and to dissolve substantial amounts of dispersants used.
    [0097] Preferably, alcohols such as methanol, ethanol and isopropyl alcohol (IPA) can be used as polar solvents. However, various glycols and the like can also be used. Step 3
    [0098] Normally, water or an aqueous solvent can be used to purify the dispersion resulting from Step 2 in an appropriate purification system. The introduction of the water purification system or aqueous solvent is controlled to replace the spent aqueous liquor, while maintaining the concentration of silver particles at any time below a predefined value (below 90% by weight) , and preferably below 80%, below 70% or below 60%). As a result, substantially all of the salts and most of the dispersant in the aqueous liquor is removed without damaging the shapes or agglomerating the silver particles.
    [0099] The aqueous solvent may contain, in addition to water, an organic solvent, such as a polar organic solvent. The fluxes produced in Step 3 typically include a concentrate containing most of the nanometer silver particles, and a relatively dilute flux containing a low concentration of the silver nanoparticles and, preferably, substantially none of the silver nanoparticles. In Step 3, substantially all of the salts, part of the dispersant and part of the liquid that are present with the formed silver particles are removed. Generally, specific values for the final concentration of salts (based on the weight of the silver), the dispersant (based on the weight of the silver) and the silver particles (based on the weight of the dispersion) are predefined, and the operation of Step 3 is considered completed when these default values are obtained.
    [00100] We found that Step 3 can be performed in a microfiltration system such as a membrane purification system containing at least one membrane capable of separating silver particles from aqueous liquor, without losing a fraction of silver particles in the phase water that would make the process economically unfeasible. As an alternative or in addition, Step 3 can be performed in a centrifuge purification system containing at least one centrifuge, such as a settling centrifuge.
    [00101] A microfiltration system and method of general relevance to the present invention is disclosed by Pagana et al., "Applied Pilot-Scale Studies on Ceramic Membrane Processes for the Treatment of Wastewater Streams" (Global NEST Journal, Vol.8 , No. 1, pp 23-30, 2006) and are incorporated by reference, in their entirety, to the specifications, as fully established herein.
    [00102] At least one membrane of the membrane purification system must be able to filter the silver nanometric particles in the dispersion. Therefore, the characteristic pore size of this membrane can be in a range that is appropriate to retain the nanometer silver particles. The membranes can be made of a metallic material, ceramic material, polymeric materials, or other materials that can be known to those skilled in the art. Step 4
    [00103] A volatile organic solvent can replace most of the aqueous liquor from the purified dispersion obtained in Step 3, in a method similar to the method used in Step 3. The same purification system can be used. When displacing the aqueous liquor, further purification of the silver particles is carried out, which can be essential for various products and applications.
    [00104] The volatile organic solvent can advantageously be soluble in water and can readily dissolve the dispersant or dispersants remaining from Step 3. Various solvents can be suitable as solvents for Step 4 of the process, alone or mixed with at least one additional solvent. These solvents include, among others, alcohols such as methanol, ethanol, propanol, isopropanol, and a butanol, such as 1 - butanol; acetonitrile; dimethyl sulfoxide (DMSO); alkylamines such as butylamine; ethylenediamine; dimethylacetamide; 1,4-butanediol; formic acid; and acetic acid. Step 5
    [00105] A second organic solvent, whose identity and properties can be dictated by market requirements, can be used to replace most, and generally at least 80%, or at least 90% or 95%, of the volatile organic solvent in dispersion obtained in Step 4. The solvent replacement or displacement method can be similar to the method used in Step 3 and / or Step 4, and the purification system can be similar or identical.
    [00106] However, the second organic solvent can replace the volatile organic solvent in an evaporation system, in which the volatile organic solvent evaporates, with a concomitant addition of the desired organic solvent, in order to maintain a concentration of silver particles below specific target value. Usually the concentration of silver particles is a maximum of 90%, a maximum of 85% or a maximum of 80%.
    [00107] Various solvents may be suitable as solvents for Step 5 of the process, alone or mixed with at least one additional solvent. These solvents include, but are not limited to, ethylene glycol and derivatives (for example, diethylene glycol monomethyl ether (DGME), dipropylene glycol (DPG), dipropylene glycol monomethyl ether (DPM) and tripropylene glycol methyl ether (TPM)); N-methyl-2-pyrrolidone (NMP); various alcohols, including ethanol, isopropanol, benzyl alcohol and terpineol; butyl carbitol acetate; and specific epoxy resins. A suitable solvent mixture is TPM / NMP, which can normally be used up to a weight ratio of about 85: 15.
    [00108] It was concluded that several solvents were less suitable or unsuitable for use in Step 5, including acetates such as propylene glycol methyl ether acetate (PMA), which caused the agglomeration of silver particles when used in conjunction with surfactants or dispersants.
    [00109] Thus, by preparing the nanometer silver particles as described in Steps 1 and 2 and conducting the process of obtaining gait as described in Steps 3-5, the nanometer silver dispersions of the present invention can achieve exceptional stability (with a guaranteed validity period of at least 9 months and, more commonly, at least 12 months, at least 18 months or at least 24 months). The inventive dispersions can be characterized by very low specific resistance values (maximum 6 x 10-6 ohmrcm, maximum 5 x 10-6 ohrnrcm, maximum 4 x 10-6 ohmxm, maximum 3.5 x 10-6 ohmxm, maximum 3 x 10-6 ohmrcm, or maximum 2.5 x 10-6 ohmxm), measured according to ASTM procedure F 390-98 (re-approved 2003).
    [00110] In another embodiment of the present invention, we have found that the first purification step (Step 3) can be advantageously carried out by nanofiltration or nano-separation using nano-separation membranes. Such processes can be excessively and impractically slow when the size of the filtered species approaches the size of the pore or opening of the membrane. In addition, nanofiltration membrane processes may even be substantially impossible when the size of the filtered species is equal to, or exceeds, the size of the membrane opening. Another, perhaps even more significant, impediment to the use of such nano-separation processes concerns the relative size between particles or species prevented by nano-separators (such as nanomembranes) and the species that should pass through nano-separators. We found that certain dispersants, such as PVP, can have an elongated or needle-shaped structure. While the characteristic long dimension or diameter of such molecules is too large to pass through the nano-separator openings and can be considerably larger than the silver nanoparticles themselves, the characteristic narrow size or diameter of such molecules may be smaller in orders of magnitude. Thus, the structure of the dispersant can be adapted to meet the requirements of the process in order to advantageously effect a nano-separation of the silver nanoparticle dispersant.
    [00111] Thus, according to a preferred embodiment of the present invention, the PVP dispersant has at least one characteristic narrow dimension / diameter with respect to the silver particles and with respect to the characteristic diameter of the membrane openings. This narrow size / diameter characteristic of the dispersant is preferably less than half the average secondary particle size of the silver particles.
    [00112] Thus, while the average molecular weight of polyvinylpyrrolidone should normally have an average molecular weight of less than approximately 200,000 grams per mol, in order to pass through several suitable nanomembranes, the average molecular weight of polyvinylpyrrolidone should preferably exceed about 8,000 grams per mol, in order to avoid reactivity and / or compatibility problems in one or both reaction steps. Despite the reduced separation efficiency, it is generally preferable for PVP to have an average molecular weight of at least 15,000, at least 20,000 or even at least 25,000 grams per mol.
    [00113] In some applications, for example, in which extremely fine silver particles are produced, or where high separation kinetics are desirable, PVP should preferably have an average molecular weight of less than approximately 100,000 grams per mol and, preferably less than approximately 80,000 grams per mol.
    [00114] Nanofiltration ceramic membranes have been used advantageously, but polymeric and / or metallic nanofiltration membranes can also be fundamentally suitable. Membrane systems can be static or dynamic (for example, having a vibrational mechanism to facilitate separation).
    [00115] Typical nano-separation or nanofiltration ceramic membranes, for use in conjunction with the method of the present invention, have one or more pores that are generally cylindrical, with a high ratio of length to width, through which water / solvent and fine matter can pass. In many cases, the membrane is usually shaped like a long cylinder, but other geometries may be viable.
    [00116] We have found that nanomembranes less than 200 nanometers in pore diameter may be suitable for use in the process of the present invention. In some applications, the preferred pore diameter is less than 150 nanometers, less than 120 nanometers or less than 100 nanometers. Generally, the pore diameter or nominal pore diameter of the membrane can be at least 20 nanometers and often at least 30-50 nanometers, in order to allow the passage of several species through the membrane openings, and so that the separation kinetics is not too slow.
    [00117] According to another preferred embodiment of the present invention, the size and shape of the dispersant and the size of the membrane openings can be selected in such a way that the silver nanoparticles pass through the openings, while the passage of the dispersant through the openings it is substantially hampered or impeded.
    [00118] In the last step of the separation, much smaller openings of the membrane can be selected, so that the passage of silver nanoparticles through the openings is hindered or substantially impeded, while smaller molecules, such as water, ethanol, etc., pass through the openings relatively easily. This embodiment of the present invention can be particularly effective in applications where the average particle size of the silver product is particularly low, or where a substantial fraction of the silver product has a low average secondary particle size (for example, below 30 nanometers, or even below 50 nanometers).
    [00119] In another preferred embodiment of the present invention, the formation of silver oxide and the reduction of silver oxide to produce the silver nanocrystals are carried out in a single process step. However, the specific conditions and preferred reagents and dispersants are substantially similar to those provided above for the two-phase reaction process. As an example, an aqueous solution containing potassium hydroxide can be introduced, under vigorous stirring, to a second aqueous solution containing a soluble silver compound such as silver nitrate, a dispersant such as PVP, and a reducing agent such as sodium peroxide. hydrogen. In this case, the reduction of silver ions only begins when the hydroxide solution is mixed with the second aqueous solution. EXAMPLES
    [00120] Reference is now made to the following Examples, which, together with the description above, illustrate the invention in a non-limiting way.
    [00121] The chemicals used to make these Examples are identified below: AgNO3 - Aldrich AgNO3 (containing 63.6% Ag) - Saxony (Germany) KOH - Aldrich hydrogen peroxide (~ 33% aqueous solution) - Makhteshim ( Israel) Polyvinylpyrrolidone (PVP), MW = 55,000 - Aldrich. Polyvinylpyrrolidone (PVP), MW = 8,000 - Aldrich. antifoam agent Contraspum 1012 - Zschimmer & Schwarz (Germany) abs ethanol. - Aldrich isopropyl alcohol (IPA) - Aldrich tripropylene glycol methyl ether (TPM) - Aldrich butyl carbitol acetate (BCA) - Aldrich caprylic acid - Aldrich Epoxy XY8000 - Japan Epoxy Resins Co., Ltd. (Japan). The epoxy XY8000 can be identified by CAS No. 30583-72-3 and has the chemical name of cyclohexanol, 4.4- (1-methylethylidene) bis-, polymer with (chloromethyl) oxirane.
    [00122] Aqueous solutions were prepared using deionized water, using an Ionex water purification system (PuriTech, Dessel, Belgium). All reagents and solvents were used without further purification.
    [00123] The instruments used in conjunction with the Examples are identified below:
    [00124] Particle size analyzes (d50) were performed using a Brookhaven 90Plus particle size analyzer (Brookhaven Instruments Corporation, Holtsville, New York).
    [00125] The particle size analysis (d50) in Example 3 was performed using a Malvern Master Sizer 2000.
    [00126] High Resolution Scanning Electron Microscopy (HRSEM) images were generally obtained using an HRSEM Ultra Plus Zeiss Gemini (lnlens Detector).
    [00127] Backscattered Electron Diffraction Patterns (EBSD) were obtained using an E-SEM Quanta ™ 200 (FEI, Hillsboro, Oregon). The instrument was equipped with an accessory for Channel 5 orientation microscopy (MIO) (Oxford Instruments, England).
    [00128] Evaporation was carried out using an R-2 15 Rotavapor®, equipped with a heating bath (BÜCHI Labortechnik AG, Flawil, Switzerland).
    [00129] The dispersion filtration was carried out by means of a membrane system that included the ceramic membranes (JM Separations BV, Countries). EXAMPLE 1
    [00130] 52g of AgNO3 and 3.3g of PVP (MW = 55,000) were dissolved in a mixture of 780ml of ethanol and 80ml of water (solution A). 17g of KOH were dissolved in 140ml of water (solution B). Solution B was poured into solution A, under vigorous stirring, in an ultrasonic bath, forming a colloidal precipitate of Ag2O at room temperature. After stirring the dispersion for 10 minutes, 180 ml of H2O2 (33%) were slowly pumped into the dispersion, under agitation, in a temperature range between 25 ° C to about 60 ° C, forming silver nanoparticles. The dispersion was stirred for an additional 15 minutes and transferred to a storage tank to await further treatment.
    [00131] A particle size analysis yielded an average particle size (d50) of about 80 nanometers. EXAMPLE 2
    [00132] 53g of AgNO3 and 54g of PVP (MW = 55,000) were dissolved in a mixture of 860ml of water (solution A). Five drops of an antifoam agent were also introduced. 17g of KOH were dissolved in 140ml of water (solution B). Solution B was poured into solution A, under vigorous stirring, at room temperature, forming a colloidal nanometric precipitate of Ag2O (d50 below 60 nanometers). After stirring the dispersion for 10 minutes, 180ml of H2O2 (33%) was slowly pumped directly into the dispersion under stirring, in situ, reducing the silver oxide to silver, at which point the reaction mixture heated from 25 ° C to about 60 ° C. The dispersion was stirred for another 15 minutes and was transferred to a storage tank to await further treatments.
    [00133] An analysis of silver particle size yielded an average particle size (d50) of about 50 nanometers. EXAMPLE 3
    [00134] Two liters of aqueous solution containing 170 g / l of AgNO3 and 90 g / l of hydrogen peroxide (33%) were dripped, under intense agitation, into a liter of aqueous KOH solution with a concentration of 56 g / l, time when the reaction mixture warms from 25 ° C to about 60 ° C. The silver particles produced were agglomerated.
    [00135] A particle size analysis yielded an average particle size (d50) of about 1.5 microns (1500 nanometers). EXAMPLE 4
    [00136] One liter of aqueous KOH solution with a concentration of 56 g / l was dripped, under intense agitation, into two liters of aqueous solution containing 170 g / l of AgNO3, 90 g / l of hydrogen peroxide (33% ) and 170 grams of PVP (W = 55,000). During the reaction, the temperature increased in the range from about 25 ° C to about 60 ° C. The dispersion was stirred for another 15 minutes and was transferred to a storage tank to await further treatments.
    [00137] An analysis of the size of silver particles yielded an average particle size (d50) of about 90 nanometers. EXAMPLE 5
    [00138] 53g AgNO3 and 100g of PVP (MW = 55,000) were dissolved in a mixture of 850ml of water (solution A). Five drops of an antifoam agent were also introduced. 17g of KOH were dissolved in 140ml of water (solution B). Solution B was poured into solution A, under vigorous stirring, forming a colloidal nanometric precipitate of Ag2O. After stirring the dispersion for 10 minutes, 180ml of H2O2 (33%) was slowly pumped directly into the dispersion and stirred in situ, reducing the silver oxide to silver in the temperature range between 25 ° C and about 60 ° C.
    [00139] The silver particles produced were agglomerates. EXAMPLE 6 Example 2 was repeated, but using triplicate amounts. 159g of AgNO3 and 162g of PVP (MW = 55,000) were dissolved in a mixture of 2580ml of water (solution A). Fifteen drops of a defoaming agent were also introduced. 51g of KOH were dissolved in 420ml water
    [00140] (solution B). Solution B was poured into solution A, under vigorous stirring, forming a colloidal nanometric precipitate of Ag2O. After stirring the dispersion for 10 minutes, 540ml of H2O2 (33%) was slowly pumped directly into the dispersion under agitation, in situ, reducing the silver oxide to silver at a temperature ranging between 25 ° C and about 60 ° C. The dispersion was stirred for another 15 minutes and was transferred to a storage tank to await further treatments.
    [00141] A particle size analysis of the produced silver particles yielded an average particle size (d50) of about 50 nanometers of a relatively narrow distribution. EXAMPLE 7: Concentrating a dispersion
    [00142] 1000 ml of the dispersion of the product of Example 6, containing about 25g of nanometer silver particles, were pumped out of the top of the storage tank in which the dispersion was kept without any mixing, to ensure that large particles, if any, they were precipitated to the bottom of the storage tank and are avoided in subsequent treatments. The dispersion was washed in a membrane separation system, gradually and continuously feeding about 20 liters of water to the membrane system and simultaneously gradually and continuously removing a similar volume of spent washing liquor from the membrane system, in such a way that the concentration of silver particles never exceeded 90% (and preferably less than 60%), by weight. The membrane system included ceramic membranes (JM Separations BV) with pores or separation capillaries having a nominal pore diameter of 100 nanometers. Water and ionic and dispersant matter were selectively passed through the membranes, leaving the nanometric silver particles in the dispersion.
    [00143] The washing process was continued until the salts in the dispersion were practically eliminated, and the dispersant was reduced to a predefined concentration of 3% by weight of the silver particles.
    [00144] According to the mass balance of the water inlet to the membrane system and the spent washing liquor flowing out of the membrane system, it was deliberately changed during this washing step, in order to carry out a washing operation efficient and obtain a concentrated dispersion, the resulting washed silver dispersion contained about 25% solids by weight. A particle size analysis of the washed silver particles yielded an average particle size (d50) of about 50 nanometers; no significant change in particle size was observed between the washed and unwashed nano-silver product.
    [00145] The HRSEM image of the nanometric particles obtained is provided in Figure 2 (instrument magnification = x 100,000; image display magnification = x 40000), and the Backscattered Electron Diffraction (EBSD) pattern of these silver particles is given in Figure 3. These numbers reveal the following characteristics with respect to silver particles: 9. Most monocrystal silver particles (typically, at least 70%, at least 80%, or at least 90%, as determined by EBSD correlation); 10. Monocrystalline particles include particles with triangular faces, square faces, hexagonal faces and heptagonal faces; and 11. Monocrystalline particles that have triangular faces represent at least 2%, at least 5% and, normally, between 2% and 15% of silver particles, based on the number of particles (determined by manual particle counting in SEM fields). EXAMPLE 8: Replacing Water with a Volatile Organic Solvent (Water-Ethanol solvent exchange)
    [00146] A 100ml portion of a dispersion of silver particles in water, containing approximately
    [00147] 150g of silver particles, which was prepared in a similar manner as in Example 7, was concentrated to 500 ml, using the same membrane separation system as in Example 7. 400 ml of ethanol were then added, and the dispersion it was concentrated again to 500 ml by withdrawing the required volume of liquid. This cycle, in which 400 ml of ethanol is added and about 400 ml of the ethanol and water mixture is removed, was repeated until the ethanol concentration reached 94% - 95% by weight (which is close to the composition of an azeotropic mixture water-ethanol). The resulting 500ml of silver dispersion contained about 150g of nanometer silver and about 300g of the ethanol-water mixture.
    [00148] A particle size analysis of the silver dispersion after the water and ethanol exchange yielded an average particle size (d50) of about 80 nanometers.
    [00149] Most of the particles obtained were single crystals. EXAMPLE 9: Replacing Water with a Volatile Organic Solvent (IPA)
    [00150] Example 8 was repeated with isopropyl alcohol (IPA) instead of ethanol.
    [00151] A particle size analysis of the silver dispersion after the exchange of water and isopropyl alcohol yielded an average particle size (d50) of about 90 nanometers.
    [00152] Most of the particles obtained were single crystals. EXAMPLE 10: Replacing the Volatile Organic Solvent with a Non-Volatile Organic Solvent (TPM ethanol-solvent exchange)
    [00153] The 500ml silver dispersion of Example 8, which contains about 150g of silver particles and about 300g of solvent (mixture of ethanol and water), were transferred to a 1 liter bottle. 150g of tripropylene glycol methyl ether (TPM) was added to the flask (in order to finally obtain a final dispersion containing about 50% solids by weight). The flask was connected to a Rotavapor® device, and the ethanol was evaporated under vacuum (at 20mm Hg; 60 ° C; 80 rpm). The resulting dispersion of silver in TPM containing 49.5% (by weight) of silver, with an average particle size (d50) of about 50 nanometers (as well as traces of ethanol and water). This specific dispersion had an expiration date of more than one year (and up to two years). In addition, after drying and thermal sintering, the specific resistance, as measured according to ASTM standard procedure F390 - 98, was below 4 x 10-6 ohmxm, which is considered an excellent value for applications such as conductive inks .
    [00154] An HRSEM image showing the nanometric silver particles obtained is provided in Figure 4 (instrument magnification = x 100,000; image display magnification = x 40000). It is evident that the general appearance of the silver particles has not been visibly changed from the appearance of the particles obtained in Example 7.
    [00155] The viscosity of the dispersion was measured, for the different concentrations of silver particles (metal charge). The results are provided in Table 1. TABLE 1
    * The% metal charge is defined as the weight of the metal particles (silver) x 100, divided by the weight of the dispersion. EXAMPLE 11: Replacing the Volatile Organic Solvent (IPA) with an Organic Solvent - BCA (IPA - BCA solvent exchange)
    [00156] The 500ml silver dispersion of Example 9, which contains about 150g of silver particles and about 300g of solvent (mixture of IPA and water), were transferred to a 1 liter bottle. 150g of butyl carbitol acetate (BCA) was added to the flask (in order to obtain, eventually, a final dispersion containing about 50% solids, by weight). The flask was connected to a Rotavapor® device, and the IPA was evaporated under vacuum (at 20mm Hg; 60 ° C; 80 rpm). The resulting silver dispersion in the BCA contained particles of 49.7% (by weight) of silver, having an average particle size (d50) of about 60 nanometers. The silver dispersion also contained traces of IPA and water. EXAMPLE 12: Replacing the Volatile Organic Solvent (IPA) with an Epoxy Resin (Epoxy Resin-IPA exchange)
    [00157] The 500ml silver dispersion of Example 9, which contains about 150g of silver particles and about 300g of solvent (mixture of IPA and water), were transferred to a 1 liter flask and 15g of acid was added caprylic. The flask was connected to a Rotavapor® device, which was rotated for 15 minutes at 80 ° C, at 80 rpm). Subsequently, 150g of Epoxy resin XY8000 were added to the flask (in order to obtain, eventually, a final dispersion containing about 50% solids, by weight). Rotavapor was reactivated (at 20mm Hg, 80 ° C and 80 rpm) and, after 1 hour, most of the IPA-water solvent was evaporated.
    [00158] The resulting silver dispersion in the epoxy resin contained particles of 48% (by weight) of silver, having an average particle size (d50) of about 70 nanometers. The silver dispersion also contained traces of IPA and water.
    [00159] Most of the particles obtained were single crystals. EXAMPLE 13
    [00160] The presence of single crystals was demonstrated qualitatively by means of Backscattered Electron Diffraction (EBSD).
    [00161] EBSD produces a diffraction pattern on the surface of the silver nanoparticle sample. The procedure, which will be readily understood by those skilled in the EBSD technique, is as follows: 12. The sample is checked using a scanning electron microscope (SEM) Quanta ™ 200, usually at a working distance of 18mm and 20 eV , to obtain an image or a diffraction pattern. The stitch size is 4.5; the probe current is about 0.5; the collection time for EBSD standard: 300 msec; integration: 50. 13. Diffraction image interpretation is performed using the instrument's software (comparing basic silver crystallographic data); 14. The diffraction "solution" is matched, representing the orientation of the crystal, correlating each line of kikuchi to its crystallographic plane of fitting into the crystalline structure. If there is a perfect correspondence between the kikuchi lines and the crystallographic planes (according to the theoretical data), the diffraction determines the orientation of a single crystal.
    [00162] In the case of nanometric silver particles, it is not always possible to obtain a perfect solution; sometimes there is no solution. This may indicate that the beam is in a grain boundary. Alternatively, it is not possible to obtain a perfect solution when the bundle is located between two grains. EXAMPLE 14
    [00163] Following the procedure of Example 13, we quantified the presence of nanometer silver monocrystals within each nanometer silver sample. Quantification was achieved by conducting a plurality (at least 5 and preferably at least 10) of scans at randomly chosen points. By testing the different dispersions of the present invention, at least 30% or at least 50% of the scans produce a substantially perfect match for a silver monocrystal. More generally, at least 80%, at least 90%, or substantially 100% of the scans produces a substantially perfect match for a silver monocrystal.
    [00164] We found that if at least 30% of the scans produce a substantially perfect match for a silver monocrystal, then most nanometric silver particles are monocrystalline (based on the number of particles). If at least 50% of the scans produce a substantially perfect match for a silver monocrystal, then at least 60% and, normally, at least 70% of the nanometer silver particles are monocrystalline. If at least 60% of the scans produce a substantially perfect match for a silver monocrystal, then at least 70% and, normally, at least 80% of the nanometer silver particles are monocrystalline. If at least 80% of the scans produce a substantially perfect match for a silver monocrystal, then at least 90% and, normally, at least 95% of the nanometer silver particles are monocrystalline.
    [00165] In theory, these quantitative EBSD scanning methods can provide a quantitative assessment of an upper layer or cross-section of the sample. In practice, however, this quantitative assessment closely reflects the fraction of silver particles that contains a monocrystalline character, particularly for samples that do not have an extremely wide particle size distribution. EXAMPLE 15:
    [00166] Figure 5 is a SEM image of a sample containing nanometric silver particles, produced according to the present invention. Randomly chosen locations in the sample were scanned. In five of the six locations, a perfect match for a single silver crystal was obtained.
    [00167] Figure 6 provides five illustrations of the 3D crystal orientation for the five locations where a perfect match was obtained. Each of the diffractions produced had a different orientation. In addition, the orientation distribution obtained was not very close to the theoretical random distribution, indicating that there is no preferential orientation in nanometric silver particles in the sample. EXAMPLE 16
    [00168] Inventive dispersions of silver particles were prepared for specific resistance testing as follows:
    [00169] The dispersion is poured onto a glass substrate with dimensions of ~ 3cm x 3cm, using a pipette, until the substrate is completely covered. Heat treatment (in air) is carried out at 130 ° C for 10 minutes, followed by 640 ° C for 20 minutes. The thermally sintered sample is removed immediately from the oven. Typically, the film thickness is about 10 micrometers.
    [00170] Using a four-point probe measurement, specific resistance is obtained. EXAMPLE 17
    [00171] An inventive dispersion of silver particles in tripropylene glycol monomethyl ether (TPM) was prepared for specific strength tests according to the procedure provided in Example 16. The sample had a metal charge of about 50%.
    [00172] The specific resistance, determined according to the procedure provided in Example 16, was about 3.5 x 10-6 ohmxm, just a little more than twice the specific resistance of bulk silver.
    [00173] The term "mean secondary particle size" used here, in the specification and in the following claims section, is used in relation to silver oxide and silver particles and refers to the average diameter of the silver particles and the silver oxide, and has the specific objective of including the diameters of the agglomerated particles.
    [00174] As used in this specification and in the following claims section, the term "average diameter", used in relation to silver oxide and silver particles, refers to an equivalent spherical particle size (dso), calculated using the Einstein-Stokes equation, by a Brookhaven 90Plus particle size analyzer (Brookhaven Instruments Corporation, Holtsville, New York) or, if unavailable, by a functionally equivalent particle size analyzer suitable for measuring the size of equivalent spherical particle across the range of 5 to 2ooo nanometers.
    [00175] When determining the average diameter, the particle size analysis is performed professionally and can be reproduced using the particle size analyzer by trained and qualified personnel to operate the particle size analyzer and under the following conditions : 15. a representative sample of the solid particles (silver oxide, silver) is collected; 16. the analysis is carried out in a dispersion of solid particles in their respective liquid; 17. the analysis is done at room temperature; 18. the dispersion angle is 9o degrees.
    [00176] As used here in the specification and in the claims section that follows, the term "polyvinylpyrrolidone", also known as PVP, refers to a water-soluble polymer that has or includes the following molecular structure:
    PVP is normally made from vinylpyrrolidone monomer, which has the following structure:

    [00177] The PVP dispersant market includes polymers produced by adding (for example, grafting) PVP to other organic functions. As used herein in the specification and in the following claims section, the term "polyvinylpyrrolidone" includes such dispersants.
    [00178] As used herein in the specification and in the following claims section, the term "silver compound" and the like must include an inorganic silver salt, an organic silver salt or an organo-silver complex.
    [00179] As used herein in the specification and in the following claims section, the term "soluble silver compound", and the like, refers to a silver compound with a solubility of at least 10 grams / liter in water or ethanol at 25 ° C. Preferably, the soluble silver compound has a solubility of at least 25 grams / liter in water or in ethanol at 25 ° C and, preferably, a solubility of at least 50 grams / liter in water or ethanol at 25 ° C.
    [00180] As used herein in the specification and in the following claims section, the term "volatile solvent", as a volatile organic solvent, refers to a solvent that, in pure form, has a boiling point of less than 105 ° C, and usually at 100 C or less, at atmospheric or ambient pressure.
    [00181] As used here in the specification and in the following claims section, the term "non-volatile solvent", as a non-volatile organic solvent, refers to a solvent that, in pure form, has a boiling point above 105 ° C, and usually above 110 ° C, at atmospheric or ambient pressure.
    [00182] As used herein in the specification and in the following claims section, the term "single crystal" "monocrystal", and the like, with respect to silver particles, refers to a monocrystal silver particle as determined by the standard Backscattered Electron Diffraction (EBSD) method described in Example 13 above. Any quantitative assessment of a fraction or percentage of monocrystalline particles within a sample, as used here in the specification and in the claims section below, can be performed according to the quantitative method of determining EBSD described in Example 14. While in theory this quantitative scanning method EBSD provides a quantitative assessment of a top layer or cross section of the sample, in practice, this quantitative assessment closely reflects the fraction of silver particles that have a monocrystalline character, particularly for samples that do not have a distribution of extremely wide particle size.
    [00183] Thus, as used here in the specifications and in the following claims section, the term "majority", with respect to silver particles, refers to at least one of the following: at least 30% of scans of Randomly selected EBSD produces a substantially perfect match for a silver monocrystal, according to the procedure described in Example 14, or more than 50% of the silver particles, based on the number of silver particles.
    [00184] As used here in the specifications and in the following claims section, the term "standard sintering" or "standard thermal sintering" refers to the sintering process described in Example 16.
    [00185] It will be taken into account that certain characteristics of the invention, which are, for greater clarity, described in the context of the separate modalities, can also be combined into a single modality. On the other hand, several characteristics of the invention, which, for the sake of brevity, are described in the context of a single embodiment, can be provided separately or in any suitable subcombination. Likewise, the content of a claim, depending on one or more specific claims, can generally depend on other unspecified claims, or the content of such claims can be combined, in the absence of any specific evident incompatibility between them.
    [00186] Although the invention has been described in conjunction with specific modalities thereof, it is evident that many alternatives, modifications and variations will be clear to those skilled in the art. In this sense, the invention intends to cover all these alternatives, modifications and variations that are within the spirit and scope of the added claims. All publications, patents and patent applications mentioned in these specifications, including US Patent No. 6,277,169 and Patent Publication No. WO 2003/080231, are hereby incorporated, in their entirety, by reference to the specifications, to the same extent. that each individual publication, patent or patent application has been specifically and individually nominated to be incorporated herein by reference. Furthermore, citation or identification of any reference in the present application cannot be interpreted as an admission that such reference is available as a state of the art of the present invention.
    权利要求:
    Claims (10)
    [0001]
    1. Concentrated dispersion of nanometric silver particles, the dispersion comprising: (a) a first solvent; (b) a plurality of nanometer silver particles, where a majority of at least 50% of such particles are monocrystalline silver particles, such a plurality of nanometer silver particles having an average secondary particle size (d50) within one range of 30 to 300 nanometers, such particles disposed in said solvent; and (c) at least one dispersant, characterized by the fact that a concentration of such nanometric silver particles in the concentrated dispersion is within a range of 30 to 75%, by weight, where a concentration of such dispersant within the dispersion is within a range of 0.2% to 30% of such concentration of such nanometer silver particles, by weight.
    [0002]
    2. Dispersion according to claim 1, characterized by the fact that said concentration of such dispersant within the dispersion is at most 5%.
    [0003]
    3. Dispersion according to claim 1, characterized by the fact that a dispersion viscosity at 25 ° C is less than 120cP.
    [0004]
    4. Dispersion according to claim 1, characterized by the fact that said average secondary particle size is at least 50 nanometers.
    [0005]
    5. Dispersion according to claim 1, characterized by the fact that at least 70% of such nanometer silver particles are such monocrystalline silver particles.
    [0006]
    6. Dispersion according to any one of claims 1 to 5, characterized by the fact that at least one dispersant is selected from the group of dispersants, consisting of a polyvinylpyrrolidone (PVP), gum arabic, polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyalylamine (PAAm), polysodium styrene sulfonate (PSS), 3- (aminopropyl) trimethoxysilane (APS), a fatty acid, lauryl amine, cetyltrimethylammonium bromide (CTAB) and tetraoctylamonium bromide (TOAB).
    [0007]
    Dispersion according to any one of claims 1 to 5, characterized in that the concentrated dispersion contains at least 40% by weight of said plurality of nanometric silver particles.
    [0008]
    8. Method for producing the dispersion of nanometric silver particles defined in any one of claims 1 to 7, characterized by the fact that it comprises the steps of: (a) reaction of silver nitrate with potassium hydroxide in an aqueous medium, in an presence of polyvinylpyrrolidone, to produce solid silver oxides with an average secondary particle size below 1200 nanometers; (b) reaction of such solid silver oxides with hydrogen peroxide in an aqueous medium, in the presence of polyvinylpyrrolidone, to produce a first dispersion of silver particles, which have an average secondary particle size below 300 nanometers; and (c) removing up to 90% of said aqueous medium from the particles, while maintaining the concentration of the silver particles below 90% by weight, to produce the dispersion.
    [0009]
    9. Method according to claim 8, characterized by the fact that it further comprises the step of particle concentration to form a second dispersion, concentrated in relation to such a first dispersion, in which a concentration of such nanometric silver particles in the dispersion is within a range of 30% to 75% by weight.
    [0010]
    Method according to claim 8 or 9, characterized in that the dispersion has been aged for at least 6 months, at least 9 months, at least 12 months, at least 18 months or at least 24 months.
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    同族专利:
    公开号 | 公开日
    GB201020556D0|2011-01-19|
    KR101932781B1|2018-12-27|
    RU2013130145A|2015-01-20|
    EP2649621A2|2013-10-16|
    CN103282969B|2016-08-10|
    US10984920B2|2021-04-20|
    CN103282969A|2013-09-04|
    WO2012078590A2|2012-06-14|
    EP2649621B1|2020-08-12|
    US20170128900A1|2017-05-11|
    US20220044838A1|2022-02-10|
    BR112013013885A2|2016-09-13|
    RU2593311C2|2016-08-10|
    JP2014505784A|2014-03-06|
    KR20140010935A|2014-01-27|
    US9556350B2|2017-01-31|
    WO2012078590A3|2012-08-16|
    JP6067573B2|2017-01-25|
    EP2649621A4|2018-04-04|
    GB2486190A|2012-06-13|
    US20130270490A1|2013-10-17|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-04-07| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: H01B 1/22 , B22F 9/24 , C09D 11/00 , C09D 5/24 , C08K 3/08 Ipc: B22F 1/00 (2006.01), C09D 11/00 (2014.01), C09D 5/ |
    2020-04-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GB1020556.5A|GB2486190A|2010-12-06|2010-12-06|Concentrated dispersion of nanometric silver particles|
    GB1020556.5|2010-12-06|
    PCT/US2011/063459|WO2012078590A2|2010-12-06|2011-12-06|Stable dispersions of monocrystalline nanometric silver particles|
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