Patent Application
20150218059
1. Technical Field
The embodiments herein generally relate to fertilizers and particularly to polymer coated fertilizers. The embodiments herein more particularly relate to a system and method for manufacturing polymer-coated fertilizers with a controlled release mechanism for plants and crops.
2. Description of the Related Art
A fertilizer is an organic or inorganic material of natural or synthetic origin that is added to a soil to supply one or more plant nutrients essential for the growth of the plants. Fertilizers are broadly divided into organic fertilizers (composed of plants or animal matters), or inorganic/commercial fertilizers. Plants absorb the required nutrients only when they are present in a form of easily dissolved chemical compounds. Both the organic and inorganic fertilizers provide the same chemical compounds that are needed. The organic fertilizers provide both macro and micro nutrients. The macro and micro nutrients are released as the organic matter decay. The decay may take months or years. Further the organic fertilizers have lower concentrations of plant nutrients and have the usual problems of economical collection, treatment, transportation and distribution. Inorganic fertilizers are readily dissolved and applied to the soil. The dissolved inorganic fertilizers is readily taken by the plant roots.
Most of the commercially available fertilizers, when applied to the lawns or agricultural crops, dissolve rapidly in the moisture of the soil. Often, such fertilizers dissolve at a rate that exceeds the rate in which it is absorbed by the plants. This causes a number of significant problems. First, the excess fertilizer can leach into the groundwater thereby generating a potentially serious environmental damage. In addition to the above, an excessive concentration of the fertilizers in the vicinity of a plant may result in a burning or damage of the plant roots. Because of these problems, it is often necessary to apply these fertilizers in several light doses throughout the growing season, rather than in a single heavy application. However, the need for repeated applications increases a cost of the labor. At worse, the repeated applications may cause a physical damage to the growing plants because the fertilizer spreading equipment must pass over the plants for several times.
In order to minimize the loss of fertilizer into the environment and to avoid the need for the repeated applications, various slow or controlled release fertilizers have been developed. The U.S. Pat. Nos. 4,042,366, 5,147,443, 5,435,821, and 6,231,633 disclose such controlled release fertilizers. These fertilizers are applied at the beginning of the growing season to facilitate a higher release of fertilizer in the initial growing period followed by a slower release or gradual release of fertilizer throughout the growing season. The slow or controlled release fertilizers are widely used on the agriculture crops, home lawns, public lawns, golf courses, home gardens, plant nurseries, and for horticultural crops.
The polymer coated fertilizers are the most technically advanced controlled release fertilizers. Many manufacturing methods are developed and used to produce polymer-coated fertilizers and they are disclosed in the U.S. Pat. Nos. 4,019,890, 4,369,055, 5,176,734, 5,211,985, 5,374,292, 5,858,094, 6,338,746, and 8,211,201. The polymer coated controlled release fertilizers are typically produced by coating a water insoluble semi-permeable polymer layer onto the fertilizer granules. The fertilizer is released over a time period into the soil by diffusion through this semi-permeable coating.
One of the popular methods of manufacturing the polymer-coated fertilizers is by reacting the chemical monomers onto the surface of the granule to form a polymer film. This method is called a reactive layer coating in which a polyurethane polymer is formed. Another popular method of manufacturing the polymer coated fertilizers is by spraying a solution of polymer onto the fertilizer granules and evaporating the solvent thereby forming a polymer film coating. This method is called fluidized bed coating and it requires an expensive solvent and a solvent recovery system.
The most critical aspect of the controlled-release fertilizers is the moisture permeability of the coating, which is affected by the thickness of the coated polymer. The release of fertilizer takes place via diffusion through the coating and the uniformity of the release rate depends on the uniformity of the coating thickness. An uneven coating thickness will have uneven moisture transmission rate and hence the quality of the controlled-release products will also vary.
Another critical shortcoming of the existing coating technologies is that these coating processes spray polymer solution onto a plurality of fertilizer granules which are tumbling and rolling in a random fashion inside a rotary drum or in a vertical column of fluidized bed. The uneven shaped granules produce completely random rolling pattern thus the coating cannot be directed and this results into an uneven coating thickness. This problem worsens when the shape is extremely uneven or non-spherical such as the fertilizer products made by compaction process, which have highly uneven shape. Thus all existing coating technologies require expensive premium grade round fertilizer granule with smooth surfaces (U.S. Pat. No. 6,039,781 A & U.S. Pat. No. 6,139,597 A) so that non-uniformity of the coating can be minimized.
The disadvantages suffered by the existing process are that either these methods are polymer specific such as polyurethane processes or the process requires an expensive solvent to produce the coating in case of fluidized bed coating. All these methods produce the products that are very expensive and sometimes the cost is equal to 4-6 times the prices of the conventional fertilizers. The primary reason for the expensive nature is the use of expensive polymers or the use of an expensive solvent or both. Yet another disadvantage is that most of these manufacturing processes are batch type processes, which are expensive.
Another disadvantage with the existing processes is that they require multiple applications of polymer to increase the thickness of the polymer coating around the fertilizer, as disclosed in U.S. Pat. No. 7,018,441 B2. For example, it requires nearly 16 applications of the polyurethane polymer to achieve a coating thickness of 8%. A coating thickness 0.5% only is achieved in each application and hence more time and energy are required for multiple applications thereby increasing the production cost.
Yet another disadvantage of the existing coating technologies is that the fertilizer granules with lower compression or crushing strength cannot be coated due to turbulence in the coating system.
A manufacturing process is disclosed in the U.S. Pat. No. 8,211,201 to overcome the above-mentioned disadvantages. But one disadvantage of this process is the use of molten fertilizer as a feed to produce the coated fertilizers thereby leaving a majority of fertilizer granules including fertilizers in tablet, spikes, pellet, or briquette form. The melting and solidifying of the fertilizer granules requires a substantial amount of energy, which increase the production cost and many fertilizers cannot be produced in melt form for use in this process. Additionally the process produces the coated products in hemispherical or pasttile shape which may not be appealing to many users.
Hence there is a need for an economical system and method for manufacturing polymer coated controlled release fertilizers continuously to enable the use any available fertilizer granule in any shape and form for producing polymer coated products with uniform coating thickness
The above mentioned shortcomings, disadvantages and problems are addressed herein and which will be understood by reading and studying the following specification.
The primary object of the embodiments herein is to provide a system and method for manufacturing a polymer coated controlled release fertilizers with a desired coating of uniform thickness in a single pass and in a high speed.
Another object of the embodiments herein is to develop a system and method for manufacturing polymer coated granules to enable a use of fertilizer granule of even and irregular shapes.
Yet another object of the embodiments herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to enable a use of fertilizers in tablets, spikes, briquettes, or pellets shape.
Yet another object of the embodiments herein is to develop a system and method for manufacturing polymer-coated fertilizers to obtain a polymer coated fertilizer that prevents caking or agglomeration during transportation.
Yet another object of the embodiments herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to enable a use of any commercially available polymer to coat the fertilizer without requiring any solvent or curing, or catalyst for forming the coating onto the fertilizer granule.
Yet another object of the embodiments herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to allow a complete control of coating application onto the fertilizer granules to achieve a uniform and precise coating thickness.
Yet another object of the embodiments herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to apply multiple polymer layers simultaneously thereby allowing the manufacturer to produce the fertilizers coated with multiple polymer layers.
Yet another object of an embodiment herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to obtain the polymer coated fertilizer and fertilizer products with a desired coating thickness in a single pass thereby saving time, space and energy.
Yet another object of an embodiment herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to obtain the polymer coated fertilizers and fertilizer products with a desired water vapor transmission rate (WVTR) thereby making a highly effective controlled release fertilizer products.
Yet another object of an embodiment herein is to develop a system and method for manufacturing a polymer coated controlled release fertilizers to obtain polymer coated fertilizers and fertilizer products with a desired duration of biodegradation so that the coating is degraded in a predetermined duration.
These and other objects and advantages of the embodiments herein will become readily apparent from the following detailed description taken in conjunction with the accompanying drawings.
The various embodiments herein, provide a system and method for manufacturing polymer-coated fertilizers. According to an embodiment herein, the fertilizer granules are coated in two steps. In the first step, the fertilizer granules are partially coated by a first polymer film. Thereafter a second polymer film is applied onto the remaining uncoated surface of the fertilizer granule to encapsulate the fertilizer between the two polymer films. The encapsulated fertilizer between the first polymer film and the second polymer film is releasable over a time period or interval by diffusion through the first polymer film or the second polymer film.
According to an embodiment herein, a system for coating a plurality of articles in a continuous process using a polymer melt is provided. The system comprises a feeding mechanism connected to a first chill roll to supply a plurality of articles. The first chill roll comprises a plurality of first cavities on a peripheral surface and the plurality of first cavities houses and holds a plurality of articles. A first machine is provided for producing a first molten film and applying the first molten film on the plurality of articles held in the plurality of first cavities in the first chill roll to partially coat the plurality of articles with the first molten film. A second chill roll is placed at a side of the first chill roll or the second chill roll is placed on a top side of the first chill roll to receive a plurality of articles partially coated with a first molten film. A second machine is provided for producing and applying the second molten film on the plurality of articles held in the plurality of second cavities in the second chill roll and partially coated with the first molten film. A collector mechanism is provided to receive the plurality of articles coated with the first molten film and the second molten film from the second chill roll.
According to an embodiment herein, a system for coating a plurality of articles in a continuous process using a polymer melt is provided. The system comprises a first chill roll, a second chill roll, a first machine, a second machine, a feeding mechanism and a collector mechanism.
According to an embodiment herein, the first chill roll comprises a plurality of first cavities on a peripheral surface and the plurality of first cavities houses and holds a plurality of articles.
According to an embodiment herein, the second chill roll is identical to the first chill roll. The second chill roll is placed at a side of the first chill roll or the second chill roll is placed on a bottom side of the first chill roll. The second chill roll comprises a plurality of second cavities on a peripheral surface. The plurality of second cavities houses and holds a plurality of articles received from the first chill roll. The plurality of second cavities in the second chill roll matches with the plurality of first cavities in the first chill roll. The plurality of second cavities hi the second chill roll and the plurality of first cavities in the first chill roll are arranged to face each other.
According to an embodiment herein, the system comprises a first machine for producing a first molten film and applying the first molten film on the plurality of articles held in the plurality of first cavities in the first chill roll to partially coat the plurality of articles with the first molten film. The first molten film has a desired thickness, width and chemical properties. The first machine comprises a first polymer extruder and a first film molding die. The first polymer extruder mixes, melts and extrudes a polymer to generate a homogenous melt of polymer. The first film molding die is attached to an end of the first polymer extruder for receiving a molten feed from the first polymer extruder to produce the first molten film of desired thickness and width. The polymer is a single polymer or a blend of polymers.
According to an embodiment herein, the system comprises a second machine for producing a second molten film and applying the second molten film on the plurality of articles held in the plurality of second cavities in the second chill roll. The second molten film has a desired thickness, width and chemical properties. The second machine comprises a second polymer extruder and a second film molding die. The second polymer extruder mixes, melts and extrudes a polymer to generate a homogenous melt of polymer. The second film molding die is attached to an end of the polymer extruder for receiving a molten feed from the second polymer extruder to produce the second molten film of desired thickness and width. The polymer is a single polymer or a blend of polymers.
According to an embodiment herein, the system comprises a feeding mechanism for feeding the plurality of articles to the first chill roll and a collection mechanism for collecting the plurality of articles from the second chill roll. The plurality of articles collected from the second chill roll are coated with the first polymer film at one side of the plurality of articles and with the second polymer film at an opposite side of the plurality of articles so that the plurality of articles are encapsulated within the first polymer film and the second polymer film. The plurality of articles is a controlled release article.
According to an embodiment herein, the plurality of articles is selected from a group consisting of a fertilizer, a pharmaceutical tablet, a detergent tablet, a biocide tablet, a pesticide granule, an animal feed and a food particle. The plurality of articles is water soluble. The plurality of articles is selected from a group consisting of a polymer coated articles.
According to an embodiment herein, the mean article size is within the range of 1 mm to 150 mm.
According to an embodiment herein, the system further comprises a cutting mechanism provided at the first chill roll and the second chill roll to cut the first polymer film and the second polymer film after application on the plurality of articles. The cutting mechanism is a sharp cutting edge provided on the surface of the first chill roll and the second chill roll.
According to an embodiment herein, the system further comprises a rotary pin to push the plurality of articles held at the plurality of second cavities in the second chill roll, when the second polymer film is applied on the plurality of the articles coated partially with the first polymer film.
According to an embodiment herein, the first chill roll is rotated in a clockwise direction through a desired angle for receiving the plurality of articles at the plurality of first cavities. The second chill roll is rotated in an anti-clockwise direction through a desired angle for receiving the plurality of articles at the plurality of cavities. The first chill roll and the second chill roll are rotated in a synchronized manner in the clockwise direction and in the anti-clockwise direction respectively so that at least one of the plurality of first cavities in the first chill roll is arranged opposite to at least one of the plurality of second cavities in the second chill roll to transfer the plurality of articles in the first cavities of the first chill roll to the plurality of second cavities in the second chill roll.
According to an embodiment herein, the first chill roll and the second chill roll comprise an internal fluid circulation mechanism for circulating a fluid to control a surface temperature of the first chill roll. The first chill roll and the second chill roll comprise a non-stick coating on an outer surface to avoid a sticking of the molten film onto the surface of the chill roll. The first chill roll and the second chill roll are rotatable cylindrical drums.
According to an embodiment herein, each of the plurality of first cavities and each of the plurality of second cavities hold one article. The plurality of first cavities and the pluralities of the second cavities are arranged in a shape selected from a group consisting of a tablet, spike, circular, rectangular, square and hexagonal shapes. Each one of the plurality of first cavities and each one of the plurality of second cavities holds at-least one article by a vacuum. The plurality of first cavities and the plurality of second cavities comprise an opening or hole in a bottom to provide the vacuum for holding the plurality of articles. A size of the plurality of first cavities is larger than a size of the plurality of articles and a size of the plurality of second cavities is larger than a size of the plurality of articles. The plurality of first cavities and the plurality of second cavities comprise a compressable cushion ring in a bottom. The cushion ring is made up of a material selected from a group consisting of a soft rubber material or a rubber like material.
According to an embodiment herein, the first polymer film die and the second polymer film die is any one of a curtain coating and a slot dye. The first polymer film die and the second polymer film die produce a single layer polymer film or a multilayer polymer film. According to an embodiment herein, the polymer is melt processed into a molten film of desired thickness.
According to an embodiment herein, the first polymer film is coated on the surface of the plurality of articles in a range of 1%-99%. The second polymer film is coated on the surface of the plurality of articles coated partially with the first polymer film in a range of 1%-99%.
According to an embodiment herein, the first polymer film and the second polymer film comprise one or more additives. The one or more additives are selected from a group consisting of hydrophilic additives, surfactants, inorganic minerals, biodegradable additives, pigments and water soluble additive. The hydrophilic additives are added for increasing a moisture permeability of the first polymer film and the second polymer film.
According to an embodiment herein, the inorganic mineral is selected from a group consisting of talc, calcium carbonate, mica, silica and their derivatives. The inorganic minerals are added for modifying a moisture permeability, reducing a temperature induced expansion of the first polymer film and the second polymer film, and reducing a tackiness of the first polymer film and the second polymer film, and preventing a caking or agglomeration of the plurality of articles coated with the first polymer film and the second polymer film.
According to an embodiment herein, wherein the biodegradable additives are added for adding a biodegradable characteristics to the first polymer film and the second polymer film and for expediting a biodegradation of the first polymer film and the second polymer film. The additives are added to the first polymer film and the second polymer film layer in a range of 0.01%-50% of a combined dry weight of the first polymer film and the second polymer film.
According to an embodiment herein, the desired thickness of the first polymer film and the second polymer film is within a range of 5 microns to 300 microns. The desired temperature of the first molten polymer film and the second molten polymer film is within a range of 50° C. to 500° c. The desired chemical property of the first polymer film and the second polymer film is water vapor transmission rate (WVTR). The desired WVTR of the first polymer film and the second polymer film is within a range of 0.001 g/(m2·day) to 20000 g/(m2·day).
According to an embodiment herein, a method is provided for coating a plurality of articles in a continuous process using a polymer. The method comprises extruding and applying a first coating layer with a first molten polymer film on a plurality of articles held on a plurality of first cavities in a first chill roll for generating a plurality of articles coated partially with the first polymer film. The plurality of articles coated partially with the first polymer film is transferred from the first chill roll to a second chill roll. An uncoated portion of the plurality of articles coated partially with the first polymer film is exposed. A second coating layer of a second molten polymer film is extruded and applied on the plurality of articles held on a plurality of second cavities in the second chill roll for generating a plurality of articles fully coated with the first polymer film and the second polymer film. The plurality of articles is encapsulated between the first coating layer and the second coating layer by sealing the first polymer film and the second polymer film coated on the plurality of articles by melt fusing the second polymer film with the first polymer film on an overlapping area of the first polymer film and the second polymer film. The encapsulated plurality of articles is released over a time period by a diffusion of the encapsulated plurality of articles through the first polymer film or the second polymer film.
According to an embodiment herein, the plurality of articles are held in the plurality of first cavities and in the plurality of second cavities by a vacuum suction adopted at a bottom of the plurality of first cavities and at the plurality of second cavities. A pulling force of the vacuum suction under the plurality of articles is adapted to pull the first polymer film and the second polymer film around the plurality of articles and to adhere the first polymer film and the second polymer film respectively to an opposing surface of the plurality of articles.
According to an embodiment herein, the mean article size is within 1 mm to 150 mm.
According to an embodiment herein, the first polymer film is coated on the surface of the plurality of articles in a range of 1%-99%. The second polymer film is coated on the surface of the plurality of articles coated partially with the first polymer film in a range of 1%-99%.
According to an embodiment herein, the polymer is melt processed into a molten film.
According to an embodiment herein, the first polymer film and the second polymer film comprises one or more additives. The one or more additives are selected from a group consisting of hydrophilic additives, surfactants, inorganic minerals, biodegradable additives, pigments and water soluble additive. The hydrophilic additives or surfactants are added for increasing a moisture permeability of the first polymer film and the second polymer film.
According to an embodiment herein, the inorganic mineral is selected from a group consisting of talc, calcium carbonate, mica, silica and their derivatives. The inorganic minerals are added for modifying a moisture permeability, reducing a temperature induced expansion of the first polymer film and the second polymer film, and reducing a tackiness of the first polymer film and the second polymer film, and preventing a caking or agglomeration of the plurality of articles coated with the first polymer film and the second polymer film.
According to an embodiment herein, the biodegradable additives are added for adding a biodegradable characteristic to the first polymer film and the second polymer film and for expediting a biodegradation of the first polymer film and the second polymer film.
According to an embodiment herein, the additives are added to the first polymer film and the second polymer film layer in a range of 0.01%-50% of a combined dry weight of the first polymer film and the second polymer film.
According to an embodiment herein, the desired thickness of the first polymer film and the second polymer film is within a range of 5 microns to 300 microns. The desired temperature of the first molten polymer film and the second molten polymer film is within a range of 50° C. to 500° C. The desired chemical property of the first polymer film and the second polymer film is water vapour transmission rate (WVTR). The WVTR value of the first polymer film and the second polymer film is within a range of 0.01 g/(m2·day) to 20,000 g/(m2·day).
According to an embodiment herein, the first chill roll and the second chill roll are rotatable cylindrical drums.
According to an embodiment herein, a method for manufacturing a controlled release fertilizer involves placing the fertilizer granules onto a surface and applying a first layer of polymer onto the exposed surface of the fertilizer granule. Then the uncoated portion of fertilizer is exposed and a second layer of polymer is applied to encapsulate the fertilizer granule between the first polymer layer and the second polymer layer such that the fertilizer granules are releasable over a time by a diffusion through at least one of the first polymer film or the second polymer film.
According to one embodiment herein, the manufacturing process of polymer-coated fertilizers has two main steps. In the first step, the fertilizer granules are partially coated by a first polymer film. Thereafter a second polymer film is applied onto the remaining uncoated fertilizer granule surface thereby encapsulating the fertilizer between the two polymer films.
According to one embodiment herein, an apparatus for coating plurality of articles in a continuous process using polymer melt comprises a first chill roll, a second identical chill roll, a first machine, a second machine, a feeding mechanism and a collection mechanism. The first chill roll comprises a plurality of cavities placed side by side and on the periphery of the first chill roll. The cavities are capable of holding the articles. The second identical chill roll comprises plurality of cavities placed side by side and on the periphery of second chill roll and the cavities of first and second chill rolls are facing each other. The first machine is used for producing a molten film of desired thickness, width and properties. The first polymer film is placed in such a way that the molten polymer film is applied directly onto the articles held in the cavity of the first chill roll. The second machine is adapted for producing a molten film of desired thickness, width and property. The second machine is placed in such a way that the molten film is applied directly onto the articles held in the cavity of the second chill roll. The feeding mechanism is for feeding the articles onto the first chill roll. The collection mechanism is for collecting coated articles from the second chill roll.
According to one embodiment herein, the chill roll is a cylindrical drum capable of rotating. The chill roll has a plurality of cavities on the circumferential surface of the roll. The chill roll has an internal fluid circulation to control a surface temperature of the chill roll. The chill roll has a non stick coating applied on the surface of the roll. The chill roll rotates in a synchronized way so that cavities on the surface of the first chill roll always face the identical cavities on the second chill roll.
The cavity of the chill roll is of any shape and dimension. The cavity of the chill roll is suitable for holding the articles being coated. The shape of the cavity is chosen from a tablet, spike, circular, rectangular, square or hexagonal shape. The cavities are distributed all over the circumference of the first and second chill roll. Further the cavities are of larger dimension than that of the articles being coated. The cavities have soft rubber or rubber like compressable cushion rings in the bottom. The cavity has an opening/hole in the bottom through which a vacuum suction is provided to hold the articles. Further the articles are housed in the cavity and held with the vacuum suction in the cavity. Only one article is housed per cavity.
According to one embodiment herein, the first and second machine used for producing a molten film comprises a polymer extruder and a film die. The polymer extruder is capable of mixing, melting and extruding any commercially available polymer or blend of polymers or additives and creating a homogenous melt. The polymer film die is capable of producing a molten film of desired thickness width and properties from the polymer film melt produced by the extruder. The die is attached to the end of the extruder.
According to one embodiment herein, the film die is a curtain coating die or slot die capable of producing a polymer film using polymer melt. The film die has a single layer or multilayer polymer film extrusion capability. The film die is a commercially available extrusion die capable of producing a molten polymer film of desired thickness, and width.
According to one embodiment herein, the method for coating the fertilizers is initiated by feeding the articles on the first chill roll where the articles are held in the cavities by the vacuum suction at the bottom of the cavity. The next step is extruding a first layer of molten polymer film on the articles. The pull of vacuum suction under the said articles pulls the molten polymer layer around the articles to adhere the molten film to the surface of the article to create a partially coated article. Further the partially coated articles are transferred to the cavity of the second chill roll and the uncoated portion of the partially coated particles is exposed. A second layer of molten polymer is extruded and applied on the uncoated portion of the partially coated articles in such a way that second coating layer overlaps the first coating layer and the high temperature of the molten second layer helps in laminating the second layer with the overlapping area of the first layer. Hence the fertilizer particle or an article is sealed or encapsulated between the first polymer layer and second polymer layer.
According to one embodiment herein, the articles are any commercially available fertilizer granule in any dimension and shape. Further the articles is any one selected from a group consisting of a detergent tablet of any shape and dimension, a biocide tablet of any shape and dimension, a pesticide granule of any shape and dimension, an animal feed of any shape and dimension, and a food particle of any shape and dimension. The articles have even or uneven shape. The articles chosen are water soluble.
According to one embodiment herein, the first and second polymer film is any extrusion grade polymer, capable of producing a film of desired thickness and properties. The molten polymer film withstands a temperature range of 50° C.-500° C. The thickness of the polymer film is in the range of 5-300 micron. Further, the desired chemical property of the first polymer film and the second polymer film is water vapor transmission rate (WVTR). The WVTR value of the first polymer film and the second polymer film is within a range of 0.01 g/(m2·day) to 20,000 g/(m2·day).
According to one embodiment herein, the partially coated articles have the polymer coat covering in the range of 1%-99% of the surface area. Further the second polymer film coating on the partially coated articles have polymer coat covering in the range of 1%-99% of the surface area, of the coated article.
According to one embodiment herein, a method of producing the controlled release delivery systems comprises coating a first layer of polymer onto the surface of the article creating partially coated articles. The remaining uncoated portion of the surface area is exposed and applied with a second coating layer. The article is sealed between the first coating layer and the second coating layer by melt fusing the second coating layer with the first coating layer in the overlapping area of the first coating layer and the second coating layer. The article is encapsulated between the first coating layer and the second coating layer. The encapsulated article between the first coating layer and second coating layer is releasable over the time by diffusion through the first coating layer or the second polymer film.
According to one embodiment herein, the first polymer film and second polymer film have multiple film layers forming a single laminated coating layer. The first or second polymer films have additives into the film structure. The additives are selected from the group consisting of hydrophilic additives, surfactants, inorganic minerals, biodegradable additives and pigments. The hydrophilic additives or surfactants are added for increasing the moisture permeability of the coating layer. Inorganic minerals such as talc, calcium carbonate, mica or silica or their derivatives are added for modifying moisture permeability, reducing a temperature induced expansion of the polymer coating, and reducing a caking or agglomeration of the coated articles. The biodegradation additives are added for expediting the biodegradation of the coating layer. The pigments are added for providing a color to the coating films. The amount of additives added to the polymer layer is within a range of 0.01%-50% of the combined dry weight of the first or second coating layer.
According to one embodiment herein, the first or second polymer film has multiple film layers co-extruded to form a single coating layer. Further the multilayer coated films are of different thickness or different additives or have additive loading levels.
According to one embodiment herein, cheap polymers are used to coat the fertilizer granules. Further the dry fertilizer granules in any shape, form are coated, thereby eliminating the need for using expensive spherical fertilizer granules. The method of coating the fertilizer granules does not involve any solvent or catalyst. The method gives a uniform coating on the fertilizer granules. Furthermore the method allows an application of multiple polymers simultaneously thereby allowing the manufacturer to produce a fertilizer coated with multiple polymer layers. The method has ability to apply a coating film with desired weight in a single time thereby saving time, space and energy to produce coated products.
These and other aspects of the embodiments herein will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following descriptions, while indicating preferred embodiments and numerous specific details thereof, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
The other objects, features and advantages will occur to those skilled in the art from the following description of the preferred embodiment and the accompanying drawings in which:
Although the specific features of the present invention are shown in some drawings and not in others. This is done for convenience only as each feature may be combined with any or all of the other features in accordance with the present invention.
In the following detailed description, a reference is made to the accompanying drawings that form a part hereof, and in which the specific embodiments that may be practiced is shown by way of illustration. These embodiments are described in sufficient detail to enable those skilled in the art to practice the embodiments and it is to be understood that the logical, mechanical and other changes may be made without departing from the scope of the embodiments. The following detailed description is therefore not to be taken in a limiting sense.
The various embodiments herein, provide a system and method for manufacturing polymer-coated fertilizers. According to an embodiment herein, the fertilizer granules are coated in two steps. In the first step, the fertilizer granules are partially coated by a first polymer film. Thereafter a second polymer film is applied onto the remaining uncoated surface of the fertilizer granule to encapsulate the fertilizer between the two polymer films. The encapsulated fertilizer between the first polymer film and the second polymer films is releasable over a time period or interval by diffusion through the first polymer film or the second polymer film.
According to an embodiment herein, a system for coating a plurality of articles in a continuous process using a polymer melt is provided. The system comprises a feeding mechanism connected to a first chill roll to supply a plurality of articles. The first chill roll comprises a plurality of first cavities on a peripheral surface and the plurality of first cavities houses and holds a plurality of articles. A first machine is provided for producing a first molten film and applying the first molten film on the plurality of articles held in the plurality of first cavities in the first chill roll to partially coat the plurality of articles with the first molten film. A second chill roll is placed at a side of the first chill roll or the second chill roll is placed on a bottom side of the first chill roll to receive a plurality of articles partially coated with a first molten film. A second machine is provided for producing and applying the second molten film on the plurality of articles held in the plurality of second cavities in the second chill roll and partially coated with the first molten film. A collector mechanism is provided to receive the plurality of articles coated with the first molten film and the second molten film from the second chill roll.
According to an embodiment herein, a system for coating a plurality of articles in a continuous process using a polymer melt is provided. The system comprises a first chill roll, a second chill roll, a first machine, a second machine, a feeding mechanism and a collector mechanism.
According to an embodiment herein, the first chill roll comprises a plurality of first cavities on a peripheral surface and the plurality of first cavities houses and holds a plurality of articles.
According to an embodiment herein, the second chill roll is identical to the first chill roll. The second chill roll is placed at a side of the first chill roll or the second chill roll is placed on a bottom side of the first chill roll. The second chill roll comprises a plurality of second cavities on a peripheral surface. The plurality of second cavities houses and holds a plurality of articles received from the first chill roll. The plurality of second cavities in the second chill roll matches with the plurality of first cavities in the first chill roll. The plurality of second cavities in the second chill roll and the plurality of first cavities in the first chill roll a arranged to face each other.
According to an embodiment herein, the system comprises a first machine for producing a first molten film and applying the first molten film on the plurality of articles held in the plurality of first cavities in the first chill roll to partially coat the plurality of articles with the first molten film. The first molten film has a desired thickness, width and chemical properties. The first machine comprises a first polymer extruder and a first film molding die. The first polymer extruder mixes, melts and extrudes a polymer to generate a homogenous melt of polymer. The first film molding die is attached to an end of the first polymer extruder for receiving a molten feed from the first polymer extruder to produce the first molten film of desired thickness and width. The polymer is a single polymer or a blend of polymers.
According to an embodiment herein, the system comprises a second machine for producing a second molten film and applying the second molten film on the plurality of articles held in the plurality of second cavities in the second chill roll. The second molten film has a desired thickness, width and chemical properties. The second machine comprises a second polymer extruder and a second film molding die. The second polymer extruder mixes, melts and extrudes a polymer to generate a homogenous melt of polymer. The second film molding die is attached to an end of the polymer extruder for receiving a molten feed from the second polymer extruder to produce the second molten film of desired thickness and width. The polymer is a single polymer or a blend of polymers.
According to an embodiment herein, the system comprises a feeding mechanism for feeding the plurality of articles to the first chill roll and a collection mechanism for collecting the plurality of articles from the second chill roll. The plurality of articles collected from the second chill roll are coated with the first polymer film at one side of the plurality of articles and with the second polymer film at an opposite side of the plurality of articles so that the plurality of articles are encapsulated within the first polymer film and the second polymer film. The plurality of articles is a controlled release article.
According to an embodiment herein, the plurality of articles is selected from a group consisting of a fertilizer, a pharmaceutical tablet, a detergent tablet, a biocide tablet, a pesticide granule, an animal feed and a food particle. The plurality of articles is water soluble.
According to an embodiment herein, the plurality of articles is selected from a group consisting of a polymer coated articles.
According to an embodiment herein, the mean article size is within the range of 1 mm to 150 mm.
According to an embodiment herein, the system further comprises a cutting mechanism provided at the first chill roll and the second chill roll to cut the first polymer film and the second polymer film after application on the plurality of articles. The cutting mechanism is a sharp cutting edge provided on the surface of the first chill roll and the second chill roll.
According to an embodiment herein, the system further comprises a rotary pin to push the plurality of articles held at the plurality of second cavities in the second chill roll, when the second polymer film is applied on the plurality of the articles coated partially with the first polymer film.
According to an embodiment herein, the first chill roll is rotated in a clockwise direction through a desired angle for receiving the plurality of articles at the plurality of first cavities. The second chill roll is rotated in an anti-clockwise direction through a desired angle for receiving the plurality of articles at the plurality of cavities. The first chill roll and the second chill roll are rotated in a synchronized manner in the clockwise direction and in the anti-clockwise direction respectively so that at least one of the plurality of first cavities in the first chill roll is arranged opposite to at least one of the plurality of second cavities in the second chill roll to transfer the plurality of articles in the first cavities of the first chill roll to the plurality of second cavities in the second chill roll.
According to an embodiment herein, the first chill roll and the second chill roll comprise an internal fluid circulation mechanism for circulating a fluid to control a surface temperature of the first chill roll. The first chill roll and the second chill roll comprise a non-stick coating on an outer surface to avoid a sticking of the molten film. The first chill roll and the second chill roll are rotatable cylindrical drums.
According to an embodiment herein, each of the plurality of first cavities and each of the plurality of second cavities hold one article. The plurality of first cavities and the pluralities of the second cavities are arranged in a shape selected from a group consisting of a tablet, spike, circular, rectangular, square and hexagonal shapes. Each one of the plurality of first cavities and each one of the plurality of second cavities holds at-least one article by a vacuum. The plurality of first cavities and the plurality of second cavities comprise an opening or hole in a bottom to provide the vacuum for holding the plurality of articles. A size of the plurality of first cavities is larger than a size of the plurality of articles and a size of the plurality of second cavities is larger than a size of the plurality of articles. The plurality of first cavities and the plurality of second cavities comprise a compressable cushion ring in a bottom. The compressible cushion ring is made up of a material selected from a group consisting of a soft rubber material or a rubber like material.
According to an embodiment herein, the first polymer film die and the second polymer film die is any one of a curtain coating and a slot dye. The first polymer film die and the second polymer film die produce a single layer polymer film or a multilayer polymer film.
According to an embodiment herein, the polymer is melt processed into a molten film of desired thickness.
According to an embodiment herein, the first polymer film is coated on the surface of the plurality of articles in a range of 1%-99%. The second polymer film is coated on the surface of the plurality of articles coated partially with the first polymer film in a range of 1%-99%.
According to an embodiment herein, the first polymer film and the second polymer film comprise one or more additives. The one or more additives are selected from a group consisting of synthetic or natural hydrophilic additives, surfactants, inorganic minerals, biodegradable additives, pigments and water soluble additive. The hydrophilic additives and surfactants are added for increasing a moisture permeability of the first polymer film and the second polymer film.
According to an embodiment herein, the inorganic mineral is selected from a group consisting of talc, calcium carbonate, mica, silica and their derivatives. The inorganic minerals are added for modifying a moisture permeability, reducing a temperature induced expansion of the first polymer film and the second polymer film, and reducing a tackiness of the first polymer film and the second polymer film, and preventing a caking or agglomeration of the plurality of articles coated with the first polymer film and the second polymer film.
According to an embodiment herein, wherein the biodegradable additives are added for adding a biodegradable characteristics to the first polymer film and the second polymer film and for expediting a biodegradation of the first polymer film and the second polymer film. The additives are added to the first polymer film and the second polymer film layer in a range of 0.01%-50% of a combined dry weight of the first polymer film and the second polymer film.
According to an embodiment herein, the desired thickness of the first polymer film and the second polymer film is within a range of 5 microns to 300 microns. The desired temperature of the first molten polymer film and the second molten polymer film is within a range of 50° C. to 500° C. The desired chemical property of the first polymer film and the second polymer film is water vapor transmission rate (WVTR). The WVTR value of the first polymer film and the second polymer film is within a range of 0.01 g/(m2·day) to 20,000 g/(m2·day).
According to an embodiment herein, a method is provided for coating a plurality of articles in a continuous process using a polymer. The method comprises extruding and applying a first coating layer with a first molten polymer film on a plurality of articles held on a plurality of first cavities in a first chill roll for generating a plurality of articles coated partially with the first polymer film. The plurality of articles coated partially with the first polymer film is transferred from the first chill roll to a second chill roll. An uncoated portion of the plurality of articles coated partially with the first polymer film is exposed. A second coating layer of a second molten polymer film is extruded and applied on the plurality of articles held on a plurality of second cavities in the second chill roll for generating a plurality of articles fully coated with the first polymer film and the second polymer film. The plurality of articles is encapsulated between the first coating layer and the second coating layer by sealing the first polymer film and the second polymer film coated on the plurality of articles by melt fusing the second polymer film with the first polymer film on an overlapping area of the first polymer film and the second polymer film. The encapsulated plurality of articles is released over a time period by a diffusion of the encapsulated plurality of articles through the first polymer film or the second polymer film.
According to an embodiment herein, the plurality of articles are held in the plurality of first cavities and in the plurality of second cavities by a vacuum suction adopted at a bottom of the plurality of first cavities and at the plurality of second cavities. A pulling force of the vacuum suction under the plurality of articles is adapted to pull the first polymer film and the second polymer film around the plurality of articles and to adhere the first polymer film and the second polymer film respectively to an opposing surface of the plurality of articles.
According to an embodiment herein, the first polymer film is coated on the surface of the plurality of articles in a range of 1%-99%. The second polymer film is coated on the surface of the plurality of articles coated partially with the first polymer film in a range of 1%-99%.
According to an embodiment herein, the polymer is melt processed into a molten film.
According to an embodiment herein, the first polymer film and the second polymer film comprises one or more additives. The one or more additives are selected from a group consisting of hydrophilic additives, surfactants, inorganic minerals, biodegradable additives, pigments and water soluble additive. The hydrophilic additives or surfactants are added for increasing a moisture permeability of the first polymer film and the second polymer film.
According to an embodiment herein, the inorganic mineral is selected from a group consisting of talc, calcium carbonate, mica, silica and their derivatives. The inorganic minerals are added for reducing a moisture permeability, reducing a temperature induced expansion of the first polymer film and the second polymer film, and reducing a tackiness of the first polymer film and the second polymer film to prevent a caking of the plurality of articles coated with the first polymer film and the second polymer film.
According to an embodiment herein, the biodegradable additives are added for adding a biodegradable characteristic to the first polymer film and the second polymer film and for expediting a biodegradation of the first polymer film and the second polymer film.
According to an embodiment herein, the additives are added to the first polymer film and the second polymer film layer in a range of 0.01%-50% of a combined dry weight of the first polymer film and the second polymer film.
According to an embodiment herein, the desired thickness of the first polymer film and the second polymer film is within a range of 5 microns to 300 microns. The desired temperature of the first polymer film and the second polymer film is within a range of 50° C. to 500° C. The desired chemical property of the first polymer film and the second polymer film is water vapor transmission rate (WVTR). The WVTR value of the first polymer film and the second polymer film is within a range of 0.01 g/(m2·day) to 20,000 g/(m2·day).
According to an embodiment herein, the first chill roll and the second chill roll are rotatable cylindrical drums.
According to an embodiment herein, a method for manufacturing a controlled release fertilizer involves placing the fertilizer granules onto a surface and applying a first layer of polymer onto the exposed surface of the fertilizer granule. Then the uncoated portion of fertilizer is exposed and a second layer of polymer is applied to encapsulate the fertilizer granule between the first polymer layer and the second polymer layer such that the fertilizer granules are releasable over a time by a diffusion through at least one of the first polymer film or the second polymer film.
According to one embodiment herein, the manufacturing process of polymer-coated fertilizers has two main steps. In the first step, the fertilizer granules are partially coated by a first polymer film. Thereafter a second polymer film is applied onto the remaining uncoated fertilizer granule surface thereby encapsulating the fertilizer between the two polymer films.
According to one embodiment herein, an apparatus for coating plurality of articles in a continuous process using polymer melt comprises a first chill roll, a second identical chill roll, a first machine, a second machine, a feeding mechanism and a collection mechanism. The first chill roll comprises a plurality of cavities placed side by side and on the periphery of the first chill roll. The cavities are capable of holding the articles. The second identical chill roll comprises plurality of cavities placed side by side and on the periphery of second chill roll and the cavities of first and second chill rolls are facing each other. The first machine is used for producing a molten film of desired thickness, width and properties. The first polymer film is placed in such a way that the molten polymer film is applied directly onto the articles held in the cavity of the first chill roll. The second machine is adapted for producing a molten film of desired thickness, width and property. The second machine is placed in such a way that the molten film is applied directly onto the articles held in the cavity of the second chill roll. The feeding mechanism is for feeding the articles onto the first chill roll. The collection mechanism is for collecting coated articles from the second chill roll.
According to one embodiment herein, the chill roll is a cylindrical drum capable of rotating. The chill roll has a plurality of cavities on the circumferential surface of the roll. The chill roll has an internal fluid circulation to control a surface temperature of the chill roll. The chill roll has a non stick coating applied on the surface of the roll. The chill roll rotates in a synchronized way so that cavities on the surface of the first chill roll always face the identical cavities on the second chill roll.
The cavity of the chill roll is of any shape and dimension. The cavity of the chill roll is suitable for holding the articles being coated. The shape of the cavity is chosen from a tablet, spike, circular, rectangular, square or hexagonal shape. The cavities are distributed all over the circumference of the first and second chill roll. Further the cavities are of larger dimension than that of the articles being coated. The cavities have soft rubber or rubber like compressable cushion rings in the bottom. The cavity has an opening/hole in the bottom through which a vacuum suction is provided to hold the articles. Further the articles are housed in the cavity and held with the vacuum suction in the cavity. Only one article is housed per cavity.
According to one embodiment herein, the first and second machine used for producing a molten film comprises a polymer extruder and a film die. The polymer extruder is capable of mixing, melting and extruding any commercially available polymer or blend of polymers or additives and creating a homogenous melt. The polymer film die is capable of producing a molten film of desired thickness width and properties from the polymer film melt produced by the extruder. The die is attached to the end of the extruder.
According to one embodiment herein, the film die is a curtain coating die or slot die capable of producing a polymer film using polymer melt. The film die has a single layer or multilayer polymer film extrusion capability. The film die is a commercially available extrusion die capable of producing a molten polymer film of desired thickness, width and properties.
According to one embodiment herein, the method for coating the fertilizers is initiated by feeding the articles on the first chill roll where the articles are held in the cavities by the vacuum suction at the bottom of the cavity. The next step is extruding a first layer of molten polymer film on the articles. The pull of vacuum suction under the said articles pulls the molten polymer layer around the articles to adhere the molten film to the surface of the article to create a partially coated article. Further the partially coated articles are transferred to the cavity of the second chill roll and the uncoated portion of the partially coated particles is exposed. A second layer of molten polymer is extruded and applied on the uncoated portion of the partially coated articles in such a way that second coating layer overlaps the first coating layer and the high temperature of the molten second layer helps in laminating the second layer with the overlapping area of the first layer. Hence the fertilizer panicle or an article is sealed or encapsulated between the first polymer layer and second polymer layer.
According to one embodiment herein, the articles are any commercially available fertilizer granule in any dimension and shape. Further the articles is any one selected from a group consisting of a detergent tablet of any shape and dimension, a biocide tablet of any shape and dimension, a pesticide granule of any shape and dimension, an animal feed of any shape and dimension, and a food particle of any shape and dimension. The articles have even or uneven shape. The articles chosen are water soluble.
According to one embodiment herein, the first and second polymer film is any extrusion grade polymer, capable of producing a film of desired thickness and properties. The desired temperature of the first polymer film and the second polymer film is within a range of 50° C. to 500° C. Further the thickness of the polymer film is in the range of 5-300 micron. The desired chemical property of the first polymer film and the second polymer film is water vapor transmission rate (WVTR). The WVTR value of the first polymer film and the second polymer film is within a range of 0.01 g/(m2·day) to 20,000 g/(m2·day).
According to one embodiment herein, the partially coated articles have the polymer coat covering in the range of 1%-99% of the surface area. Further the second polymer film coating on the partially coated articles have polymer coat covering in the range of 1%-99% of the surface area, of the partially coated article.
According to one embodiment herein, a method of producing the controlled release delivery systems comprises coating a first layer of polymer onto the surface of the article creating partially coated articles. The remaining uncoated portion of the surface area is exposed and applied with a second coating layer. The article is sealed between the first coating layer and the second coating layer by melt fusing the second coating layer with the first coating layer in the overlapping area of the first coating layer and the second coating layer. The article is encapsulated between the first coating layer and the second coating layer. The encapsulated article between the first coating layer and second coating layer is releasable over the time by diffusion through the first coating layer or the second polymer film.
According to one embodiment herein, the first polymer film and second polymer film have multiple film layers forming a single laminated coating layer. The first or second polymer films have additives into the film structure. The additives are selected from the group consisting of hydrophilic additives, inorganic minerals, biodegradable additives and pigments. The hydrophilic additives are added for increasing the moisture permeability of the coating layer. Inorganic minerals such as talc, calcium carbonate, mica or silica or their derivatives are added for reducing moisture permeability, reducing a temperature induced expansion of the polymer coating and reducing a tackiness of the coating to prevent a caking of the coated articles. The biodegradation additives are added for expediting the biodegradation of the coating layer. The pigments are added for providing a color to the coating films. The amount of additives added to the polymer layer is within a range of 0.0%-50% of the combined dry weight of the first or second coating layer.
According to one embodiment herein, the first or second polymer film has multiple film layers laminated to form a single coating layer. Further the multilayer coated films are of different thickness or different additives or have additive loading levels.
According to one embodiment herein, cheap polymers are used to coat the fertilizer granules. Further the dry fertilizer granules in any shape, form are coated, thereby eliminating the energy cost of granulating the fertilizer. The method of coating the fertilizer granules does not involve any solvent or catalyst. The method gives a uniform coating on the fertilizer granules. Furthermore the method allows an application of multiple polymers simultaneously thereby allowing the manufacturer to produce a fertilizer coated with multiple polymer layers. The method has ability to apply a coating film with desired weight in a single time thereby saving time, space and energy to produce coated products.
According to one embodiment herein, the first chill roll 103a and the second chill roll 103b is replaced with a perforated steel belt with vacuum.
According to one embodiment herein, the cavity 102a is made of electrically conductive metal while the first chill roll 103a and the second chill roll 103b have a coating of electrically neutral material. According to one embodiment herein, the charged fertilizer granule are attracted towards the cavity 102a and the fertilize granules 101 are held in its place without the use of vacuum suction 104a, when electrically charged fertilizer granules 101 are fed onto the chill roll 103a.
According to one embodiment herein, the extruder 106a or extruder 106b have co-extrusion facility with an ability to extrude multiple layers of polymers.
According to one embodiment herein the extruders 106a and 106b are replaced with a suitable coating devices such as, but not limited to, spray coating, curtain coating, powder coating, rod coating, thermal lamination coating, or UV lamination coating devices.
According to one embodiment herein, the fertilizer granule 101 is any one of rectangular, tablet, hemispherical, split pea, spike, shapes or any shape in which the fertilizers are available commercially.
According to one embodiment herein, the cavity 101 is rectangular, tablet, square, hemispherical, spike, or such shapes.
According to one embodiment herein, the steel belt is used to eliminate the use of first chill roll. In yet another embodiment of the invention a series of soft cushion protective rollers can be used on the surface of the chill roll gently pressing the granules onto the cylinder so that the granules do not fly off due to a centrifugal force of the rotating chill roll. Alternatively an air cushion is used to generate air jets or electrostatic charge on the granules to prevent a flying off of the granules from the rotating chill roll.
According to one embodiment herein, the layer of polymer contains various types of additives to enhance the properties of polymer such as fertilizer release rate through the polymer layer, biodegradation of the polymer layer, UV resistance of the polymer layer, resistance of temperature induced fertilizer release through the layer using talc and other minerals.
According to one embodiment herein, the surface of the coated granules comprises of water absorption chemicals such as superabsorbent.
According to one embodiment herein, the surface of the chemicals contains paper particles or cellulose particles attached to the surface of the coated granules. These cellulose particles are used to carry pesticides by absorbing the pesticides onto the cellulose particles attached to the coated surface.
According to one embodiment herein, the polymer film comprises of many polymer layers co-extruded as a single layer of polymer.
The foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the appended claims.
Although the embodiments herein are described with various specific embodiments, it will be obvious for a person skilled in the art to practice the invention with modifications. However, all such modifications are deemed to be within the scope of the claims. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the embodiments described herein and all the statements of the scope of the embodiments which as a matter of language fall there between.
The present application claims the priority of the U.S. Provisional Patent Application with Ser. No. 61/691,051 filed on Aug. 20, 2012, and the U.S. Provisional Patent Application with Ser. No. 61/766,041 filed on Feb. 18, 2013. The contents of all the above mentioned documents are incorporated entirely by reference herein.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US13/55486 | 8/17/2013 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61691051 | Aug 2012 | US | |
| 61766041 | Feb 2013 | US |
