Abstract:
A process for making particles is provided. In embodiments, a suitable process includes a mixing tank for mixing a plurality of droplets dispersed within a liquid media. The process further includes a drop ejector controlling unit in operable communication with a drop ejector array for launching a plurality of droplets, the plurality of droplets including the plurality of particles, and an outlet port for receiving the plurality of droplets.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    The present application relates to co-pending U.S. patent application Ser. No. ______ filed ______ , (20071377-US-NP (1515-251)) entitled Method and Apparatus of Rapid Continuous Process to Produce Chemical Toner and Nano-Composite Particles, the disclosure of which is hereby incorporated by reference in its entirety. 
     
    
     BACKGROUND 
       [0002]    The present disclosure relates to processes for producing toners suitable for electrophotographic apparatuses. 
         [0003]    Numerous processes are within the purview of those skilled in the art for the preparation of toners. Emulsion aggregation (EA) is one such method. These toners may be formed by aggregating a colorant with a latex polymer formed by emulsion polymerization. For example, U.S. Pat. No. 5,853,943, the disclosure of which is hereby incorporated by reference in its entirety, is directed to a semi-continuous emulsion polymerization process for preparing a latex by first forming a seed polymer. Other examples of emulsion/aggregation/coalescing processes for the preparation of toners are illustrated in U.S. Pat. Nos. 5,403,693, 5,418,108, 5,364,729, and 5,346,797, the disclosures of each of which are hereby incorporated by reference in their entirety. Other processes are disclosed in U.S. Pat. Nos. 5,527,658, 5,585,215, 5,650,255, 5,650,256 and 5,501,935, the disclosures of each of which are hereby incorporated by reference in their entirety. 
         [0004]    EA toner processes include coagulating a combination of emulsions, i.e., emulsions including a latex, wax, pigment, and the like, with a flocculent such as polyaluminum chloride and/or aluminum sulfate, to generate a slurry of primary aggregates which then undergoes a controlled aggregation process. The solid content of this primary slurry dictates the overall throughput of the EA toner process. The solids content of the primary slurry is conventionally between about 11% and about 14%. While an even higher solids content may be desirable, it may be difficult to achieve due to high viscosity of the emulsions and poor mixing, which may lead to the formation of unacceptable primary aggregates (high coarse particle content). 
         [0005]    Experimental data has shown that the aggregation step generally includes two stages. In the first stage, the primaries come together to form small clusters about 1-3 microns in size (i.e., aggregates). This stage is relatively fast (i.e., the process typically completes in about 5 minutes). For the second stage of aggregation, the so-formed 1-3 micron sized clusters further aggregate into 5-8 micron toner sized particles. The process speed of this second stage is relatively slow. In the past, there have been various theories/hypotheses for the explanation of this process. Whatever the reason, the long process time increases the cost of manufacturing and limits the rate of throughput of a toner plant. 
         [0006]    Consequently, improved methods for producing toners, which reduce the number of stages and materials, remain desirable. Such processes may reduce production costs for such toners and may be environmentally friendly. 
       SUMMARY 
       [0007]    The present disclosure provides processes for making toner particles. In embodiments, a process of the present disclosure includes a system for chemical toner production including a mixing tank for mixing a plurality of particles dispersed within a liquid media; a drop ejector controlling unit in operable communication with a drop ejector array for launching a plurality of droplets including the plurality of particles; and an outlet port for receiving the plurality of droplets. The plurality of droplets launched from the drop ejector array form one or more continuous droplet streams possessing droplets of a uniform size. 
         [0008]    In embodiments, a process of the present disclosure includes a method for mixing a plurality of particles dispersed within a liquid media via a mixing tank; launching a plurality of droplets using a drop ejector controlling unit in operable communication with a drop ejector array, the plurality of droplets including the plurality of particles; and receiving the plurality of droplets via an outlet port; wherein the plurality of droplets launched from the drop ejector array form one or more continuous droplet streams possessing droplets of a uniform size. 
         [0009]    In other embodiments,a process of the present disclosure includes a method for forming a plurality of particles including a resin, an optional colorant, and an optional wax; mixing the plurality of particles within a liquid media via a mixing tank; launching a plurality of droplets including the plurality of particles using a drop ejector controlling unit in operable communication with a drop ejector array and receiving the plurality of droplets via an outlet port, wherein the plurality of droplets launched from the drop ejector array form one or more continuous droplet streams possessing droplets of a uniform size. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0010]    Various embodiments of the present disclosure will be described herein below with reference to the figures wherein: 
           [0011]      FIG. 1  is a schematic diagram of a chemical toner production process that utilizes a drop ejector array and drying process, in accordance with the present disclosure; and 
           [0012]      FIG. 2  is a schematic diagram of heating and separation sections of the chemical toner production process of  FIG. 1 , in accordance with the present disclosure. 
       
    
    
     DETAILED DESCRIPTION 
       [0013]    The present disclosure proposes a method and apparatus for a low-cost, rapid continuous process for chemical toner production. The process uses a drop ejector array and drying to force aggregation of primary or intermediate particles into a desired-sized particle product. The process is efficient and rapid, and therefore may reduce the manufacturing cost of a toner and increase a toner plant&#39;s throughput. 
       Resins 
       [0014]    Any toner resin may be utilized in the processes of the present disclosure. Such resins, in turn, may be made of any suitable monomer or monomers via any suitable polymerization method. In embodiments, the resin may be prepared by a method other than emulsion polymerization. In further embodiments, the resin may be prepared by condensation polymerization. 
         [0015]    In embodiments, the resin may be a polyester, polyimide, polyolefin, polyamide, polycarbonate, epoxy resin, and/or copolymers thereof. In embodiments, the resin may be an amorphous resin, a crystalline resin, and/or a mixture of crystalline and amorphous resins. The crystalline resin may be present in the mixture of crystalline and amorphous resins, for example, in an amount of from 0 to about 50 percent by weight of the total toner resin, in embodiments from 5 to about 35 percent by weight of the toner resin. The amorphous resin may be present in the mixture, for example, in an amount of from about 50 to about 100 percent by weight of the total toner resin, in embodiments from about 65 to about 95 percent by weight of the toner resin. In embodiments, the resin may be a polyester crystalline and/or a polyester amorphous resin. 
         [0016]    In embodiments, the polymer utilized to form the resin may be a polyester resin, including the resins described in U.S. Pat. Nos. 6,593,049 and 6,756,176, the disclosures of each of which are hereby incorporated by reference in their entirety. Suitable resins may also include a mixture of an amorphous polyester resin and a crystalline polyester resin as described in U.S. Pat. No. 6,830,860, the disclosure of which is hereby incorporated by reference in its entirety. 
         [0017]    In embodiments, the resin may be a polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst. For forming a crystalline polyester, suitable organic diols include aliphatic diols with from about 2 to about 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, ethylene glycol, combinations thereof, and the like. The aliphatic diol may be, for example, selected in an amount of from about 40 to about 60 mole percent, in embodiments from about 42 to about 55 mole percent, in embodiments from about 45 to about 53 mole percent of the resin. 
         [0018]    Examples of organic diacids or diesters selected for the preparation of the crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, dodecanedioic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, a diester or anhydride thereof, and combinations thereof. The organic diacid may be selected in an amount of, for example, in embodiments from about 40 to about 60 mole percent, in embodiments from about 42 to about 55 mole percent, in embodiments from about 45 to about 53 mole percent. 
         [0019]    Examples of crystalline resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, mixtures thereof, and the like. Specific crystalline resins may be polyester based, such as poly(ethylene-adipate), poly(propylene-adipate), poly(butylene-adipate), poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate), poly(ethylene-succinate), poly(propylene-succinate), poly(butylene-succinate), poly(pentylene-succinate), poly(hexylene-succinate), poly(octylene-succinate), poly(ethylene-sebacate), poly(propylene-sebacate), poly(butylene-sebacate), poly(pentylene-sebacate), poly(hexylene-sebacate), poly(octylene-sebacate), alkali copoly(5-sulfoisophthaloyl)-copoly(ethylene-adipate), poly(decylene-sebacate), poly(decylene-decanoate), poly-(ethylene-decanoate), poly-(ethylene-dodecanoate), poly(nonylene-sebacate), poly(nonylene-decanoate), copoly(ethylene-fumarate)-copoly(ethylene-sebacate), copoly(ethylene-fumarate)-copoly(ethylene-decanoate), and copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate). The crystalline resin may be present, for example, in an amount of from about 5 to about 50 percent by weight of the toner components, in embodiments from about 10 to about 35 percent by weight of the toner components. 
         [0020]    The crystalline resin may possess various melting points of, for example, from about 30° C. to about 120° C., in embodiments from about 50° C. to about 90° C. The crystalline resin may have a number average molecular weight (Mn), as measured by gel permeation chromatography (GPC) of, for example, from about 1,000 to about 50,000, in embodiments from about 2,000 to about 25,000, and a weight average molecular weight (Mw) of, for example, from about 2,000 to about 100,000, in embodiments from about 3,000 to about 80,000, as determined by Gel Permeation Chromatography using polystyrene standards. The molecular weight distribution (Mw/Mn) of the crystalline resin may be, for example, from about 2 to about 6, in embodiments from about 3 to about 4. 
         [0021]    Examples of diacid or diesters selected for the preparation of amorphous polyesters include dicarboxylic acids or diesters such as terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, and combinations thereof. The organic diacid or diester may be present, for example, in an amount from about 40 to about 60 mole percent of the resin, in embodiments from about 42 to about 55 mole percent of the resin, in embodiments from about 45 to about 53 mole percent of the resin. 
         [0022]    Examples of diols utilized in generating the amorphous polyester include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(2-hydroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl)oxide, dipropylene glycol, dibutylene, and combinations thereof. The amount of organic diol selected may vary, and may be present, for example, in an amount from about 40 to about 60 mole percent of the resin, in embodiments from about 42 to about 55 mole percent of the resin, in embodiments from about 45 to about 53 mole percent of the resin. 
         [0023]    In embodiments, polycondensation catalysts may be used in forming the polyesters. Polycondensation catalysts which may be utilized for either the crystalline or amorphous polyesters include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, and dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or combinations thereof. Such catalysts may be utilized in amounts of, for example, from about 0.01 mole percent to about 5 mole percent based on the starting diacid or diester used to generate the polyester resin. 
         [0024]    In embodiments, suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, combinations thereof, and the like. Examples of amorphous resins which may be utilized include alkali sulfonated-polyester resins, branched alkali sulfonated-polyester resins, alkali sulfonated-polyimide resins, and branched alkali sulfonated-polyimide resins. Alkali sulfonated polyester resins may be useful in embodiments, such as the metal or alkali salts of copoly(ethylene-terephthalate)-copoly(ethylene-5-sulfo-isophthalate), copoly(propylene-terephthalate)-copoly(propylene-5-sulfo-isophthalate), copoly(diethylene-terephthalate)-copoly(diethylene-5-sulfo-isophthalate), copoly(propylene-diethylene-terephthalate)-copoly(propylene-diethylene-5-sulfoisophthalate), copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo -isophthalate), and copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenol A-5-sulfo-isophthalate). 
         [0025]    In embodiments, an unsaturated, amorphous polyester resin may be utilized as a latex resin. Examples of such resins include those disclosed in U.S. Pat. No. 6,063,827, the disclosure of which is hereby incorporated by reference in its entirety. Exemplary unsaturated amorphous polyester resins include, but are not limited to, poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyloxylated bisphenol co-maleate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-itaconate), poly(1,2-propylene itaconate), and combinations thereof. 
         [0026]    The amorphous resin may possess various glass transition temperatures (Tg) of, for example, from about 40° C. to about 100° C., in embodiments from about 50° C. to about 70° C. The crystalline resin may have a number average molecular weight (M n ), for example, from about 1,000 to about 50,000, in embodiments from about 2,000 to about 25,000, and a weight average molecular weight (M w ) of, for example, from about 2,000 to about 100,000, in embodiments from about 3,000 to about 80,000, as determined by Gel Permeation Chromatography (GPC) using polystyrene standards. The molecular weight distribution (M w /M n ) of the crystalline resin may be, for example, from about 2 to about 6, in embodiments from about 3 to about 4. 
         [0027]    In embodiments, a suitable amorphous polyester resin may be a poly(propoxylated bisphenol A co-fumarate) resin having the following formula (I): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein m may be from about 5 to about 1000, in embodiments from about 10 to about 500, in other embodiments from about 15 to about 200. Examples of such resins and processes for their production include those disclosed in U.S. Pat. No. 6,063,827, the disclosure of which is hereby incorporated by reference in its entirety. 
         [0028]    An example of a linear propoxylated bisphenol A fumarate resin which may be utilized as a toner resin is available under the trade name SPARII from Resana S/A Industrias Quimicas, Sao Paulo, Brazil. Other propoxylated bisphenol A fumarate resins that may be utilized and are commercially available include GTUF and FPESL-2 from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, North Carolina and the like. 
         [0029]    Suitable crystalline resins which may be utilized, optionally in combination with an amorphous resin as described above, include those disclosed in U.S. Patent Application Publication No. 2006/0222991, the disclosure of which is hereby incorporated by reference in its entirety. In embodiments, a suitable crystalline resin may include a resin formed of ethylene glycol and a mixture of dodecanedioic acid and fumaric acid co-monomers with the following formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein b is from about 5 to about 2000 and d is from about 5 to about 2000. 
         [0030]    For example, in embodiments, a poly(propoxylated bisphenol A co-fumarate) resin of formula I as described above may be combined with a crystalline resin of formula II to form a resin suitable for forming a toner. 
         [0031]    Examples of other suitable toner resins or polymers which may be utilized include those based upon styrenes, acrylates, methacrylates, butadienes, isoprenes, acrylic acids, methacrylic acids, acrylonitriles, and combinations thereof. Exemplary additional resins or polymers include, but are not limited to, poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene); poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), and poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), and combinations thereof. The polymer may be block, random, or alternating copolymers. 
         [0032]    In embodiments, the resins may include polyester resins having a glass transition temperature of from about 30° C. to about 80° C., in embodiments from about 35° C. to about 70° C. In further embodiments, the resins utilized in the toner may have a melt viscosity of from about 10 to about 1,000,000 Pa*S at about 130° C., in embodiments from about 20 to about 100,000 Pa*S. 
         [0033]    One, two, or more toner resins may be used. In embodiments where two or more toner resins are used, the toner resins may be in any suitable ratio (e.g., weight ratio) such as for instance about 10% (first resin)/90% (second resin) to about 90% (first resin)/10% (second resin). 
         [0034]    In embodiments, the resin may be formed by emulsion aggregation methods. Utilizing such methods, the resin may be present in a resin emulsion, which may then be combined with other components and additives to form a toner of the present disclosure. 
         [0035]    The polymer resin may be present in an amount of from about 65 to about 95 percent by weight, in embodiments from about 75 to about 85 percent by weight of the toner particles (that is, toner particles exclusive of external additives) on a solids basis. Where the resin is a combination of a crystalline resin and an amorphous resin, the ratio of crystalline resin to amorphous resin may be in embodiments from about 1:99 to about 30:70, in embodiments from about 5:95 to about 25:75, in some embodiments from about 5:95 to about 15:95. 
       Toner 
       [0036]    The resin described above may be utilized to form toner compositions. Such toner compositions may include optional colorants, waxes, and other additives. Toners may be formed utilizing any method within the purview of those skilled in the art. For example, a specific chemical toner production process that utilizes a drop ejector array and drying is presented below. 
       Surfactants 
       [0037]    In embodiments, resins, colorants, waxes, and other additives utilized to form toner compositions may be in dispersions including surfactants. Moreover, toner particles may be formed by emulsion aggregation methods where the resin and other components of the toner are placed in one or more surfactants, an emulsion is formed, toner particles are aggregated, coalesced, optionally washed and dried, and recovered. 
         [0038]    One, two, or more surfactants may be utilized. The surfactants may be selected from ionic surfactants and nonionic surfactants. Anionic surfactants and cationic surfactants are encompassed by the term “ionic surfactants.” In embodiments, the surfactant may be utilized so that it is present in an amount of from about 0.01% to about 5% by weight of the toner composition, for example from about 0.75% to about 4% by weight of the toner composition, in embodiments from about 1% to about 3% by weight of the toner composition. 
         [0039]    Examples of nonionic surfactants that may be utilized include, for example, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy) ethanol, available from Rhone-Poulenc as IGEPAL CA-210™, IGEPAL CA-520™, IGEPAL CA-720™, IGEPAL CO-890™, IGEPAL CO-720™, IGEPAL CO-290™, IGEPAL CA-210™, ANTAROX 890™ and ANTAROX 897™. Other examples of suitable nonionic surfactants include a block copolymer of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC PE/F, in embodiments SYNPERONIC PE/F 108. 
         [0040]    Anionic surfactants which may be utilized include sulfates and sulfonates, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl sulfates and sulfonates, acids such as abitic acid available from Aldrich, NEOGEN R™, NEOGEN SC™ obtained from Daiichi Kogyo Seiyaku, combinations thereof, and the like. Other suitable anionic surfactants include, in embodiments, DOWFAX™ 2A1, an alkyldiphenyloxide disulfonate from The Dow Chemical Company, and/or TAYCA POWER BN2060 from Tayca Corporation (Japan), which are branched sodium dodecyl benzene sulfonates. Combinations of these surfactants and any of the foregoing anionic surfactants may be utilized in embodiments. 
         [0041]    Examples of the cationic surfactants, which are usually positively charged, include, for example, alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C 12 , C 15 , C 17  trimethyl ammonium bromides, halide salts of quatemized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL™ and ALKAQUAT™, available from Alkaril Chemical Company, SANIZOL™ (benzalkonium chloride), available from Kao Chemicals, and the like, and mixtures thereof. 
       Colorants 
       [0042]    As the colorant to be added, various known suitable colorants, such as dyes, pigments, mixtures of dyes, mixtures of pigments, mixtures of dyes and pigments, and the like, may be included in the toner. The colorant may be included in the toner in an amount of, for example, about 0.1 to about 35 percent by weight of the toner, or from about 1 to about 15 weight percent of the toner, or from about 3 to about 10 percent by weight of the toner. 
         [0043]    As examples of suitable colorants, mention may be made of carbon black like REGAL 330®; magnetites, such as Mobay magnetites MO8029™, MO8060™; Columbian magnetites; MAPICO BLACKS™ and surface treated magnetites; Pfizer magnetites CB4799™, CB5300™, CB5600™, MCX6369™; Bayer magnetites, BAYFERROX 8600™, 8610™; Northern Pigments magnetites, NP604™, NP-608™; Magnox magnetites TMB-100™, or TMB-104™; and the like. As colored pigments, there may be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof. Generally, cyan, magenta, or yellow pigments or dyes, or mixtures thereof, are used. The pigment or pigments are generally used as water based pigment dispersions. 
         [0044]    Specific examples of pigments include SUNSPERSE 6000, FLEXIVERSE and AQUATONE water based pigment dispersions from SUN Chemicals, HELIOGEN BLUE L6900™, D6840™, D7080™, D7020™, PYLAM OIL BLUE™, PYLAM OIL YELLOW™, PIGMENT BLUE 1™ available from Paul Uhlich &amp; Company, Inc., PIGMENT VIOLET 1™, PIGMENT RED 48™, LEMON CHROME YELLOW DCC 1026™, E.D. TOLUIDINE RED™ and BON RED C™ available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL™, HOSTAPERM PINK E™ from Hoechst, and CINQUASIA MAGENTA™ available from E.I. DuPont de Nemours &amp; Company, and the like. Generally, colorants that may be selected are black, cyan, magenta, or yellow, and mixtures thereof. Examples of magentas are 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like. Illustrative examples of cyans include copper tetra(octadecyl sulfonamido)phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like. Illustrative examples of yellows are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide, and Permanent Yellow FGL. Colored magnetites, such as mixtures of MAPICO BLACK™, and cyan components may also be selected as colorants. Other known colorants may be selected, such as Levanyl Black A-SF (Miles, Bayer) and Sunsperse Carbon Black LHD 9303 (Sun Chemicals), and colored dyes such as Neopen Blue (BASF), Sudan Blue OS (BASF), PV Fast Blue B2G01 (American Hoechst), Sunsperse Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA (Ciba-Geigy), Paliogen Blue 6470 (BASF), Sudan III (Matheson, Coleman, Bell), Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman, Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (Hoechst), Permanent Yellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), Suco-Gelb L1250 (BASF), Suco-Yellow D1355 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (DuPont), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Toluidine Red (Aldrich), Lithol Rubine Toner (Paul Uhlich), Lithol Scarlet 4440 (BASF), Bon Red C (Dominion Color Company), Royal Brilliant Red RD-8192 (Paul Uhlich), Oracet Pink RF (Ciba-Geigy), Paliogen Red 3871K (BASF), Paliogen Red 3340 (BASF), Lithol Fast Scarlet L4300 (BASF), combinations of the foregoing, and the like. 
       Wax 
       [0045]    Optionally, a wax may also be combined with the resin and optional colorant in forming toner particles. When included, the wax may be present in an amount of, for example, from about 1 weight percent to about 25 weight percent of the toner particles, in embodiments from about 5 weight percent to about 20 weight percent of the toner particles. 
         [0046]    Waxes that may be selected include waxes having, for example, a weight average molecular weight of from about 500 to about 20,000, in embodiments from about 1,000 to about 10,000. Waxes that may be used include, for example, polyolefins such as polyethylene, polypropylene, and polybutene waxes such as commercially available from Allied Chemical and Petrolite Corporation, for example POLYWAX™ polyethylene waxes from Baker Petrolite, wax emulsions available from Michaelman, Inc. and the Daniels Products Company, EPOLENE N-15™ commercially available from Eastman Chemical Products, Inc., and VISCOL 550-P™, a low weight average molecular weight polypropylene available from Sanyo Kasei K. K.; plant-based waxes, such as carnauba wax, rice wax, candelilla wax, sumacs wax, and jojoba oil; animal-based waxes, such as beeswax; mineral-based waxes and petroleum-based waxes, such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; ester waxes obtained from higher fatty acid and higher alcohol, such as stearyl stearate and behenyl behenate; ester waxes obtained from higher fatty acid and monovalent or multivalent lower alcohol, such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetra behenate; ester waxes obtained from higher fatty acid and multivalent alcohol multimers, such as diethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryl distearate, and triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes, such as cholesteryl stearate. Examples of functionalized waxes that may be used include, for example, amines, amides, for example AQUA SUPERSLIP 6550™, SUPERSLIP 6530™ available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™, POLYSILK 14™ available from Micro Powder Inc., mixed fluorinated, amide waxes, for example MICROSPERSION 19™ also available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example JONCRYL 74™, 89™, 130™, 537™, and 538™, all available from SC Johnson Wax, and chlorinated polypropylenes and polyethylenes available from Allied Chemical and Petrolite Corporation and SC Johnson wax. Mixtures and combinations of the foregoing waxes may also be used in embodiments. Waxes may be included as, for example, fuser roll release agents. 
       Toner Preparation 
       [0047]    The toner particles may be prepared by any method within the purview of those skilled in the art. Although embodiments relating to toner particle production are described below with respect to emulsion processes and a specific chemical toner production process that utilizes a drop ejector array and drying, any suitable method of preparing toner particles may be used, including chemical processes, such as suspension and encapsulation processes disclosed in U.S. Pat. Nos. 5,290,654 and 5,302,486, the disclosures of each of which are hereby incorporated by reference in their entirety. In embodiments, toner compositions and toner particles may be prepared by aggregation and coalescence processes in which small-size resin particles are aggregated to the appropriate toner particle size and then coalesced to achieve the final toner particle shape and morphology. 
         [0048]    In embodiments, toner compositions may be prepared by emulsion aggregation processes, such as a process that includes combining a mixture of an optional colorant, an optional wax and any other desired or required additives, and emulsions including the resins described above, optionally in surfactants as described above, and then coalescing the particulate mixture. A mixture may be prepared by adding a colorant and optionally a wax or other materials, which may also be optionally in a dispersion(s) including a surfactant, to the emulsion, which may be a mixture of two or more emulsions containing the resin. The pH of the resulting mixture may be adjusted by an acid such as, for example, acetic acid, nitric acid or the like. In embodiments, the pH of the mixture may be adjusted to from about 4 to about 5. Additionally, in embodiments, the mixture may be homogenized. If the mixture is homogenized, homogenization may be accomplished by mixing at about 600 to about 4,000 revolutions per minute. Homogenization may be accomplished by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer. 
         [0049]    Following the preparation of the above mixture, an optional aggregating agent may be added to the mixture. Any suitable aggregating agent may be utilized to form a toner. Suitable aggregating agents include, for example, aqueous solutions of a divalent cation or a multivalent cation material. The aggregating agent may be, for example, polyaluminum halides, polyaluminum silicates, and water soluble metal salts. The growth and shaping of the particles following addition of the optional aggregation agent may be accomplished under any suitable conditions. 
       Chemical Toner Production Using A Drop Ejector Array 
       [0050]    In embodiments, the present disclosure provides a continuous chemical toner production process that utilizes a drop ejector array and drying to force aggregation of the primary (or intermediate) particles into desired-sized or predetermined-sized particle products. The proposed process is schematically shown in  FIGS. 1-2  described below. 
         [0051]      FIG. 1  is a schematic diagram of a chemical toner production process that utilizes a drop ejector array and drying process, in accordance with the present disclosure. 
         [0052]    The schematic diagram  10  includes a materials feed  12 , a mixing tank  14 , particles  16 , an air inlet port  18 , a drop ejector controlling unit  20 , a drop ejector array  22 , droplets  24 , and air flow  26 . Air flow  26  may be referred to as an outlet port. 
         [0053]    Furthermore, the particles  16  are of different sizes in  FIG. 1  because they represent different types of particles. For example, latex particles  16 A, pigment particles  16 B, and wax particles  16 C are shown, where the latex particles  16 A are bigger than the pigment particles  16 B and wax particles  16 C. 
         [0054]      FIG. 2  is a schematic diagram of heating and separation sections of the chemical toner production process of  FIG. 1 , in accordance with the present disclosure. 
         [0055]    The schematic diagram  40  includes a passage  42  for passage of air flow  26 . The passage  42  is divided into a first section  44  for heating for evaporation, drying, and compacting, and a second section  46  for heating for coalescence. The schematic diagram  40  further includes a cyclone separator  56  having cooling coils  48  and a finished toner product  50  positioned between the first door  52  and the second door  54 . The air flow  26  (see  FIG. 1 ) is transported through first section  44 , second section  46 , and the cyclone separator  56  to create a final air flow  58  released to a vacuum blower (not shown). 
         [0056]    In schematic diagram  10  of  FIG. 1 , the system is maintained at a pressure lower than that of ambient conditions (i.e., kept in a low-level vacuum state, for example, from about 0 Torr to about −250 Torr, in embodiments from about −10 Torr to about −150 Torr, in other embodiments from about from about −20 Torr to about −120 Torr). This desired pressure set point of the system may be achieved through a proper balance between the a final air flow  58  shown in  FIG. 2  and the openings of air inlet  18  shown in  FIG. 1 . 
         [0057]    As noted above with reference to  FIG. 1 , the proposed system includes mixing tank  14  that agitates the suspension and maintains the liquid media homogeneous and the dispersed droplets  16 , located within, well-mixed and well-dispersed. Ideally, the liquid suspension inside the mixing tank  14  would contain a higher solids content (latex, pigments, wax, etc.) than that in current EA toner processes. For example, the solids content may be from about 16% solids to around 35% solids, in embodiments from about 20% solids to about 30% solids. The material may be kept at an elevated temperature, for example, from about 30° C. to around 50° C., in embodiments from about 35° C. to about 45° C. The mixing tank  14  in  FIG. 1  may be separated from the drop ejector array  22  (or nozzle) so that the pressure drop in the drop ejector array  22  area would not affect the latex suspension. 
         [0058]    Air flow from an ink jet type of nozzle may eject liquid drops with a very uniform size distribution. The uniform sizes of the droplets  24  in the air flow  26  may generate uniform sizes of solids that are formed after all the liquid has been extracted. This is advantageous compared to typical non-uniform spray nozzles, as there is no need to separate different sizes by either spinning the nozzle head and/or filtering to remove unwanted sizes. The throughput rate thus increases accordingly. 
         [0059]    The drop ejector array may produce a continuous stream of droplets. Suitable drop ejectors include, for example, ink-jet types of printhead arrays, piezoelectric, pneumatic, electrostatic, mechanical, hydraulic methods and arrays, combinations thereof, and the like. Suitable commercial printheads which may be used as drop ejectors may have openings as large as several millimeters by several millimeters, with hundreds of jetting nozzles. It is relatively easy to build an array with tens or dozens of these types of printheads, and thus for tens of thousands of ejectors together. 
         [0060]    In  FIG. 2 , the air flow  42  is guided to a heating section  44  where the air flow  42  is first heated (from about 50° C. to around 100° C., in embodiments from about 60° C. to about 90° C.) to evaporate the carrier liquid medium (in an EA process, water) and then heated at a second heating section  46  (from about 60° C. to around 150° C., in embodiments from about 75° C. to about 130° C.) with hot air injection, for example, for the particulate content (i.e., the aggregates) to coalesce into the desired final droplet morphology. 
         [0061]    During the drying and heating process, the droplets  24  loading into the air stream  42  may be kept small as a dilute suspension to minimize the possible collisions within the air flow  26 . Alternatively, the heating process does not have to be separated in two different steps. An alternative may be a path of gradually increased temperature. If necessary, the mixing tank  14 , the pipeline to the drop ejector array  122 , and the drop ejector array  22  itself may also be heated to an elevated temperature (from about 50° C. to about 120° C., in embodiments from about 60° C. to about 80° C.) to facilitate the droplet drying process. It should be emphasized that, in evaporation and drying, the volume of droplets  24  shrinks. The surface tension of droplets  24  helps compact the particulate content (e.g., latex, pigments, wax, additives, etc.) in the air flow  26  to form a compact aggregate. It should be noted that these droplets are downstream at  42  in  FIG. 2 . 
         [0062]    After the heating  46  for coalescence is completed, the air flow  42  (now carrying finished toner droplets) enters a cyclone separator  56  (or a bag-house filtering system) where the toner particles are separated from the air. As indicated in  FIG. 2 , the cyclone separator  56  may be equipped with a double-door lock  52 ,  54  that helps maintain a vacuum in the system  40 . The finished toner product at the bottom of the cyclone separator  56  is then cooled to room temperature. The drop ejector array  22  may be used for not only EA toner production, but also for other nano-particle composites. For example, it may be used to coat gold nano-particles with polymers. 
         [0063]    Alternatively, another application of the apparatus and methods of the present disclosure includes polyester chemical toner processes, using solvent evaporation-inducing coalescence. During air-flow drying, coalescence induced by organic solvent evaporation could be utilized. In the polyester EA process, phase-inversion emulsification may be used to prepare a polyester emulsion. A difficult part of this process is removing organic solvents. In accordance with the present disclosure, it may not be necessary to remove the solvents from the emulsion. Instead, the solvents could be kept in aggregation. During the drop-ejector drying process, solvents may be evaporated off, thus inducing coalescence to form toner particles. With organic solvents, the entire process could be done at lower temperature, and the coalescence process for producing the polyester toner could be simplified, which potentially leads to low-cost polyester manufacturing. 
       Throughput and Cost of Chemical Toner Production Using a Drop Ejector Array 
       [0064]    If drop-on-demand (DOD) ejectors are used, the throughput of the exemplary embodiments scales linearly with the jetting frequency and the number of jets. The higher the frequency and the more the number of jets, the higher the throughput. Though there is an upper bound for jetting frequency (depending on the jetting technology used), there is no limit of how many jets may be used. And, since it scales linearly, there is no asymptote of throughput with respect to the number of jets. Furthermore, the proposed embodiments do not have to be limited to DOD ejectors. The proposed embodiments may use continuous inkjets (CIJ), spray nozzles, or any other type of technology within the purview of those skilled in the art. CIJ and spray nozzles may produce many more droplets per unit time than DOD can, and thus increase the production rate significantly. 
         [0065]    Additionally, the droplet producing jets (DOD, CIJ, spray nozzles, and the like) do not have to be bundled into a big unit, but may be designed into multiple smaller modules where each of them is a self-contained unit (including its own draying duct and cyclone separator, etc.). The multiple units may process the production demand in parallel. In this way, the rate of production may be adjustable by turning on and off different modular units depending on the required throughput. Thus, the throughput that the proposed exemplary embodiments may deliver depends on how many modules need to be turned on. 
       Particles 
       [0066]    In evaporation and drying, the volume of the droplet shrinks. The surface tension of the droplet helps compacting the particulate content (e.g., latex, pigments, wax, additives, etc.) in the droplet into a compact aggregate. This forced aggregation process is different from the process the in current EA manufacturing. This proposed new process is efficient and fast and therefore can reduce the toner manufacturing cost and increase a toner plant&#39;s throughput (i.e., green manufacturing). 
       Shell Resin 
       [0067]    In embodiments, prior to or after the coalescence, the formed aggregates/particles can also be coated with an outer/shell layer for desired functionalities. Resins which may be utilized to form the shell include, but are not limited to, the amorphous resins described above for use in the core. 
         [0068]    In some embodiments, the amorphous resin utilized to form the shell may be crosslinked. For example, crosslinking may be achieved by combining an amorphous resin with a crosslinker, sometimes referred to herein, in embodiments, as an initiator. Examples of suitable crosslinkers include, but are not limited to, for example free radical or thermal initiators such as organic peroxides and azo compounds. Examples of suitable organic peroxides include diacyl peroxides such as, for example, decanoyl peroxide, lauroyl peroxide and benzoyl peroxide, ketone peroxides such as, for example, cyclohexanone peroxide and methyl ethyl ketone, alkyl peroxyesters such as, for example, t-butyl peroxy neodecanoate, 2,5-dimethyl 2,5-di(2-ethyl hexanoyl peroxy)hexane, t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxy acetate, t-amyl peroxy acetate, t-butyl peroxy benzoate, t-amyl peroxy benzoate, oo-t-butyl o-isopropyl mono peroxy carbonate, 2,5-dimethyl 2,5-di(benzoyl peroxy)hexane, oo-t-butyl o-(2-ethyl hexyl)mono peroxy carbonate, and oo-t-amyl o-(2-ethyl hexyl)mono peroxy carbonate, alkyl peroxides such as, for example, dicumyl peroxide, 2,5-dimethyl 2,5-di(t-butyl peroxy)hexane, t-butyl cumyl peroxide, α-α-bis(t-butyl peroxy)diisopropyl benzene, di-t-butyl peroxide and 2,5-dimethyl 2,5di(t-butyl peroxy)hexyne-3, alkyl hydroperoxides such as, for example, 2,5-dihydro peroxy 2,5-dimethyl hexane, cumene hydroperoxide, t-butyl hydroperoxide and t-amyl hydroperoxide, and alkyl peroxyketals such as, for example, n-butyl 4,4-di(t-butyl peroxy)valerate, 1,1-di(t-butyl peroxy) 3,3,5-trimethyl cyclohexane, 1,1-di(t-butyl peroxy)cyclohexane, 1,1-di(t-amyl peroxy)cyclohexane, 2,2-di(t-butyl peroxy)butane, ethyl 3,3-di(t-butyl peroxy)butyrate and ethyl 3,3-di(t-amyl peroxy)butyrate, and combinations thereof. Examples of suitable azo compounds include 2,2,′-azobis(2,4-dimethylpentane nitrile), azobis-isobutyronitrile, 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethyl valeronitrile), 2,2′-azobis(methyl butyronitrile), 1,1′-azobis(cyano cyclohexane), other similar known compounds, and combinations thereof. 
         [0069]    The crosslinker and amorphous resin may be combined for a sufficient time and at a sufficient temperature to form the crosslinked polyester gel. In embodiments, the crosslinker and amorphous resin may be heated to a temperature of from about 25° C. to about 99° C., in embodiments from about 30° C. to about 95° C., for a period of time of from about 1 minute to about 10 hours, in embodiments from about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell. 
         [0070]    Where utilized, the crosslinker may be present in an amount of from about 0.001% by weight to about 5% by weight of the resin, in embodiments from about 0.01% by weight to about 1% by weight of the resin. The amount of CCA may be reduced in the presence of crosslinker or initiator. 
         [0071]    A single polyester resin may be utilized as the shell or, in embodiments, a first polyester resin may be combined with other resins to form a shell. Multiple resins may be utilized in any suitable amounts. In embodiments, a first amorphous polyester resin may be present in an amount of from about 20 percent by weight to about 100 percent by weight of the total shell resin, in embodiments from about 30 percent by weight to about 90 percent by weight of the total shell resin. Thus, in embodiments, a second resin may be present in the shell resin in an amount of from about 0 percent by weight to about 80 percent by weight of the total shell resin, in embodiments from about 10 percent by weight to about 70 percent by weight of the shell resin. 
       Coalescence 
       [0072]    Following aggregation to the desired particle size and application of an optional shell resin described above, the particles may then be coalesced to the desired final shape. 
         [0073]    The air flow carrying droplets of correct size (indicated as 2 in  FIG. 2 ) is guided to a heating section where the droplets are first heated (from about 50° C. to about 100° C.) to evaporate the carrier liquid medium (in embodiments, water) and then heated (from about 60° C. to about 150° C.) with hot air injection, for example, for the particulate content (i.e., the aggregates) to coalesce into the final morphology. During the drying and heating process, the droplet loading in the air stream can be kept small, in embodiments as dilute suspension, to minimize the possible collisions between the droplets. The heating process does not have to be separated in two different steps. An alternative can be a path of gradually increased temperature. This temperature may, in embodiments, be from about 40° C. to about 99° C., in embodiments from about 50° C. to about 95° C. Higher or lower temperatures may be used, it being understood that the temperature is a function of the resins used. 
         [0074]    After the heating for coalescence, the air flow (now carrying finished toner particles) enters a cyclone separator (or a bag-house filtering system) where the toner particles are separated from the air. The cyclone separator is equipped with a double-door lock that helps maintain a vacuum in the system. The finished toner product at the bottom of the cyclone separator is then cooled to room temperature. The device of the present disclosure can be used not only for EA toner production, but also for the production of other nano-composite particles. For example, it can be used to coat gold nano-particles with polymers. 
       Additives 
       [0075]    In embodiments, the toner particles may also contain other optional additives, as desired or required. For example, there can be blended with the toner particles external additive particles including flow aid additives, which additives may be present on the surface of the toner particles. Examples of these additives include metal oxides such as titanium oxide, silicon oxide, tin oxide, mixtures thereof, and the like; colloidal and amorphous silicas, such as AEROSIL®, metal salts and metal salts of fatty acids inclusive of zinc stearate, aluminum oxides, cerium oxides, and mixtures thereof. Each of these external additives may be present in an amount of from about 0.1 percent by weight to about 5 percent by weight of the toner, in embodiments of from about 0.25 percent by weight to about 3 percent by weight of the toner. Suitable additives include those disclosed in U.S. Pat. Nos. 3,590,000, 3,800,588, 6,214,507, and 7,452,646 the disclosures of each of which are hereby incorporated by reference in their entirety. Again, these additives may be applied simultaneously with the shell resin described above or after application of the shell resin. 
         [0076]    Additives may be combined with the toner particles as part of a dispersion; in embodiments such additives in a dispersion may be referred to as a particle dispersion. In embodiments, such a particle dispersion may be an aqueous dispersion and may include electronically conductive or semiconductive particles. 
         [0077]    In embodiments, toners of the present disclosure may be utilized as ultra low melt (ULM) toners. In embodiments, the dry toner particles having a shell of the present disclosure may, exclusive of external surface additives, have the following characteristics: 
         [0078]    (1) Volume average diameter (also referred to as “volume average particle diameter”) of from about 3 to about 25 μm, in embodiments from about 4 to about 15 μm, in other embodiments from about 5 to about 12 μm. 
         [0079]    (2) Number Average Geometric Size Distribution (GSDn) and/or Volume Average Geometric Size Distribution (GSDv) of from about 1.05 to about 1.55, in embodiments from about 1.1 to about 1.4. 
         [0080]    (3) Circularity of from about 0.93 to about 1, in embodiments from about 0.95 to about 0.99 (measured with, for example, a Sysmex FPIA 2100 analyzer). 
         [0081]    The characteristics of the toner particles may be determined by any suitable technique and apparatus. Volume average particle diameter D 50v , GSDv, and GSDn may be measured by means of a measuring instrument such as a Beckman Coulter Multisizer 3, operated in accordance with the manufacturer&#39;s instructions. Representative sampling may occur as follows: a small amount of toner sample, about 1 gram, may be obtained and filtered through a 25 micrometer screen, then put in isotonic solution to obtain a concentration of about 10%, with the sample then run in a Beckman Coulter Multisizer 3. 
         [0082]    Toners produced in accordance with the present disclosure may possess excellent charging characteristics when exposed to extreme relative humidity (RH) conditions. The low-humidity zone (C zone) may be about 10° C./15% RH, while the high humidity zone (A zone) may be about 28° C./85% RH. 
       Developers 
       [0083]    The toner particles thus obtained may be formulated into a developer composition. The toner particles may be mixed with carrier particles to achieve a two-component developer composition. The toner concentration in the developer may be from about 1% to about 25% by weight of the total weight of the developer, in embodiments from about 2% to about 15% by weight of the total weight of the developer. 
       Carriers 
       [0084]    Examples of carrier particles that can be utilized for mixing with the toner include those particles that are capable of triboelectrically obtaining a charge of opposite polarity to that of the toner particles. Illustrative examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrites, iron ferrites, silicon dioxide, and the like. Other carriers include those disclosed in U.S. Pat. Nos. 3,847,604, 4,937,166, and 4,935,326. 
         [0085]    The selected carrier particles can be used with or without a coating. In embodiments, the carrier particles may include a core with a coating thereover which may be formed from a mixture of polymers that are not in close proximity thereto in the triboelectric series. The coating may include fluoropolymers, such as polyvinylidene fluoride resins, terpolymers of styrene, methyl methacrylate, and/or silanes, such as triethoxy silane, tetrafluoroethylenes, other known coatings and the like. For example, coatings containing polyvinylidenefluoride, available, for example, as KYNAR 301F™, and/or polymethylmethacrylate, for example having a weight average molecular weight of about 300,000 to about 350,000, such as commercially available from Soken, may be used. In embodiments, polyvinylidenefluoride and polymethylmethacrylate (PMMA) may be mixed in proportions of from about 30 to about 70 weight % to about 70 to about 30 weight %, in embodiments from about 40 to about 60 weight % to about 60 to about 40 weight %. The coating may have a coating weight of, for example, from about 0.1 to about 5% by weight of the carrier, in embodiments from about 0.5 to about 2% by weight of the carrier. 
         [0086]    In embodiments, PMMA may optionally be copolymerized with any desired comonomer, so long as the resulting copolymer retains a suitable particle size. Suitable comonomers can include monoalkyl, or dialkyl amines, such as a dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, or t-butylaminoethyl methacrylate, and the like. The carrier particles may be prepared by mixing the carrier core with polymer in an amount from about 0.05 to about 10 percent by weight, in embodiments from about 0.01 percent to about 3 percent by weight, based on the weight of the coated carrier particles, until adherence thereof to the carrier core by mechanical impaction and/or electrostatic attraction. 
         [0087]    Various effective suitable means can be used to apply the polymer to the surface of the carrier core particles, for example, cascade roll mixing, tumbling, milling, shaking, electrostatic powder cloud spraying, fluidized bed, electrostatic disc processing, electrostatic curtain, combinations thereof, and the like. The mixture of carrier core particles and polymer may then be heated to enable the polymer to melt and fuse to the carrier core particles. The coated carrier particles may then be cooled and thereafter classified to a desired particle size. 
         [0088]    In embodiments, suitable carriers may include a steel core, for example of from about 25 to about 100 μm in size, in embodiments from about 50 to about 75 μm in size, coated with about 0.5% to about 10% by weight, in embodiments from about 0.7% to about 5% by weight, of a conductive polymer mixture including, for example, methylacrylate and carbon black using the process described in U.S. Pat. Nos. 5,236,629 and 5,330,874. 
         [0089]    The carrier particles can be mixed with the toner particles in various suitable combinations. The concentrations are may be from about 1% to about 20% by weight of the toner composition. However, different toner and carrier percentages may be used to achieve a developer composition with desired characteristics. 
       Imaging 
       [0090]    The toners can be utilized for electrostatographic or xerographic processes, including those disclosed in U.S. Pat. No. 4,265,990, the disclosure of which is hereby incorporated by reference in its entirety. In embodiments, any known type of image development system may be used in an image developing device, including, for example, magnetic brush development, jumping single-component development, hybrid scavengeless development (HSD), and the like. These and similar development systems are within the purview of those skilled in the art. 
         [0091]    Imaging processes include, for example, preparing an image with a xerographic device including a charging component, an imaging component, a photoconductive component, a development component, a transfer component, and a fusing component. In embodiments, the development component may include a developer prepared by mixing a carrier with a toner composition described herein. The xerographic device may include a high speed printer, a black and white high speed printer, a color printer, and the like. 
         [0092]    Once the image is formed with toners/developers via a suitable image development method such as any one of the aforementioned methods, the image may then be transferred to an image receiving medium such as paper and the like. In embodiments, the toners may be used in developing an image in an image-developing device utilizing a fuser roll member. Fuser roll members are contact fusing devices that are within the purview of those skilled in the art, in which heat and pressure from the roll may be used to fuse the toner to the image-receiving medium. In embodiments, the fuser member may be heated to a temperature above the fusing temperature of the toner, for example to temperatures of from about 70° C. to about 160° C., in embodiments from about 80° C. to about 150° C., in other embodiments from about 90° C. to about 140° C., after or during melting onto the image receiving substrate. 
         [0093]    The present disclosure describes a method and apparatus of a low-cost, rapid continuous process for the production of chemical toners or nano-particle composites. The proposed method eliminates the traditional aggregation process associated with chemical/EA toner production. Instead, the exemplary embodiments of the present disclosure use an inkjet drop ejector and drying process to force aggregation of primaries (or intermediates) to form desired-sized particles. The drop ejector process is efficient, and may reduce the toner manufacturing cost and increase a toner plant&#39;s throughput. The high efficiency of the proposed production method and the resulting savings could even be more significant in polyester EA toner production than in acrylate-based EA. 
         [0094]    In summary, the present disclosure is equally applicable in styrene-acrylate EA and polyester EA toner productions. The drop ejector is small and suitable for fast-turnaround toner production. The drop ejector may be used for other applications such as nano-particle composite, and a commercial drop ejector may be used to illustrate a way of producing uniform droplets. The drop ejector mechanism includes, but is not limited to, piezoelectric, pneumatic, electrostatic, and mechanical methods. Additionally, the surface tension on the droplets is utilized for formation and compacting the formed aggregate. If desired, prior to or after the coalescence, the formed aggregates/particles may also be coated with an outer/shell layer for desired functionalities. 
         [0095]    Another advantage of the present disclosure is that the drop ejector process may scale up and down. This is especially true when a printhead configuration is used. In addition to the production scale as described previously, one may scale down to pilot or even laboratory applications where small quantities of samples are frequently made and have to be made as low cost as possible. This technology of the exemplary embodiments of the present disclosure may be used to produce precise amounts of different samples quickly and cost effectively. In particular, when DOD printheads are used, the ability to control the process and particle formation is so good that it may closely meet the number of particles specified by an application. This unique characteristic is attractive in at least pharmaceutical and bio-/nano-technology laboratories. 
         [0096]    The following Examples are being submitted to illustrate embodiments of the present disclosure. These Examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. Also, parts and percentages are by weight unless otherwise indicated. As used herein, “room temperature” refers to a temperature of from about 20° C. to about 30° C. 
       EXAMPLES 
     Example 1 
       [0097]    Example: A toner production line equipped with the technology proposed in the exemplary embodiments of the present disclosure is aimed to produce 5 μm polyester EA toner. The radius r of a 5 μm spherical toner is 2.5 μm. The volume of a single toner particle is: 
         [0000]    
       
         
           
             
               
                 ( 
                 
                   4 
                   3 
                 
                 ) 
               
                
               
                 π 
                 · 
                 
                   r 
                   3 
                 
               
             
             = 
             
               65.45 
                
               
                   
               
                
               
                 
                   µm 
                   3 
                 
                 . 
               
             
           
         
       
     
         [0098]    Since the density of polyester is 1400 kg/m 3 , the mass of one toner particle is 1400*65.45/(10 6 ) 3  kg=9.163×10 −14  kg. Assuming the solid loading of the jetted droplets is 10%, the volume of a droplet would have to be 654.5 μm 3 . This corresponds to a droplet radius of 5.4 μm. Thus, the jetting/spraying systems need to produce droplets that are 10.8 μm in size. 
         [0099]    Where DOD ejectors are used, a drop-on-demand ejector may operate at 60 KHz. The production rate is then 60000*9.163×10 −14  kg/second/jet, which is 4.35×10 −5  lb/hour/jet. If it is assumed that one process module contains 100000 jets (which may be MEMS fabricated ejectors), the unit may produce 4.35 lb/hour. Also, if it is assumed that on the day of operation the production line uses 20 units, the throughput may be 87 lb/hour, and daily production is 2088 pounds. 
         [0100]    Where CIJ is used, a CIJ may produce 165000 droplets per second per jet. The production rate is 165000*9.163×10 −14  kg/sec/jet; which is 1.2×10 4  lb/hour/jet. If it is assumed that one modular unit contains 100000 jets, the unit may produce 12 lb/hour. Also, if it is assumed that on that day of operation the production line uses 20 units, the throughput is then 240 lb/hour, and daily production is 5760 pounds. 
         [0101]    The above calculations demonstrate that the proposed embodiments that use inkjet printheads may indeed achieve a throughput suitable for production. Furthermore, the spray nozzle system could potentially be designed to reach an even higher production rate because (1) the droplet size-control function is separated from the nozzle design and therefore the design requirement of the nozzles may be relaxed to focus on throughput; and (2) higher operation pressures may be used. 
         [0102]    The cost effectiveness of the proposed embodiments comes from the fact that the jetting heads of DOD and CIJ are the same kind as those used in inkjet printers of which the fabrication has become a mature technology, and has been tailored to massive production with extremely low unit cost. Only the cost of a high pressure spray system is difficult to estimate since, unlike the DOD and CIJ heads, the spray head and the size classifier may not be available as commercial devices. In terms of operation cost, the modular unit concept described above provides a flexible manufacturing process that may be tuned to optimal condition when the throughput demands change. This flexibility is desirable and may significantly reduce the overall manufacturing cost. 
         [0103]    It will be appreciated that variations of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.