TWI784705B - Composite nano-substance of cocoa-charcoal cladded conjugate structure and manufacturing method for yarn thereof - Google Patents

Abstract

A composite nano-substance of a cocoa-charcoal cladded conjugate structure and a manufacturing method for a yarn thereof are provided. The manufacturing method includes subjecting cocoa shells to a carbonization process to form nanometer cocoa charcoal particulates; subjecting the nanometer cocoa charcoal particulates to reduction and oxidation to have a surface oxidized to form nanometer charcoal particulates containing hydroxyl groups, carboxyl groups, and epoxy groups; and further subjecting the nanometer cocoa charcoal particulate to rection through mixing with nickel chloride in glycol solution to form a composite of nanometer nickel particle reduced nanometer cocoa charcoal particulates. Further, a surfactant adding process, a polymer blending process, and a yarn drawing process may be additionally implemented to form a multipurpose textile yarn featuring ultraviolet resistance, odor resistance, strong moisture absorption, and electromagnetic wave resistance.

Description

Cocoa charcoal-coated conjugated nanocomposite and its yarn manufacturing method

The invention relates to a cocoa charcoal-coated conjugated composite nano-material and its yarn manufacturing method, especially to a carbonized material obtained by carbonizing chocolate-derived waste (such as: cocoa bean shell) at high temperature Cocoa charcoal particles) are then reduced and oxidized, so that the surface of the nano-cocoa charcoal particles has a granular structure with oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups, and finally the nano-cocoa charcoal particles and nickel chloride in ethylene glycol The phases are mixed in the solution to carry out the reaction, which is to complete the composite of nano-nickel particles reducing nano-cocoa carbon particles (that is, composite nano-materials coated with conjugated structure), and this composite nano-material has anti-ultraviolet, anti- Odor, moisture absorption and anti-electromagnetic wave multiple functions; to further blend the nano-nickel particle-reduced nano-cocoa carbon particle composite with another polymer and draw yarn to obtain a textile yarn, the textile yarn is The same has multiple benefits of anti-ultraviolet, anti-odor, moisture absorption and anti-electromagnetic wave.

With the improvement of living standards, people have higher and higher requirements for the fiber fabrics of daily necessities, especially the fiber fabrics used in bedding products, the fiber fabrics used in clothing or the fiber fabrics of household products...etc; Cloth, which is often in contact with the human body, will inevitably leave sweat, stains, etc. on its surface, which will easily breed bacteria or attach to viruses, and become a hotbed for germ cultivation.

Therefore, the conventional technology is to develop a kind of adding antibacterial substances in the fiber cloth, so as to reduce the growth of bacteria and viruses on the fiber cloth, and avoid harming human health.

In addition, another industry has developed another anti-electromagnetic wave fabric. The main reason is that as people are often exposed to electronic products such as induction cookers, microwave ovens, hair dryers, mobile phones, etc., electromagnetic waves around life are everywhere. Anti-electromagnetic wave fabrics mainly use textile The principle of yarn is to interweave conductive and magnetic metal fibers into a protective fabric with both conductivity and magnetic conductivity to prevent electromagnetic radiation and endow clothes with superior functions and health indicators of anti-electromagnetic waves.

However, in the production process of known conductive and magnetic metal fibers, ferromagnetic particles are often directly added to polymers (such as: polyester (PET) or nylon (PA6)); After polyester or nylon is drawn, the overall weight of the yarn will increase, and the hardness of the yarn will also increase, which is not conducive to the light weight requirements of today's textile products.

In addition, the current chocolate production process will produce a lot of waste, such as: cocoa pods, cocoa bean shells, if the waste produced by chocolate is not recycled, it will form an alternative environmental pollutant.

Therefore, how to develop a carbonized material that can be produced by carbonizing the shell of cocoa bean waste, and then mix it with nickel chloride for reaction to complete the composite of nano-nickel particles reducing nano-cocoa carbon particles (ie cocoa carbon coating Composite nanoparticles with conjugated structures) is the problem to be solved by the present invention.

The object of the present invention is to provide a kind of cocoa charcoal-coated composite nano-material with conjugated structure and its manufacturing method including:

1. Preparation of cocoa charcoal particles: the cocoa bean shells are subjected to a carbonization procedure to obtain a cocoa charcoal particle, and then the cocoa charcoal particles are subjected to a grinding procedure to obtain nano cocoa charcoal particles.

2. Reductive oxidation of nano cocoa carbon particles: Take nano cocoa carbon particles in an acidic solution and add a strong oxidant for mixed reaction to obtain surface oxidation to form oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups The granular structure of nano-cocoa charcoal particles.

3. Combining nano-nickel particles with nano-cocoa carbon particles: take the nano-cocoa carbon particles in the second step and dissolve them in ethylene glycol solution to obtain an ethylene glycol solution with nano-cocoa carbon particles, and then take the chlorinated Nickel is dissolved in another ethylene glycol solution to obtain an ethylene glycol solution with nickel chloride, and the ethylene glycol solution with nano-cocoa carbon particles and the ethylene glycol solution with nickel chloride are mixed for reaction , to complete the composite of nano-nickel particles reducing nano-cocoa carbon particles (that is, composite nano-materials coated with cocoa-carbon structures).

Thus, the above-mentioned method for manufacturing composite nanoparticles coated with cocoa charcoal is mainly to use the waste derived from the chocolate manufacturing process (such as: cocoa bean shell) to be carbonized at high temperature, and the resulting carbonized material (i.e. nano rice cocoa carbon particles) and then reduced and oxidized, so that the surface of the nano cocoa carbon particles has a granular structure of oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups, and finally the nano cocoa carbon particles and nickel chloride in B The two phases are mixed in the diol solution to carry out the reaction, that is, the composite of nano-nickel particles reduced to nano-cocoa carbon particles (that is, a composite nano-material with a conjugated structure coated with cocoa carbon), this composite nano-material has anti-ultraviolet, anti-ultraviolet, The multiple benefits of anti-odor, moisture absorption and anti-electromagnetic wave; at the same time, the waste derived from the chocolate manufacturing process can be effectively used again to avoid increasing environmental pollutants.

Furthermore, another object of the present invention is to provide a method for manufacturing composite nanoparticles with a cocoa charcoal-coated conjugated structure and its yarn, which includes the above-mentioned cocoa charcoal-coated conjugated Steps 1 to 3 of the manufacturing method of composite nanostructures; then proceed to step 4. Put the composite of nano-nickel particles reduced by nano-cocoa carbon particles into a solution and add an interface agent. 5. The compound of nano-nickel particles coated with interface agent and reduced nano-cocoa carbon particles is blended with another polymer, and then the textile yarn is obtained by yarn drawing. This textile yarn has the same The multiple benefits of anti-ultraviolet, anti-odor, moisture absorption and anti-electromagnetic wave, and further make the articles woven from this yarn also have the functions of anti-ultraviolet, anti-odor, moisture absorption and anti-electromagnetic wave, endowing the fiber fabric with better Health advantages and indicators of anti-electromagnetic waves.

1: Nano cocoa charcoal particles

2: Nano nickel particles

The first picture: the scanning electron microscope picture of carbonized cocoa charcoal grains of the present invention after preliminary mechanical grinding and pulverization.

The second picture: the Raman spectrum of cocoa charcoal after carbonization of the present invention, 1400cm-1 has a defect vibration mode (D-band) peak; 1600cm-1 has a schematic diagram of a stretch vibration mode (G-band) peak .

The third figure is a schematic diagram of a nano-cocoa charcoal oxidized by a strong oxidant in the present invention to form a granular structure with oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy.

Figure 4: It is a transmission electron microscope image of a nano-nickel particle deposited on the surface of a nano-cocoa carbon particle according to the present invention.

The fifth figure: is the energy dispersive x-ray spectrum diagram of a nano-nickel particle combined with a nano-cocoa carbon particle according to the present invention.

The sixth figure: the present invention tries to give a nano-nickel particle loaded on the nano-cocoa carbon particle Schematic diagram of preparation and procedure.

The seventh figure is a flow chart of a manufacturing method of a cocoa charcoal-coated conjugated nanocomposite in the present invention.

Figure 8: It is a flowchart of the method for manufacturing a cocoa charcoal-coated conjugated composite nano-material and its yarn according to the present invention.

In order for your examiners to easily understand the other features and advantages of the present invention and the effects achieved, the features and advantages of the present invention are described in detail with the accompanying drawings. The following embodiments are The viewpoint of the present invention is further described in detail, but the scope of the present invention is not limited by any viewpoint.

Please refer to Figures 1 to 7. The present invention discloses a cocoa charcoal-coated conjugated nanocomposite and its yarn manufacturing method. Firstly, the cocoa charcoal-coated conjugated nanocomposite Its manufacturing methods include:

The first step: preparing cocoa charcoal particles: the cocoa bean shells are subjected to a carbonization procedure to obtain a cocoa charcoal particle, and then the cocoa charcoal particles are subjected to a grinding procedure to obtain nano cocoa charcoal particles 1 .

According to the first step, the present invention gives an example. The carbonization procedure is as follows: put the cocoa bean shells in an oven at 60°C to 90°C for drying to ensure that no moisture remains; Put the bean shell into a high-temperature furnace, set the gas flow rate in the high-temperature furnace to be 50-80sccm under nitrogen environment, and raise the temperature to 800-1000°C at a heating rate of 5-10°C/min, and keep the temperature for 1-4hr, and wait for carbonization After that, the cocoa charcoal particles can be obtained; after that, the cocoa charcoal particles are mechanically ground and pulverized, and the cocoa charcoal particles are photographed with a scanning electron microscope (as shown in Figure 1). It is worth noting that carbonized cocoa charcoal particles are conductive, and Raman spectroscopy can be used to check whether there are D-band, G-band or other carbon material signals, because the shell of cocoa beans is mainly composed of carbon, and carbon The conductive form of the graphite structure is the graphite structure. The general graphite structure mainly checks whether there is a signal in the D-band and G-band under the Raman spectrum. (As shown in Figure 2) is the Raman spectrum of the carbonized cocoa carbon particles , it can be seen that at around 1400cm _-1 , the peak of the defective vibration mode (D-band) is produced; and at around 1600cm _-1 , the peak of the stretching vibration mode (G-band) is produced, and the D-band and G The smaller the -band ratio (that is, the smaller the I _D / _IG / value), the higher the degree of graphitization and the higher its conductivity. In addition, the mechanically ground cocoa carbon particles can be further ground to a size below 200 nanometers through a wet grinding method through zirconia balls to form nano cocoa carbon particles 1 .

The second step: reducing and oxidizing the nano-cocoa carbon particles 1 of the first step: taking the nano-cocoa carbon particles 1 in an acidic solution and adding a strong oxidizing agent for a mixed reaction to obtain surface oxidation to form a compound with hydroxyl, carboxyl and Nano cocoa carbon particle 1 with a granular structure of oxygen-rich functional groups such as epoxy groups.

According to the description of the second step, the present invention tries to give an embodiment: get 10.5 ~ 10g of nano cocoa charcoal particles and disperse them in 20 ~ 80ml concentration of sulfuric acid aqueous solution (i.e. the acidic solution) that is 2M ~ 10M, and make The sulfuric acid aqueous solution is separated from water and kept in a constant temperature ice bath with a temperature of 5 to 30 degrees, while ensuring that the reaction temperature of the sulfuric acid aqueous solution is lower than 25°C; after that, adding 0.25 to 3g of sodium nitrate and 2 ~10g potassium permanganate (i.e. the strong oxidizing agent) to obtain a mixed sulfuric acid aqueous solution, while avoiding that the reaction temperature is lower than 20°C, and the mixed sulfuric acid aqueous solution needs to be stirred for 20 to 60 minutes to ensure its uniform dispersion; After the sulfuric acid aqueous solution is evenly dispersed, raise the constant temperature water bath to 30-70 degrees, let the reaction last for 20-60 hours; Heat the constant temperature water bath to 70~90℃, add 10~30ml deionized water to the mixed sulfuric acid aqueous solution at least three times or more, and stir for 10~30 minutes, at this time, the mixed sulfuric acid aqueous solution will rise to 80~90℃, The color of the mixed sulfuric acid aqueous solution is dark brown; add 100~500ml deionized water to the mixed sulfuric acid aqueous solution, and stir for 1~4 hours; add 3~20ml hydrogen peroxide solution (concentration is 15~50wt %), the reaction of the mixed sulfuric acid aqueous solution will stop now, and the color of the mixed sulfuric acid aqueous solution will turn from dark brown to bright brownish yellow; the mixed sulfuric acid aqueous solution will be centrifuged at 5000~10000rpm for 20~60 minutes to repeat this action, and the alcohol will Add the sulfuric acid aqueous solution that mixes and wash 2 ~ 4 times, then with 10000 ~ 15000rpm, centrifuge after 20 ~ 60 minutes, there will be muddy precipitate at the bottom of described mixed sulfuric acid aqueous solution, remove upper liquid, take out bottom muddy precipitate (ie The surface is oxidized to form nano-cocoa carbon particles with a granular structure of oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups 1), and the entire reaction is completed. Finally, observe the muddy nano-cocoa charcoal particles 1 with a high-resolution transmission electron microscope (HR TEM), (as shown in Figure 3), it is observed that the particle size is below 300nm, and the nano-cocoa charcoal particles 1 After being oxidized by a strong oxidant, the surface is oxidized to form a granular structure with oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups.

The third step: combine nano-nickel particles with nano-cocoa carbon particles 1: Take the nano-cocoa-carbon particles 1 after reduction and oxidation in the second step and dissolve them in ethylene glycol solution to obtain ethylene glycol with nano-cocoa-carbon particles Alcohol solution, then take nickel chloride and dissolve it in another ethylene glycol solution to obtain an ethylene glycol solution with nickel chloride, mix the ethylene glycol solution with nano-cocoa carbon particles and the ethylene glycol solution with nickel chloride The alcohol solution is mixed to carry out the reaction, that is to complete the composite of nano-nickel particles 2 reducing nano-cocoa carbon particles 1 (that is, composite nano-materials coated with cocoa carbon).

According to the description of the third step, the present invention gives an example: take the dried muddy nano-cocoa charcoal particles 1 (2~10 mg) prepared in the second step, put them in 10~20ml of ethylene glycol solution, And treated with ultrasonic shock for 40~90 minutes to get the ethylene glycol solution of nano-cocoa charcoal particles; take nickel chloride (NiCl ₂ ) and dissolve it in another ethylene glycol solution with a concentration of 30~200mM and a capacity of 10 ~40ml of ethylene glycol solution of nickel chloride. At this time, the color of the ethylene glycol solution of nickel chloride is light green; mix the ethylene glycol solution of nano-cocoa carbon particles and the ethylene glycol solution of nickel chloride (referred to as : mixed ethylene glycol solution), and stirred at 200~600rpm for 40~90 minutes, at this time, the mixed ethylene glycol solution was uniformly light yellowish brown; prepared 2~10M sodium hydroxide aqueous solution, poured the sodium hydroxide aqueous solution Add the mixed ethylene glycol solution, and observe the pH value of the mixed ethylene glycol solution until it is 10~12, then stop adding; the mixed ethylene glycol solution is stirred at a high speed with a magnet rotor, the rotating speed is 200~800rpm, and the time is 40~90 Minutes, after the stirring is completed, move the mixed ethylene glycol solution to a constant temperature water bath, set the temperature at 40~80 degrees, and prepare 0.5~10ml of hydrazine aqueous solution (80%) and add it to the mixed ethylene glycol solution, and the magnet rotor Stir at high speed for 20-80 minutes, rotate at 200-800rpm, and react for 40-90 minutes; after the above reaction starts, the solution will turn from yellow-brown to black, and the black substance produced in the solution is the product nano-nickel particles reduced nano-cocoa carbon Particle complex reaction; take 300~1000ml of absolute alcohol and add the mixed ethylene glycol solution, and centrifuge at 5000~10000rpm for 20~80 minutes, observe the black precipitate at the bottom, remove the upper part of the alcohol, repeat this action, add the alcohol to the mixed ethylene glycol solution Wash with diol solution for 2 to 6 times, and finally use a powerful NdFeB magnet (such as: 10000~20000 Gauss) to separate the product (ie, the composite of nano-nickel particles 2 reduced by nano-cocoa carbon particles 1) from the reaction solution. Let the product (precipitate) at the bottom of the mixed ethylene glycol solution be taken out, and the entire reaction is completed; after that, the composite of nano-nickel particles 2 and nano-cocoa carbon particles 1 can be placed in a ceramic dish and placed at 70~80°C Oven drying, after drying, black powder can be obtained. The preparation of the nano-nickel particles 2 to reduce the composite of nano-cocoa carbon particles 1, as shown in the TEM image of FIG. 2 is deposited on the surface of nano cocoa carbon particle 1. Through energy dispersive x-ray spectroscopy (EDX) spectroscopy, the elemental composition of the nanocomposite can be analyzed. From Figure 5, it can be seen that nano-nickel particles 2 combined with nano-cocoa carbon particles do indeed contain nickel metal element.

In this way, through the above-mentioned first to third steps, the waste derived from the chocolate manufacturing process (such as: cocoa bean shell) is mainly used for high-temperature carbonization, and the obtained carbonized material (ie, nano-cocoa charcoal particles 1) is then reduced. Oxidation, let the nano-cocoa carbon particles 1 have a granular structure with oxygen-rich functional groups such as hydroxyl, carboxyl and epoxy groups on the surface, and finally mix the nano-cocoa carbon particles 1 with nickel chloride in ethylene glycol solution To carry out the reaction, that is to complete the composite of nano-nickel particles 2 reducing nano-cocoa carbon particles 1 (that is, a composite nano-material coated with conjugated structure), this composite nano-material has anti-ultraviolet, anti-odor, and absorbing properties. Multiple effects of moisture and anti-electromagnetic waves; at the same time, it can effectively use the waste derived from the chocolate manufacturing process again to avoid increasing environmental pollutants.

Another object of the present invention is to provide a cocoa charcoal-coated conjugated composite nano-material and its yarn manufacturing method, the manufacturing method comprising:

The first step: preparing cocoa charcoal particles (the content is the same as the first step above, so it will not be repeated).

The second step: reducing and oxidizing the nano-cocoa charcoal particles 1 in the first step (the content is the same as the second step above, so it will not be repeated here).

The third step: combining the nickel nano particles 2 with the cocoa carbon nano particles 1 (the content is the same as that of the second step above, so it will not be repeated here).

The fourth step: adding an interface agent. Procedure: dissolve the complex of nano-nickel particles 2 reduced by nano-cocoa carbon particles 1 in a solution (such as water) and add an interface agent to make the nano-nickel particles 2 The outer surface of the composite of reduced nano-cocoa carbon particles 1 is additionally attached There is an interface agent to stabilize the nanoparticles so that the nanoparticles will not be combined with other particles (agglomeration).

The interface agent can be selected from cationic surfactant (Cetyl trimethylammonium bromide, referred to as CTAB), sodium dodecyl sulfate (Sodium Dodecyl Sulfate, referred to as SDS), polyvinylpyrrolidone (Polyvinylpyrrolidone, referred to as PVP), 3- (Trimethoxysilyl) propyl acrylate (3-(trimethoxysilyl)propyl methacrylate), methanesulfonic acid (MSMA, Sodium Hydrogen.Methylsulfonate), L-(-)-dibenzoyl tartrate Dibenzoyl-L- tartaric acid (DBTA), aminopropyltrimethoxysilane (3-aminopropyltrimethoxy-silane, referred to as APTMS), (3-mercaptopropyl) trimethoxysilane ((3-Mercaptopropyl) trimethoxysilane, referred to as (MPTMS)).. . Wait for one or more of them.

The fifth step: Yarn drawing process; blending the composite with nano-nickel particles 2 with interface agent and reduced nano-cocoa carbon particles 1 with another polymer, and through a plastic master Granulation process equipment, and finally make a plastic masterbatch with a composite of nano-nickel particles 2 and reduced nano-cocoa carbon particles 1, and then use this plastic masterbatch to obtain a composite of cocoa charcoal-coated conjugated structure by yarn drawing Yarns of Nanoparticles.

The polymer can be a plastic material, such as: PET (polyethylene terephthalate), PA6 (polyamide (NYLON)), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile -Butadiene-styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polystyrene), PES (polyether sulfide), PVC (polyvinyl chloride), PAN ( Polyacrylonitrile) and other plastic polymers.

Therefore, the yarn made through the first to fifth steps above contains nano-nickel particles 2 Reduction of the composite of nano cocoa charcoal particles 1, this composite nano-material has multiple benefits of anti-ultraviolet, anti-odor, moisture absorption and anti-electromagnetic wave, so the yarn made has the same anti-ultraviolet, anti-odor, moisture absorption And the multiple benefits of anti-electromagnetic waves, and further, the articles woven from this yarn also have the functions of anti-ultraviolet, anti-odor, moisture absorption and anti-electromagnetic waves, endowing the fabric with better anti-electromagnetic wave advantages and health indicators.

1: Nano cocoa charcoal particles

2: Nano nickel particles

Claims (3)

A method for manufacturing yarns using cocoa charcoal-coated composite nanoparticles with a conjugated structure. The manufacturing method includes: the first step: preparing cocoa charcoal particles: taking cocoa bean shells and performing a carbonization process. The carbonization process is to The cocoa bean shell is placed in a high-temperature furnace, and the gas flow rate in the high-temperature furnace is set to be 50-80 sccm in a nitrogen environment, and the temperature is raised to 800-1000°C at a heating rate of 5-10°C/min, and is obtained after carbonization. A cocoa carbon particle, and then subjecting the cocoa carbon particle to a grinding process to obtain nano-cocoa carbon particles; the second step: reducing and oxidizing the nano-cocoa carbon particles: taking the nano-cocoa carbon particles in an acidic solution and add a strong oxidant to carry out the mixed reaction. The acidic solution is an aqueous solution of sulfuric acid containing 20-80ml with a concentration of 2M-10M. The strong oxidant is 0.25-3g sodium nitrate and 2-10g potassium permanganate to obtain surface oxidation. Form the nano cocoa carbon particles with hydroxyl, carboxyl and epoxy groups; the third step: combine the nano nickel particles with the nano cocoa carbon particles; take the nano cocoa carbon particles in the second step and dissolve them in ethylene glycol Alcohol solution to obtain the ethylene glycol solution with the nano-cocoa carbon particles, and then dissolve nickel chloride in another ethylene glycol solution to obtain the ethylene glycol solution with the nickel chloride. The ethylene glycol solution of nano-cocoa carbon particles and the ethylene glycol solution with the nickel chloride are mixed for reaction, and the composite of nano-nickel particles reducing the nano-cocoa carbon particles is completed; the fourth step: the The composite of nano-nickel particles reduced to nano-cocoa carbon particles is dissolved in a solution and an interface agent is added, so that the external surface of the composite of nano-nickel particles reduced to nano-cocoa-carbon particles is additionally attached with an interface agent; Step 5: Blending the composite of the nano-nickel particles and reduced nano-cocoa carbon particles attached with an interface agent with another polymer of plastic material, and through a plastic masterbatch process equipment, A plastic masterbatch of a composite of nano-nickel particles reduced to nano-cocoa carbon particles is prepared, and the plastic masterbatch is then drawn into a yarn to obtain a composite nano-material yarn coated with cocoa-carbon conjugated structure. The cocoa charcoal-coated conjugated structure composite nano-material and its yarn manufacturing method as described in claim 1, wherein the interface agent is a cationic surfactant (CTAB), sodium dodecyl sulfate (SDS), Polyvinylpyrrolidone (PVP), 3-(trimethoxysilyl)propyl methacrylate, methylsulfonic acid (MSMA), L-(-)-diphenyl One or more of formyl tartaric acid (DBTA), aminopropyltrimethoxysilane (APTMS), (3-mercaptopropyl)trimethoxysilane (MPTMS)). As described in Claim 1, the cocoa charcoal-coated conjugated structure composite nano-material and its yarn manufacturing method, wherein the plastic material is PET (polyethylene terephthalate), PA6 (polyamide ( NYLON)), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile-butadiene-styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polyethylene Styrene), PES (polyether sulfide), PVC (polyvinyl chloride), PAN (polyacrylonitrile) or one or more.

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