Method for producing silver nanoparticles

Abstract

To provide a manufacturing method for a silver nanoparticle with a small and uniform particle size at a low cost in a manufacturing method for a silver nanoparticle by microwave irradiation of a reaction mixture.SOLUTION: A manufacturing method for a silver nanoparticle including a step of irradiating a reaction mixture with microwaves relates to a method comprising (i) a step of irradiating a reaction mixture with microwaves having a power density of 10 W / mL to 50 W / mL based on the total volume of the reaction mixture to cause the temperature of the reaction mixture to reach the reaction temperature, and (ii) a step of stopping the irradiation of the microwave after the temperature of the reaction mixture has reached the reaction temperature in the step (i), and (iii) a step of maintaining the temperature of the reaction mixture at the reaction temperature after the irradiation of microwaves to the reaction mixture is stopped in the step (ii).SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to a method for producing silver nanoparticles.

Background Art

[0002] In recent years, metal nanoparticles having properties different from those of bulk materials have been used in various applications such as catalysts and electronic component members.

[0003] In the field of electronics mounting, metal nanoparticles are being studied as lead-free bonding materials that can be bonded at low temperatures. Although lead-free solder is difficult to bond at 250°C or lower, lead-free solder containing metal nanoparticles utilizes the characteristics of metal nanoparticles, that is, while having a lower melting point compared to bulk materials, when used for bonding and sintered, it has the melting point of a bulk material, enabling bonding at 250°C or lower.

[0004] As a method for preparing such metal nanoparticles, for example, Patent Document 1 discloses a method for producing metal fine particles in which a reaction solution containing a metal precursor and a reducing agent for the metal precursor is circulated through a flow tube disposed in a microwave irradiation space, and a uniform and concentrated microwave is irradiated toward the flow tube in the microwave irradiation space. By this microwave irradiation, the reaction solution in the flow tube in the microwave irradiation space is uniformly heated over the entire length in the flow direction to generate metal fine particles. The production method includes using a flow tube having an inner diameter smaller than 2.9 mm for the flow tube passing through the microwave irradiation space when the frequency of the microwave is 5.8 GHz, and introducing the reaction solution that has passed through the microwave irradiation space into a temperature regulator. Further, the following (a) to (e) (a) The addition amount of the metal precursor into the reaction solution (b) The addition amount of the reducing agent into the reaction solution (c) The addition amount of the additive into the reaction solution (d) The flow rate of the reaction solution (e) The irradiation conditions of the microwave Disclosed is a method for producing metal fine particles, including adjusting at least one of them.

[0005] Patent Document 2 discloses a method for producing silver nanoparticles, which is characterized by reducing silver ions of 40 mM or more in a reaction solution with a reducing agent for silver ions in the presence of a particle protecting agent and an element nobler than silver.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In order to use metal nanoparticles, particularly silver nanoparticles having various excellent physical and chemical properties on the functional surface, as a high heat-resistant bonding material, it is necessary to make the melting point of the silver nanoparticles constant. In order to make the melting point of the silver nanoparticles constant, it is desirable to reduce the particle size of the silver nanoparticles and further narrow the particle size distribution.

[0008] Although the development of silver nanoparticles applicable to such various uses is progressing, in the method of producing silver nanoparticles by irradiating a reaction solution with microwaves, it is difficult to prepare silver nanoparticles with a small and uniform particle size (here, uniform particle size means a narrow particle size distribution) at low cost.

[0009] Therefore, an object of the present invention is to provide a method for producing silver nanoparticles capable of inexpensively preparing silver nanoparticles having a small and uniform particle size in a method of producing silver nanoparticles by irradiating a reaction solution with microwaves.

Means for Solving the Problems

[0010] As a result of various studies on means for solving the above problems, the inventors of the present invention have found that in a method for producing silver nanoparticles by irradiating a reaction solution with microwaves, the output of the microwaves irradiated to the reaction solution is adjusted, and when the reaction solution reaches the reaction temperature, the irradiation of the microwaves to the reaction solution is stopped, and then the temperature of the reaction solution is maintained at the reaction temperature by a heater. As a result, it has been found that silver nanoparticles having a small and uniform particle size can be stably prepared in the reaction solution, and the present invention has been completed.

[0011] That is, the gist of the present invention is as follows. (1) A method for producing silver nanoparticles including a step of irradiating a reaction solution with microwaves, comprising: (i) irradiating the reaction solution with microwaves having a power density of 10 W / mL to 50 W / mL based on the total volume of the reaction solution to reach the reaction temperature of the reaction solution; (ii) after reaching the reaction temperature of the reaction solution in the step (i), stopping the irradiation of the microwaves; and (iii) after stopping the irradiation of the microwaves to the reaction solution in the step (ii), maintaining the temperature of the reaction solution at the reaction temperature by a heater The method comprising. (2) The method according to (1), wherein the reaction temperature is 25°C or higher and lower than the boiling point of the solvent. (3) The method according to (1) or (2), wherein the reaction solution contains a raw material for silver nanoparticles, a solvent, a protective agent, and a reducing agent. (4) The method according to (3), wherein the raw material for silver nanoparticles is silver nitrate. (5) The method according to (3) or (4), wherein the protective agent is tannic acid. (6) The method according to any one of (3) to (5), wherein the reducing agent is citric acid and / or a salt thereof. [Effect of the Invention]

[0012] According to the present invention, there is provided a method for producing silver nanoparticles by irradiating a reaction solution with microwaves, which can inexpensively prepare silver nanoparticles having a small and uniform particle size.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0014] Hereinafter, preferred embodiments of the present invention will be described in detail. In this specification, the features of the present invention will be described with reference to the drawings as appropriate. Note that the method for producing silver nanoparticles of the present invention is not limited to the following embodiments, and can be implemented in various forms with modifications and improvements that can be made by those skilled in the art without departing from the gist of the present invention.

[0015] The present invention relates to a method for producing silver nanoparticles including a step of irradiating a reaction solution with microwaves, the method including: (i) irradiating the reaction solution with microwaves having a power density of 10 W / mL to 50 W / mL based on the total volume of the reaction solution until the temperature of the reaction solution reaches a reaction temperature; (ii) after the temperature of the reaction solution reaches the reaction temperature in step (i), stopping the irradiation of microwaves; and (iii) after stopping the irradiation of microwaves to the reaction solution in step (ii), maintaining the temperature of the reaction solution at the reaction temperature with a heater.

[0016] Each of steps (i) to (iii) will be described below.

[0017] (i) irradiating the reaction solution with microwaves having a power density of 10 W / mL to 50 W / mL based on the total volume of the reaction solution to reach the reaction temperature of the reaction solution In the step of (i), the reaction solution is irradiated with microwaves having a power density of 10 W / mL to 50 W / mL based on the total volume of the reaction solution to reach the reaction temperature of the reaction solution.

[0018] Here, as the reaction solution used in the present invention, the composition of the reaction solution that can be used in the method for producing silver nanoparticles by irradiating conventional microwaves can be used, and is not limited. For example, examples of the materials contained in the reaction solution are given below.

[0019] First, the reaction solution contains a raw material for silver nanoparticles. The raw material for silver nanoparticles is not limited as long as it can be dissolved in a solvent to generate silver ions. For example, inorganic salts such as hydrochlorides, sulfates, nitrates, and phosphates of silver, organic salts such as carboxylates and sulfonates, and the like can be mentioned. The raw material for silver nanoparticles may be prepared by dissolving a material containing metallic silver or a silver salt in an acid such as nitric acid or aqueous ammonia. It is preferable to use silver nitrate, which is inexpensive, as the raw material for silver nanoparticles.

[0020] The concentration of silver ions in the reaction solution is not limited, but is usually 0.1 mmol / L (mM) to 300 mM, preferably 0.1 mM to 100 mM.

[0021] By setting the concentration of silver ions in the reaction solution within the above range, the variation in the obtained silver nanoparticles becomes small. In other words, the particle size distribution of the obtained silver nanoparticles becomes narrow.

[0022] Furthermore, the reaction solution contains a solvent. The solvent used in the reaction solution is not limited as long as it can dissolve materials such as raw materials, protecting agents, and reducing agents of silver nanoparticles and can further absorb microwaves. Examples of the solvent used in the reaction solution include low-boiling solvents with a boiling point of 300 °C or lower. Examples of the low-boiling solvent include, but are not limited to, water, alcohols such as methanol and ethanol, polyhydric alcohol solvents such as ethylene glycol, ketone solvents such as acetone, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), other organic solvents, or low-boiling polar solvents such as mixtures of two or more of these. Water is preferred as the solvent used in the reaction solution.

[0023] By using a low-boiling solvent as the solvent used in the reaction solution, the handleability of the solvent can be improved and the environmental load can be reduced.

[0024] Furthermore, the reaction solution contains a protecting agent. The protecting agent used in the reaction solution is a compound that binds to a part or the whole surface of the silver nanoparticles generated in the reaction solution and is a compound that suppresses the aggregation of silver nanoparticles. Examples of the protecting agent include, but are not limited to, polyvinylpyrrolidone (PVP), thiol-based polymers, polyvinyl alcohol (PVA), tannic acid, etc. Tannic acid is preferred as the protecting agent.

[0025] The amount of the protecting agent is not limited and can be changed according to the desired particle size of the silver nanoparticles, but it is usually 0.1 to 20 times, preferably 0.2 to 10 times the amount of silver in terms of the amount of substance.

[0026] By using the protecting agent, the aggregation of the generated silver nanoparticles can be suppressed.

[0027] Furthermore, the reaction solution contains a reducing agent. The reducing agent is a material that can reduce silver ions to silver with an oxidation number of 0 by an oxidation-reduction reaction.

[0028] Examples of the reducing agent include, but are not limited to, citric acid or its salts such as trisodium citrate, disodium citrate, monosodium citrate, oxalic acid or its salts such as sodium oxalate, ascorbic acid or its salts such as sodium ascorbate, and mixtures of two or more thereof. As the reducing agent for silver ions, citric acid and / or its salts are preferred.

[0029] The amount of the reducing agent is not limited as long as it can reduce silver ions to a metal with an oxidation number of 0 by a redox reaction. However, it is usually 1.0 to 20 equivalents, preferably 4.0 to 15 equivalents, relative to silver ions. Note that when the reducing agent for silver ions contains one or more functional groups capable of interacting with a metal, such as a carboxy group, a hydroxy group, or an ether group, it can also act as a protecting agent. When the reducing agent also acts as a protecting agent, the reaction solution may not contain the protecting agent described above, and the amount of the reducing agent for silver ions may be an amount exceeding the amount necessary to reduce silver ions to a metal with an oxidation number of 0 by a redox reaction.

[0030] The reaction solution may be composed of the raw material, solvent, protecting agent, and reducing agent of the silver nanoparticles described above. However, in addition to these materials, it can also contain additives that can be usually used in reaction solutions used in conventional methods for producing silver nanoparticles by irradiating microwaves.

[0031] For example, the reaction solution may further contain a chelating agent, such as ethylenediaminetetraacetic acid (EDTA) and / or its salts, as an additive.

[0032] The pH of the reaction solution is not limited, but is usually pH 3 to pH 12.

[0033] In the present invention, the order of addition, addition temperature, mixing method, mixing time, etc. of each material in the preparation of the reaction solution are not limited, and they are mixed so that a uniform reaction solution is prepared. In the present invention, the reaction is started after a uniform reaction solution is prepared.

[0034] In the present invention, the reaction solution described above is irradiated with microwaves using a microwave synthesizer to proceed with the reaction. When the reaction solution is irradiated with microwaves, the polar solvent contained in the reaction solution absorbs the microwaves and generates heat by converting them into thermal energy. Therefore, in the reaction solution irradiated with microwaves, a uniform and rapid temperature rise occurs in the irradiated portion, and a uniform and rapid reaction occurs according to the temperature rise.

[0035] The microwaves are preferably irradiated uniformly on the object causing the reaction, that is, the portion of the reaction solution where the reaction occurs.

[0036] In the microwave synthesizer, the material of the container for accommodating the reaction solution is not limited as long as the reaction solution can be irradiated with microwaves uniformly. For example, when irradiating the reaction solution with microwaves from the outside of the reactor through the reactor, a material that transmits microwaves, such as ceramics, glass, etc., can be used. When irradiating the reaction solution directly with microwaves from the upper part of the reaction solution, a material that reflects microwaves, such as a metal such as aluminum or stainless steel, can be used.

[0037] The microwaves are generated from a microwave irradiation source (microwave oscillator (magnetron)), and the microwave irradiation source can be used in either a single-mode system or a multi-mode system.

[0038] The output (power density) of the microwave irradiation source is 10 W / mL to 50 W / mL based on the total volume of the reaction solution.

[0039] By adjusting the output (power density) of the microwave irradiation source to the above range and further passing through the step (iii) described below, silver nanoparticles with small and uniform particle sizes can be prepared even at a low power density.

[0040] The frequency of the microwave generated from the microwave irradiation source can be appropriately changed and is not limited, but is usually 1 GHz to 10 GHz, preferably 2 GHz to 6 GHz. In the present invention, it is preferable to use 2.45 GHz, which is the frequency of an industrial microwave power source, as the frequency of the microwave.

[0041] The microwave is preferably uniform during irradiation, and the above-mentioned microwave irradiation conditions are preferably constant while the microwave is being irradiated.

[0042] In the present invention, the temperature of the reaction solution heated by microwave irradiation is the reaction temperature, and the reaction temperature can be appropriately changed according to the reaction conditions (type of solvent, pressure during reaction, etc.) and is not limited, but is usually 25 °C or higher, preferably 80 °C or higher. The upper limit of the reaction temperature is not limited, but is usually lower than the boiling point of the solvent. The reaction temperature is, for example, in the range of usually 25 °C or higher and lower than 100 °C, preferably 80 °C to 90 °C, at atmospheric pressure when the solvent is water.

[0043] By setting the reaction temperature to 25 °C or higher, the reduction reaction from silver ions to silver nanoparticles occurs. By setting the reaction temperature to lower than the boiling point of the solvent, the disturbance of the particle size of the generated silver nanoparticles due to the non-uniformity of the reaction field that may occur due to the boiling of the reaction solution, that is, the broadening of the particle size distribution, can be prevented, and silver nanoparticles with a small and uniform particle size can be prepared.

[0044] The irradiation time of the microwave on the reaction solution is the time required for the temperature of the reaction solution to reach the reaction temperature, and is appropriately changed according to the reaction conditions (microwave conditions, type of solvent, pressure during reaction, amount of reaction solution, reaction temperature, etc.) and is not limited, but is usually 0.1 second to 300 seconds, preferably 10 seconds to 60 seconds.

[0045] By irradiating the reaction solution with microwave under the above conditions to reach the reaction temperature of the reaction solution, nuclei of silver nanoparticles are generated in the reaction solution.

[0046] (ii) After the temperature of the reaction solution reaches the reaction temperature in the step (i), stop irradiating with microwaves. In the step (ii), after the temperature of the reaction solution reaches the reaction temperature in the step (i), stop irradiating with microwaves.

[0047] Specifically, in the step (ii), as soon as it is confirmed that the temperature of the reaction solution has reached the reaction temperature in the step (i), cut off the microwaves being irradiated to the reaction solution.

[0048] By stopping the irradiation of microwaves to the reaction solution, the nucleation of silver nanoparticles in the reaction solution becomes gentle.

[0049] (iii) After stopping the irradiation of microwaves to the reaction solution in the step (ii), keep the temperature of the reaction solution at the reaction temperature using a heater. In the step (iii), after stopping the irradiation of microwaves to the reaction solution in the step (ii), keep the temperature of the reaction solution at the reaction temperature using a heater.

[0050] Specifically, after stopping the irradiation of microwaves to the reaction solution in the step (ii), in order to prevent the temperature of the reaction solution from decreasing, keep the reaction solution at the reaction temperature using a heater.

[0051] The switch from irradiating the reaction solution with microwaves to using a heater is preferably carried out immediately from the perspective of the reaction time and the like. However, even if the temperature of the reaction solution becomes lower than the reaction temperature at the time of switching, it can be returned to the reaction temperature again using a heater.

[0052] The heater used for keeping the temperature of the reaction solution is not limited as long as it can keep the temperature of the reaction solution at the reaction temperature, and a conventional heater can be used. Examples of the heater include a mantle heater, an immersion heater, a water bath, an oil bath, and the like.

[0053] The reaction solution is kept warm at the reaction temperature by a heater until the reaction is completed. The completion of the reaction can be determined by observing the absorbance of the raw material of silver nanoparticles or the absorbance derived from silver nanoparticles in the reaction solution. For example, when an inorganic salt is used as the raw material of silver nanoparticles, the change in absorbance of the reaction solution at 280 nm to 780 nm with the holding time is observed, and the time point when the absorbance no longer changes is taken as the completion time point of the reaction. Alternatively, the change in absorbance of the reaction solution at 280 nm to 780 nm derived from silver nanoparticles with the holding time is observed, and the time point when the absorbance no longer changes is taken as the completion time point of the reaction.

[0054] Therefore, the holding time until the reaction is completed can be determined as described above, but it is usually 2 minutes to 15 minutes.

[0055] In step (iii), when the reaction solution is kept warm at the reaction temperature by a heater, the nuclei of silver nanoparticles in the reaction solution generated in step (i) grow and are further homogenized (aged).

[0056] Therefore, in the present invention, silver nanoparticles with a small and uniform particle size can be produced by irradiating microwaves of 10 to 50 W / mL for a predetermined time and then keeping them warm.

[0057] In the present invention, it is preferable to stir the reaction solution through steps (i) to (iii) by a stirring mechanism, such as a propeller stirrer, a vibrating stirrer, a magnetic stirrer, etc.

[0058] By stirring the reaction solution, the silver nanoparticles generated in the reaction solution can be uniformly dispersed, and the reaction solution can be kept uniform.

[0059] In addition, the present invention may be carried out in a batch mode or a flow-through mode. In the case of the flow-through mode of the present invention, silver nanoparticles can be continuously synthesized. In the present invention, silver nanoparticles can be produced with a simple configuration of one structure capable of preferably uniformly irradiating microwaves and one holding section, and therefore, silver nanoparticles can be produced at a low equipment cost.

[0060] The dispersion liquid containing silver nanoparticles obtained by the present invention can, if necessary, be separated and purified (for example, salting out or centrifugation) by methods known in the art, etc., to obtain the target silver nanoparticles and / or the dispersion liquid containing silver nanoparticles.

[0061] The silver nanoparticles produced by the method for producing silver nanoparticles of the present invention are characterized by a small particle size and a small dispersion of particle size distribution.

[0062] The approximate average particle size of silver nanoparticles can be measured by the absorbance of the dispersion liquid containing the silver nanoparticles. The smaller the maximum value of the absorbance peak, the smaller the average particle size. Since the absorbance of the dispersion liquid containing silver nanoparticles produced by the method for producing silver nanoparticles of the present invention has a maximum peak value of 405 nm or less, the average particle size of the silver nanoparticles contained in the dispersion liquid is 10 nm or less.

[0063] The approximate particle size distribution of silver nanoparticles can be grasped by the half-value width of the absorbance peak of the dispersion liquid containing the silver nanoparticles. The smaller the half-value width, the narrower the particle size distribution, that is, the smaller the variation in particle size. The half-value width of the absorbance peak of the dispersion liquid containing silver nanoparticles indicates the distance (width) between the wavelengths at two points of absorbance that is half of the maximum value of the absorbance peak. The half-value width of the absorbance peak of the dispersion liquid containing silver nanoparticles produced by the method for producing silver nanoparticles of the present invention is 81.0 nm to 83.5 nm, which is smaller than the half-value width of the absorbance peak of the dispersion liquid containing silver nanoparticles produced by conventional microwave synthesis. That is, the particle size distribution is narrow, and the silver nanoparticles produced by the method for producing silver nanoparticles of the present invention are uniform silver nanoparticles with a small variation in particle size and a uniform particle size.

[0064] The metal nanoparticles produced by the method for producing metal nanoparticles of the present invention can be used as a high heat-resistant bonding material for electronic components and as a wiring material due to their property of being sinterable at low temperature in addition to conventional catalysts, electronic component members, etc.

Examples

[0065] Hereinafter, several examples related to the present invention will be described, but the present invention is not intended to be limited to those shown in such examples.

[0066] 1. Preparation of silver nanoparticles To 100 mL of water, which is a polar solvent, 4.3 mg of silver nitrate as a raw material for silver nanoparticles, 4.3 mg of tannic acid as a protective agent, and 147 mg of trisodium citrate as a reducing agent and a protective agent were added, and the mixture was stirred for 5 minutes to dissolve each material in water, thereby preparing a reaction solution.

[0067] The obtained reaction solution was irradiated with microwaves having a power density of 10 W / mL, 25 W / mL, 50 W / mL, 75 W / mL, or 100 W / mL based on the total volume of the reaction solution, and the temperature of the reaction solution was raised to 90 °C as the reaction temperature.

[0068] Here, the irradiation of the microwaves and subsequent heat preservation were carried out according to the following experimental condition A or experimental condition B: Experimental condition A: The above-mentioned microwaves were continuously irradiated until reaching 90 °C, and then the irradiation was stopped (trace of Patent Document 1). Experimental condition B: When the temperature of the reaction solution reached 90 °C, the irradiation of the microwaves was stopped, and the temperature of the reaction solution was kept at 90 °C using a water bath.

[0069] It was confirmed that the reaction in the reaction solution was completed by adding dimethylamine borane (DMAB), which can reduce silver ions even at room temperature, to the reaction solution and observing that the UV-vis spectrum of the reaction solution did not change before and after the addition, that is, there was no raw material for newly reduced silver nanoparticles in the reaction solution.

[0070] 2. Measurement of UV-vis spectrum of silver nanoparticle dispersion For each obtained silver nanoparticle dispersion, UV-vis spectrum measurement was performed. The results are shown in FIGS. 1 and 2. FIG. 1 shows the results of experimental condition A, and FIG. 2 shows the results of experimental condition B.

[0071] Furthermore, from FIGS. 1 and 2, the wavelength (peak wavelength) of the maximum value of the peak of each spectrum and the full width at half maximum of each peak were calculated and plotted against the power density of the microwave used for the preparation of the silver nanoparticle dispersion. FIG. 3 shows the relationship between the power density of the microwave and the peak wavelength, and FIG. 4 shows the relationship between the power density of the microwave and the full width at half maximum.

[0072] In FIG. 3, for silver nanoparticles, the peak wavelength is 405 nm or less and the average particle size is 10 nm or less, the peak wavelength is 407 nm or less and the average particle size is 20 nm or less, and the peak wavelength is 416 nm or less and the average particle size is 30 nm or less. From FIG. 3, it was found that the average particle size of the silver nanoparticles prepared under experimental condition B is smaller than that of the silver nanoparticles prepared under experimental condition A. Furthermore, from FIG. 3, by adjusting the power density of the microwave irradiated to the reaction solution to 10 W / mL to 50 W / mL based on the total volume of the reaction solution, and then keeping the temperature of the reaction solution at 90 °C, which is the reaction temperature, by the water bath under experimental condition B, it was found that silver nanoparticles with an average particle size of 10 nm or less can be prepared.

[0073] In FIG. 4, the smaller the full width at half maximum, the narrower the particle size distribution and the smaller the variation in particle size. From FIG. 4, it was found that the particle size distribution of the silver nanoparticles prepared under experimental condition B is narrower than that of the silver nanoparticles prepared under experimental condition A.

Claims

1. A method for producing silver nanoparticles, comprising the step of irradiating a reaction solution with microwaves, wherein: (i) irradiating the reaction solution with microwaves having a power density of 10 W / mL to 50 W / mL to reach the reaction temperature of the reaction solution; (ii) after reaching the reaction temperature of the reaction solution in step (i), stopping the irradiation of microwaves; and (iii) after stopping the irradiation of microwaves to the reaction solution in step (ii), maintaining the temperature of the reaction solution at the reaction temperature by means of a heater The method comprising the steps.

2. The method according to claim 1, wherein the reaction temperature is 25° C. or higher and lower than the boiling point of the solvent.

3. The method according to claim 1 or 2, wherein the reaction solution contains a raw material for silver nanoparticles, a solvent, a protective agent, and a reducing agent.

4. The method according to claim 3, wherein the raw material for silver nanoparticles is silver nitrate.

5. The method according to claim 3 or 4, wherein the protective agent is tannic acid.

6. The method according to any one of claims 3 to 5, wherein the reducing agent is citric acid and / or a salt thereof.

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