Processing, dyeing, and treating of materials, such as fabric and/or a yarn, with a supercritical fluid.
Traditional dyeing of materials relies on a large quantity of water, which can be detrimental to the fresh water supply and also result in undesired chemicals entering into the wastewater stream. As a result, use of a supercritical fluid has been explored as an alternative to the traditional water dye processes. However, a number of challenges have been encountered with the use of a supercritical fluid (“SCF”), such as carbon dioxide (“CO2”), in a dyeing process. For example, the interaction of dye materials with a SCF, including the solubility, introduction, dispersion, circulation, deposition, and characterization of the interaction, have all posed problems to industrial-scale implementation of dyeing with a SCF. U.S. Pat. No. 6,261,326 (“326 patent”) to Hendrix et. al, filed Jan. 13, 2000 and assigned to North Carolina State University attempts to address previously explored solutions to the SCF and dye material interactions. The '326 patent attempts to remedy the complications of the interaction with a separate preparation vessel for introducing the dye to a SCF and then transferring the solution of dye and SCF into a textile treatment system to dye a material. In the example of the '326 patent, the dye is introduced into the vessel containing the material to be dyed in conjunction with the SCF, which can increase the complexity of the process and componentry of the system.
Methods and systems are directed to the use of a supercritical fluid for performing a dyeing of a material such that a dye, which may be a colorant or other material finish, from a first material is used to dye a second material within a common vessel. A dye-free supercritical fluid is passed through a first material in a pressurized vessel. The supercritical fluid transports dye from the first material to at least a second material causing a dye profile of the second material to change as the dye perfuse the second material. The first material may be in contact or physically separate from the second material within the pressure vessel. Also, the dye of the first material is integral with the first material at the start of the dyeing process, in an exemplary aspect.
The present invention is described in detail herein with reference to the attached drawing figures, wherein:
Methods are directed to the use of a supercritical fluid for performing a dyeing of a material such that dye, which may be a colorant or other material finish, from a first material is used to dye a second material within a common vessel. A supercritical fluid is passed through a first material in a pressurized vessel. The supercritical fluid transports dye from the first material to at least a second material causing a dye profile of the second material to change as the dye perfuse the second material. The first material may be in contact or physically separate from the second material within the pressure vessel. Also, the dye of the first material is integral with the first material at the start of the dyeing process in an exemplary aspect.
Methods are also directed to dyeing a material by positioning at least a first sacrificial material with a first dye profile and a target material with a second dye profile in a common pressure vessel such that the first sacrificial material is not in contact with the target material. The method continues with introducing carbon dioxide within the pressure vessel such that the carbon dioxide achieves a supercritical fluid state while in the pressure vessel. Supercritical fluid carbon dioxide is used to perfuse the target material with dye from the first sacrificial material dye profile, wherein the dye from the first sacrificial material is integral with the first sacrificial material prior to introducing the carbon dioxide. Additional aspects further contemplate positioning a second sacrificial material with a third dye profile in the pressure vessel prior to achieving the supercritical fluid state of the carbon dioxide and then perfusing the target material with dye from the second sacrificial material dye profile while perfusing the target material with dye from the first sacrificial material dye profile.
An additional exemplary method contemplated is directed dyeing a material by positioning at least a first sacrificial material with a first dye profile and a target material with a second dye profile in a common pressure vessel such that the first sacrificial material is in contact with the target material. The method includes introducing carbon dioxide within the pressure vessel such that the carbon dioxide achieves a supercritical fluid state while in the pressure vessel. Supercritical fluid carbon dioxide is used to perfuse the target material with dye from the first sacrificial material dye profile. Additional aspects contemplate positioning a second sacrificial material with a third dye profile in the pressure vessel prior to achieving the SCF state and perfusing the target material with dye from the second sacrificial material dye profile while perfusing the target material with dye from the first sacrificial material dye profile.
Supercritical fluid (“SCF”) carbon dioxide (“CO2”) is a fluid state of CO2 that exhibits characteristics of both a gas and a liquid. SCF CO2 has liquid-like densities and gas-like low viscosities and diffusion properties. The liquid-like densities of SCF allows for SCF CO2 to dissolve dye material and chemistries for eventual dyeing of a material. The gas-like viscosity and diffusion properties can allow for a faster dyeing time and faster dispersion of dye material than in a traditional water-based process, for example.
While examples herein refer specifically to SCF CO2, it is contemplated that additional or alternative compositions may be used at or near a supercritical fluid phase. Therefore, while specific reference will be made to CO2 as a composition herein, it is contemplated that aspects hereof are applicable with alternative compositions and appropriate critical point values for achieving a SCF phase.
The use of SCF CO2 in a dyeing process may be achieved using commercially available machines, such as a machine offered by DyeCoo Textile Systems BV of the Netherlands (“DyeCoo”). A process implemented in a traditional system includes placing an undyed material that is intended to be dyed into a vessel capable of being pressurized and heated to achieve a SCF CO2. A powdered dyestuff that is not integrally associated with a textile (e.g., loose powder) is maintained in a holding container. The dyestuff holding container is placed in the vessel with the undyed material such that the dyestuff is not contacting the undyed material prior to pressurizing the vessel. For example, the holding container physically separates the dyestuff from the undyed material. The vessel is pressurized and thermal energy is applied to bring CO2 to a SCF (or near SCF) state, which causes the dyestuff to solubilize in the SCF CO2. In a traditional system, the dyestuff is transported from the holding container to the undyed material by the SCF CO2. The dyestuff is then diffused through the undyed material causing a dyeing of the undyed material until the SCF CO2 phase is ceased.
Aspects herein relate to a concept of dye equilibrium as a manner of controlling a dye profile that results on a material. For example, if a first material has a dye profile that may be described as a red coloration and a second material has a dye profile that may be described by an absence of coloration (e.g., bleached or white), the concept of equilibrium dyeing with SCF CO2 results in an attempted equalization between the two dye profiles such that at least some of the dyestuff forming the first dye profile is transferred from the first material to the second material. An application of this process includes using a sacrificial material having dyestuff contained thereon and/or therein (e.g., a dyed first material) that is used as a carrier for applying a specific dyestuff to a second material that is intended to be dyed by the dyestuff of the sacrificial material. For example, a first material and a second material may each have different resulting dye profiles from each other after a SCF CO2 process is applied while also having a different dye profile from their respective initial dye profiles (e.g., first dye profile and second dye profile). This lack of true equilibrium may be desired. For example, if the first material is the sacrificial material that is merely intended to be a dye carrier, the process may be carried out until the second material achieves a desired dye profile, regardless of the resulting dye profile for the first material, in an exemplary aspect.
Another example of a dyeing process using SCF CO2 may be referred to as an additive dyeing process. An example to aid in illustrating the additive dyeing process includes the first material having a dye profile that exhibits red coloration and the second material having a second dye profile that exhibits blue coloration. The SCF CO2 is effective to result in dye profiles on the first material and the second material (and/or a third material) that exhibit purple coloration (e.g., red+blue=purple).
As before, it is contemplated that the first and second materials may achieve a common dye profile when the equilibrium dye process is allowed to mature. In additional aspects, it is contemplated that the first material and the second material result in different dye profiles from each other, but the resulting dye profiles are also different from the initial dye profile for each respective material. Further, it is contemplated that the first material may be a sacrificial dye transfer material while the second material is the material for which a target dye profile is desired. Therefore, the SCF CO2 dye process may be performed until the second material achieves the desired dye profile regardless of the resulting dye profile of the first material. Further yet, it is contemplated that a first sacrificial material dye carrier having a first dye profile (e.g., red) and a second sacrificial dye carrier having a second dye profile (e.g., blue) may be placed into the system to cause a desired dye profile (e.g., purple) on a third material, in an exemplary aspect. As can be appreciated, any combination and number of materials, dye profiles, and other contemplated variables (e.g., time, SCF CO2 volume, temperature, pressure, material composition, and material type) may be altered to achieve results contemplated herein.
Aspects herein contemplate dyeing (e.g., treating with material finishes) of one or more materials using SCF CO2. The concept of two or more materials used in conjunction with each other is contemplated in aspects hereof. Further, the use of one or more materials having integral dyestuff that are not intended for traditional post-processing utilization (e.g., apparel manufacturing, shoe manufacturing, carpeting, upholstery), which may be referred to as sacrificial material or as dye carriers, are contemplated as being introduced in the system. Further, it is contemplated that any dye profile may be used. Any combination of dye profiles may be used in conjunction with one another to achieve any desired dye profile in one or more materials. Additional features and process variable for disclosed methods and systems will be provided herein.
Achieving a desired dye profile on a material may be influenced by a number of factors. For example, if there are 50 kg of a first material (e.g., spooled or rolled material) and 100 kg of a second material, the resulting dye profile per weight of the first material may be expressed as ⅓ the original color/intensity/saturation of the first dye profile when the second material original dye profile is absent of dye. Alternatively, with the same proportions of material but the original second dye profile having a comparable saturation/intensity as the first dye profile, but with a different coloration, the first dye profile may be expressed as ⅓X+⅓Y where X is the original first dye profile and Y is the original second dye profile (i.e. weight of the first material/weight of all materials). From the second material perspective using the two previous examples, the resulting dye profiles may be (⅔X)/2 for the first example and (⅔ X+⅔ Y)/2 (i.e. [weight of the first material/weight of all materials]*[weight of the first material/weight of the second material]). The previous examples are for illustration purposes only as it is contemplated that a number of additional factors are also relevant, such as yardage per kilogram, material composition, dye process length, temperature, pressure, time, material porosity, material density, winding tension of the material, and other variables that may be represented by an empirical value(s). However, the preceding is intended to provide an understanding of the intended equilibrium dyeing process to supplement the aspects provided herein. As such, the provided examples and values are not limiting but merely exemplary in nature.
Referring now to
The second material 102 has a first surface 120, a second surface 122, and a plurality of dye material 108. The dye material 108, which may be a composition/mixture of dyestuffs, is depicted as granular elements for discussion purposes; however, in actuality the dye material 108 may not be individually identifiable at the macro level from the underlying substrate of a material. Also, as will be discussed hereinafter, it is contemplated that the dyestuff may be integral with the material. Integral dyestuff is dyestuff that is chemically or physically bonded with the material. Integral dyestuff is compared to non-integral dyestuff, which is dyestuff that is not chemically or physically coupled with a material. An example of a non-integral dyestuff includes dry powdered dyestuff sprinkled and brushed on the surface of a material such that the dyestuff is removed with minimal mechanical effort.
At
With respect to
The spooled material may be a continuous yarn-like material that is effective for use in weaving, knitting, braiding, crocheting, sewing, embroidering, and the like. Non-limiting examples of spooled material include yarn, thread, rope, ribbon, filament, and cord. It is contemplated that the spooled material may be wound about a spool (e.g., conical or cylindrical) or the spooled material may be wound about itself without a secondary support structure helping form the resulting wound shape. The spooled material may be organic or synthetic in nature. The spooled material may be a plurality of individual collections of material or a singular collection of material.
In
As such,
Referring now to
At
With respect to
The second material 1104 has a first surface 1124 and a second surface 1126. The second material also is depicted as having a second dye profile with dye material 1114. The dye material 1114 may be dyestuff transferred by the SCF CO2 having passed through the first material 1102 and/or it is dyestuff associated with the second material 1104 in a previous operation, in an exemplary aspect.
As such,
Further, as will be provided herein, aspects contemplate a dyestuff integral to a material. A dyestuff is integral to a material when it is physically or chemically bonded with the material, in an example. In another example, dyestuff is integral to the material when the dyestuff is homogenized on the material. The homogenization of dyestuff is in contrast to a material on which dyestuff is applied in a non-uniform manner, such as if a dyestuff is merely sprinkled or otherwise loosely applied to the material. An example of integral dyestuff with a material is when dyestuff is embedded and maintained within the fibers of a material, such as when dyestuff perfuses a material.
The term “perfuse,” as used herein, is to coat, permeate, and/or diffuse surface finishes, such as dyestuff over and/or throughout a material. The perfusing of a material with dyestuff occurs in a pressure vessel, such as an autoclave, as is known in the art. Further, the SCF and dyestuff dissolved in the SCF may be circulated within the pressure vessel with a circulation pump, as is also known in the art. The circulation of SCF within the pressure vessel by a pump causes the SCF to pass through and around a material within the pressure vessel to cause dissolved dyestuff to perfuse the material. Stated differently, when a target material is perfused with SCF CO2 having dyestuff (e.g., finish material) dissolved therein, the dyestuff is deposited on one or more portions of the target material. For example, a polyester material, when exposed to the conditions suitable for forming SCF CO2, may “open” up allowing for portions of the dyestuff to remain embedded with the polyester fibers forming the polyester material. Therefore, adjusting the heat, pressure, circulation flow, and time affects the SCF, the dyestuff, and the target material. The variables all taken in combination, when the SCF CO2 perfuses the target material, a deposit of dyestuff throughout the material may occur.
In the example depicted in
As depicted in
While the spooled material 207 and the second material 209 are depicted on a common material holding element 204, it is contemplated that the spooled material 207 is on a first holding element and the second material 209 is on a second holding element that is different from the first holding element, in an exemplary aspect.
While only two materials are depicted in
In the example depicted in
As depicted in
While the first material 1207 and the second material 1209 are depicted as having a similar volume of material, it is contemplated that the first material 1207 may have a substantially greater volume of material than the second material 1209, which may serve as a sacrificial material in an exemplary aspect. Further, while the first material 1207 and the second material 1209 are depicted on a common holding element, it is contemplated that the first material 1207 is on a first holding element and the second material 1209 is on a second holding element that is different from the first holding element, in an exemplary aspect.
While only two materials are depicted in
As has been illustrated in
The SCF CO2 allows the polyester to be dyed with a modified dispersed dyestuff. This occurs because the SCF CO2 and/or the conditions causing the SCF state of CO2 result in the polyester fibers of the materials to swell, which allows the dyestuff to diffuse and penetrate the pore and capillary structures of the polyester fibers. It is contemplated that reactive dye may similarly be used when one or more of the materials is cellulosic in composition. In an exemplary aspect, the first material 1206 and the second material 1208 are formed from a common material type such that dyestuff is effective for dyeing both materials. In an alternative aspect, such as when one of the materials is sacrificial in nature as a dye carrier, the dyestuff may have a lower affinity for the sacrificial material than the target material, which could increase the speed of SCF CO2 dyeing. An example may include the first material being cellulosic in nature and the second material being a polyester material and the dyestuff associated with the first material being a dispersed dye type such that the dyestuff has a greater affinity for the polyester material (in this example) over the first material. In this example, a reduced dyeing time may be experienced to achieve a desired dye profile of the second material.
At a block 304, the pressure vessel may be pressurized. In an exemplary aspect, the materials are loaded into the pressure vessel and then the pressure vessel is sealed and pressurized. In order to maintain inserted CO2 in the SCF phase, the pressure, in an exemplary aspect, is raised above the critical point (e.g., 73.87 bar).
Regardless of how the pressure vessel is brought to pressure, at a block 306, SCF CO2 is introduced into the pressure vessel. This SCF CO2 may be introduced by transitioning CO2 maintained in the pressure vessel from a first state (i.e., liquid, gas, or solid) into a SCF state. As know, the state change may be accomplished by achieving a pressure and/or temperature sufficient for a SCF phase change. It is contemplated that one or more heating elements are engaged to raise the internal temperature of the pressure vessel to a sufficient temperature (e.g., 304 K, 30.85 C). One or more heating elements may also heat the CO2 as (or before) it is introduced into the pressure vessel, in an exemplary aspect.
At a block 308, the SCF CO2 is passed through each of the plurality of spooled materials and the second material. While the SCF CO2 passes through the materials, which may have different dye profiles, dyestuffs is transferred between the materials and perfuse the material(s). In an exemplary aspect, the dyestuff is dissolved in the SCF CO2 such that the SCF CO2 serves as a solvent and carrier for the dyestuff. Further, because of the temperature and pressure of the SCF CO2, the materials may alter (e.g., expand, open, swell), temporarily, to be more receptive to dyeing by the dyestuff.
It is contemplated that the passing of SCF CO2 is a cycle in which the SCF CO2 is passed through the materials multiple times, such as in a closed system with a circulation pump, in an exemplary aspect. It is this circulation that may help achieve the dyeing. In an aspect, the SCF is circulated through the materials for a period of time (e.g., 60 minutes, 90 minutes, 120 minutes, 180, minutes, 240 minutes) and then the SCF CO2 is allowed to change state (e.g., to a liquid CO2) by dropping temperature and/or pressure. After changing state of the CO2 from SCF state, the dyestuff is no longer soluble in the non-SCF CO2, in an exemplary aspect. For example, dyestuff may be soluble in SCF CO2, but when the CO2 transitions to liquid CO2, the dyestuff is no longer soluble in the liquid CO2.
At a block 310, the plurality of spooled materials and the second material are extracted from the pressure vessel. In an exemplary aspect, the pressure within the pressure vessel is reduced to near atmospheric pressure and the CO2 is recaptured from the pressure vessel for potential reuse in subsequent dyeing operations. In an example, a securing apparatus securing the materials may be moved out of the vessel after a desired dye profile is achieved for one or more of the materials.
While specific steps are discussed and depicted in
As previously discussed, it is contemplated that the material finish of the sacrificial material may be a colorant (e.g., dyestuff), a hydrophilic finish, a hydrophobic finish, and/or an anti-microbial finish. As will be illustrated in
At a block 404, carbon dioxide is introduced into the pressure vessel. The CO2 may be in a liquid or gas state when it is introduced. Further, it is contemplated that the pressure vessel is enclosed at the time of the CO2 introduction to maintain the CO2 within the pressure vessel. The pressure vessel may be at atmospheric pressure when the CO2 is introduced. Alternatively, the pressure vessel may be above or below atmospheric pressure when the CO2 is introduced.
At a block 406, the pressure vessel is pressurized allowing the introduced CO2 to achieve a SCF (or near) state. Additionally, it is contemplated that thermal energy is applied to (or within) the pressure vessel to aid in achieving the SCF state of the CO2. As discussed hereinabove, the state diagram of
At a block 408, the plurality of spooled materials are perfused with at least a portion of the material finish from the sacrificial material. The material finish is transferred to the plurality of spooled materials by way of the SCF CO2. As discussed previously, the SCF CO2 serves as a transportation mechanism for the material finish from the sacrificial material to the plurality of spooled materials. This may be assisted by circulating, such as by a circulation pump, the SCF within the pressure vessel so that it perfuses both the sacrificial material and the plurality of spooled materials. It is contemplated that the material finish may dissolve, at least partially, within the SCF allowing for their release from being bound with the sacrificial material to being deposited on/within the plurality of spooled materials. To ensure consistent application of the material finish to the plurality of spooled materials, the material finish may be integral to the sacrificial material, which ensures the intended amount of material finish is introduced within the pressure vessel. The transfer of the material finish may continue until a sufficient amount of the material finish perfuses the spooled materials.
While specific reference in
While a first and a second sacrificial material are discussed, any number of sacrificial materials may be provided. Further, it is contemplated that a quantity of the first sacrificial material and a quantity of the second sacrificial material are different depending on a desired amount of each material finish desired to be applied to the spooled material. Further, it is contemplated that the sacrificial materials will also maintain a portion of the material finish from the other materials within the pressure vessel. Therefore, it is contemplated the volume of all materials, include sacrificial, are considered when determining a quantity of surface finish to be inserted in the pressure vessel.
At a block 504, the pressure vessel is pressurized such that CO2 within the pressure vessel achieves a SCF state therein. The SCF is then effective to administer the material finish of the first sacrificial material and the second material finish of the second material to the spooled material, as depicted in a block 506.
While specific reference in
In this illustrated example, the last turn of the first material 1206 exposes a surface that is in direct contact with a surface of the first turn of the second material 1208. Stated differently, the depicted series rolling of winding 1300 allows for a limited, but available, direct contact between the first material 1206 and the second material 1208. This direct contact can be distinguished over alternative aspects in which a dye carrier or the dyestuff is physically separate from the material to be dyed. As such, the direct contact between the materials to be dyed and having the dyestuff may reduce dyeing time and reduce potential cleaning and maintenance times, in an exemplary aspect.
While only two materials are depicted in
At a block 512, the pressure vessel may be pressurized. In an exemplary aspect, the materials are loaded into the pressure vessel and then the pressure vessel is sealed and pressurized. In order to maintain inserted CO2 in the SCF phase, the pressure, in an exemplary aspect, is raised above the critical point (e.g., 73.87 bar).
Regardless of how the pressure vessel is brought to pressure, at a block 514, CO2 is introduced (or recirculated) into the pressure vessel. This CO2 may be introduced by transitioning CO2 maintained in the pressure vessel from a first state (i.e., liquid, gas, or solid) into a SCF state. As know, the state change may be accomplished by achieving a pressure and/or temperature sufficient for a SCF phase change. It is contemplated that one or more heating elements are engaged to raise the internal temperature of the pressure vessel to a sufficient temperature (e.g., 304 K, 30.85 C). One or more heating elements may also (or alternatively) heat the CO2 as (or before) it is introduced into the pressure vessel, in an exemplary aspect. The introduction of CO2 may occur during pressurization, prior to pressurization, and/or subsequent to pressurization.
At a block 516, the SCF CO2 is passed through the first material and the second material. In an exemplary aspect, the SCF CO2 is pumped into a beam about which one or more of the materials are wound. The SCF CO2 is expelled from the beam into the materials. While the SCF CO2 passes through the materials, which may have different dye profiles, dyestuffs is transferred between the materials and perfuse the material(s). In an exemplary aspect, the dyestuff is dissolved in the SCF CO2 such that the SCF CO2 serves as a solvent and carrier for the dyestuff. Further, because of the temperature and pressure of the SCF CO2, the materials may alter (e.g., expand, open, swell), temporarily, to be more receptive to dyeing by the dyestuff.
It is contemplated that the passing of SCF CO2 is a cycle in which the SCF CO2 is passed through the materials multiple times, such as in a closed system with a circulation pump, in an exemplary aspect. It is this circulation that may help achieve the dyeing. In an aspect, the SCF is circulated through the materials for a period of time (e.g., 60 minutes, 90 minutes, 120 minutes, 180, minutes, 240 minutes) and then the SCF CO2 is allowed to change state (e.g., to a liquid CO2) by dropping temperature and/or pressure. After changing state of the CO2 from SCF state, the dyestuff is no longer soluble in the non-SCF CO2, in an exemplary aspect. For example, dyestuff may be soluble in SCF CO2, but when the CO2 transitions to liquid or gas CO2, the dyestuff may no longer be soluble in the liquid or gas CO2. It is further contemplated that the CO2 is circulated internally (e.g., passed through a material holder or a beam) and/or the CO2 is circulated as a recapture process to reduce lost CO2 during phase changes (e.g., depressurization).
At a block 518, the first material and the second material are extracted from the pressure vessel. In an exemplary aspect, the pressure within the pressure vessel is reduced to near atmospheric pressure and the CO2 is recaptured from the pressure vessel for potential reuse in subsequent dyeing operations. In an example, a beam having the materials wound thereon may be moved out of the vessel after a desired dye profile is achieved for one or more of the materials.
While specific steps are discussed and depicted in
In the alternative, the second starting position of
In both the first and the second starting positions, the multiple materials are wound, in one manner or another, about one or more holding devices for positioning in a common pressure vessel, as depicted at a block 1406.
At a block 1408 the pressure vessel is pressurized to at least 73.87 bar. This pressurization may be accomplished by injection of atmospheric air and/or CO2 until the internal pressure of the pressure vessel reaches the desired pressure, such as at least the critical point pressure of CO2. For example, CO2 is inserted into the pressure vessel with a pump until the appropriate pressure is achieved within the pressure vessel.
At a block 1410, SCF CO2 is passed through the first material and the second material to cause a change in a dye profile for at least one of the first material or the second material. The dye transfer may be continued until the dyestuffs perfuse the materials(s) sufficiently to achieve a desired dye profile. An internal recirculating pump is contemplated as being effective to cycle the SCF CO2 through the beam and wound materials multiple times to achieve the equilibrium dyeing, in an exemplary aspect. This internal recirculating pump may be adjusted to achieve a desired flow rate of the SCF CO2. The flow rate provided by the internal recirculating pump may be affected by the amount of material, the density of material, the permeability of the material, and the like.
At a block 1412, the first material and the second material are extracted from the pressure vessel such that color profiles (e.g., dye profile) of the materials are different relative to the color profiles of the materials as existed at blocks 1402, 1403, or 1404. Stated differently, upon completion of the SCF CO2 passing through the materials, the dye profiles of at least one of the materials changes to reflect that it has been dyed by SCF CO2.
While specific reference in
The process of using SCF CO2 in a material dying or finishing application relies on manipulation of multiple variables. The variables include time, pressure, temperature, quantity of CO2, and flow rate of the CO2. Further, there are multiple stages in the process in which one or more of the variable may be manipulated to achieve a different result. Three of those stages include the pressurizing stage, perfusing stage, and the depressurizing stage. In an exemplary scenario, CO2 is introduced into a sealed pressure vessel with the temperature and the pressure increasing such that the CO2 is elevated to at least the critical point of 304 K and 73.87 bar. In this traditional process, the second stage of perfusing the material-to-be-finished occurs. A flow rate may be set and maintained and a time is established for the second stage. Finally, at the third stage in a traditional process, the flow rate is stopped, the application of thermal energy ceases, and the pressure is reduced, all substantially simultaneously to transition the CO2 from SCF to gas.
Improvements over a traditional process are able to be realized by adjusting the different variable. In particular, adjusting the sequence and timing of the variable changes during a stage provides better results. For example, a traditional process may cause the material finish (e.g., dyestuff) to coat the inner surfaces of the pressure vessel. The coating of the pressure vessel is inefficient and undesired as it represents material finish that was not perfused through the intended material and requires subsequent cleaning to ensure the material finish is not perfused into a subsequent material for which it is not intended. Stopping the flow rate at the initiation of the third stage causes the CO2 and the material finishes dissolved therein to become stagnate within the pressure vessel. As CO2 transitions from SCF to gas, the material finish in this stagnant environment may not find a suitable host to attach as the material finish comes out of solution with the CO2 at the phase change. Therefore, the pressure vessel itself may become the target of the surface finish as opposed to the target material. Manipulation of the variables may allow for the material finish to favor adhering/bonding/coating the intended target material as opposed to the pressure vessel itself.
In the third stage, it is contemplated that the flow rate is maintained or not ceased until the CO2 changes from the SCF to gas state. For example, if the pressure within the pressure vessel is operating at 100 bar during the perfusing stage, the CO2 may stay in SCF state in the third stage until the pressure is reduced below 73.87 bar. As a result, when the second stage is completed, instead of stopping the flow of CO2 or significantly reducing the flow rate of CO2 within the pressure vessel, the flow rate is maintained through the third stage. In an additional concept, the flow rate of the CO2 is maintained until the pressure reduces below 73.87 bar.
At least two different scenarios for the third stage are contemplated. The first scenario is a sequence where the third stage of the process initiates at the reduction in temperature of the CO2. For example, the second stage may be operating at 320 K, in an exemplary aspect, at the completion of the second stage, the temperature is allowed to decline from the operating temperature of 320 K. While a traditionally process may also stop the flow of CO2 within the pressure as the temperature begins to decline, it is contemplated that instead the flow rate is maintained, at some level, until at least the temperature falls below the critical temperature of CO2, 304 K. In this example, the CO2 may remain in the SCF until the temperature falls below 304 K; therefore, the flow rate is maintained to move the CO2 and dissolved material finishes therein around the target material. In this first scenario, the pressure may be maintained at the operating pressure (or above 73.87 bar) until the CO2 changes from SCF to another state (e.g., liquid if above 73.87 bar). Alternatively, the pressure may also be allowed to drop at the commencement of the third stage, but the flow is maintained until at least the CO2 changes to a different state.
The second scenario, while similar to the first, relies on the third stage being initiated by a decline in pressure. For example, if the operating pressure within the pressure vessel to perfuse the material is 100 bar, the third stage is initiated when the pressure drops. While a traditional process may cease the flow rate of the CO2 at this point, it is contemplated that instead the flow rate is maintained or not ceased simultaneously. Instead, at the third stage, the co2 is subject to flow until the pressure drops below at least 73.87 bar to ensure circulation of the CO2 having dissolved surface finishes contained therein the entirety of time the CO2 is at a SCF state. The temperature may also be dropped simultaneously with the pressure decline or it may be maintained until a certain pressure is achieved.
In an exemplary aspect, the third stage initiates with the pressure dropping and the temperature dropping toward the CO2 critical point, but the flow rate of the CO2 is maintained, at least in part, until the CO2 has transitioned from the SCF state. While specific temperatures and pressures are listed, it is contemplated that any temperature or pressure may be used. Further, instead of relying on the CO2 achieving a particular temperature or pressure, a time may be used for when to reduce or cease the CO2 flow rate, in an exemplary aspect.
Manipulation of the variable is not limited to the third stage. It is contemplated that a higher equilibrium saturation of surface finish may be achieved by adjusting the variables in the first and second stages. For example, the flow rate may begin before the CO2 transitions from a first state (e.g., gas or liquid) to a SCF state. It is contemplated that as CO2 transitions into a SCF state, the material finish that is to-be-dissolved in the SCF is exposed to a non-stagnate pool of CO2 allowing an for an equilibrium of solution to occur sooner, in an exemplary aspect. Similarly, it is contemplated that the thermal energy is applied to the pressure vessel internal volume before the introduction of CO2 and/or before the pressurization of the CO2 begins. As the transfer of thermal energy may slow the process because of thermal mass of the pressure vessel, it is contemplated that the addition of the thermal energy occurs, in an exemplary aspect prior to the application of pressure.
As provided herein, a sacrificial material may be used as a transport vehicle to introduce the material finish (e.g., dyestuff) intended to be perfused through the target material. In an exemplary aspect, the material finish is soluble in CO2 SCF allowing the SCF to dissolve the material finish to perfuse the material. SCF is non-polar; therefore, the chemistry of material finishes that are operable in a CO2 SCF processing system are chemistries that dissolve in a non-polar solution. For example, dyestuff suitable for dying a polyester material may dissolve in CO2 SCF, but not dissolve in water. Further, the dyestuff suitable for dyeing polyester may not have the appropriate chemistry to bond with a different material, such as an organic material like cotton. Therefore, it is contemplated that an organic material (e.g., cotton) is soaked in the material finish to be applied to a polyester material. The soaked organic material serves as the carrier material into the pressure vessel. When the CO2 SCF process is performed, the material finish is dissolved by the CO2 SCF and perfused through the polyester material. The organic material, which would require a different chemistry for material finish bonding, does not maintain the material finish and therefore the intended amounts of the material finish are available for the perfusing the target material.
In an example, a cotton material is used as a transport vehicle for dye stuff to dye a polyester material. In this example, 150 kg of polyester is desired to be dyed in a CO2 SCF process. If 1% of total target weight represents the amount of dye stuff needed to achieve a desired coloration. Then 1.5 kg of dye stuff is needed to be perfused into the polyester to achieve the desired coloration. The 1.5 kg of dye stuff may be diluted in an aqueous solution with 8.5 kg of water. Therefore, the dye stuff in solution is 10 kg. Because the dye stuff has a chemistry suitable for dissolving in a non-polar CO2 SCF, the dyestuff is merely suspended in the water as opposed to dissolved in the water, in this exemplary aspect. Cotton is highly absorbent. For example, cotton may be able to absorb up to 25 times its weight. Therefore, in order to absorb the 10 kg of dye stuff solution, a 0.4 kg portion of cotton (10/25=0.4) may serve as the carrier. However, it is contemplated that a larger portion of cotton may be used to achieve the transport of the dye stuff solution. In an exemplary aspect, a 30% absorption by weight of the cotton is contemplated. In the example above using 30% by weight absorption, the cotton is 33.3 kg to carry the 10 kg of dye stuff solution. It should be understood that the solution amount, dye stuff amount, and absorption amount may be adjusted to achieve the desired amount of material to be included in the pressure vessel for the dyeing process.
As applied to specific material finishing examples, it is contemplated that a material having different bonding chemistry needs than the target material (e.g., cotton to polyester) is submerged or otherwise soaked with a material finish solution. The soaked carrier material is then placed in the pressure vessel. The soaked carrier may be placed on a support structure or wrapped around the target material. The process of CO2 SCF finishing may be initiated. The CO2 SCF passes around and through the carrier material and dissolves the material finish for perfusing the target material with the material finish. At the completion of the material finish application, the CO2 is transitioned from the SCF state to a gaseous state (in an exemplary aspect). The material finish, which does not have a bonding chemistry for the carrier material, is attracted to and maintained by the target material, in an exemplary aspect. Therefore, at the completion of the finish process, the material finish is applied to the target material and the carrier material is void of appreciable quantities of the material finish, in an exemplary aspect.
It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.
While specific elements and steps are discussed in connection to one another, it is understood that any element and/or steps provided herein is contemplated as being combinable with any other elements and/or steps regardless of explicit provision of the same while still being within the scope provided herein. Since many possible embodiments may be made of the disclosure without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.
This application claims the benefit of U.S. Provisional Applications: 1) U.S. Provisional Patent Application 62/119,015, entitled Dyeing of Spooled Material with a Supercritical Fluid, filed on Feb. 20, 2015, 2) U.S. Provisional Patent Application 62/119,010 entitled Equilibrium Dyeing of Rolled Material with a Supercritical Fluid, filed on Feb. 20, 2015, and 3) U.S. Provisional Patent Application 62/296,987, entitled Supercritical Fluid Rolled or Spooled Material Finishing, filed on Feb. 18, 2016. The entireties of the aforementioned applications are incorporated by reference herein.
Number | Name | Date | Kind |
---|---|---|---|
5298032 | Schlenker et al. | Mar 1994 | A |
5340614 | Perman et al. | Aug 1994 | A |
5508060 | Perman et al. | Apr 1996 | A |
5798438 | Sawan et al. | Aug 1998 | A |
5938794 | Eggers | Aug 1999 | A |
5958085 | Eggers et al. | Sep 1999 | A |
6048369 | Smith et al. | Mar 2000 | A |
6183521 | Lin et al. | Feb 2001 | B1 |
6261326 | Hendrix et al. | Jul 2001 | B1 |
6615620 | Hendrix et al. | Sep 2003 | B2 |
7938865 | Fernandez Cid et al. | May 2011 | B2 |
20020119721 | Panandiker | Aug 2002 | A1 |
20070264175 | Iversen et al. | Nov 2007 | A1 |
20110138547 | Fernandez Cid et al. | Jun 2011 | A1 |
20120047665 | Yager | Mar 2012 | A1 |
20140305170 | Fetner | Oct 2014 | A1 |
Number | Date | Country |
---|---|---|
1693580 | Nov 2005 | CN |
101812809 | Aug 2010 | CN |
101812810 | Aug 2010 | CN |
102877329 | Jan 2013 | CN |
102787459 | Jan 2014 | CN |
102776739 | Apr 2014 | CN |
103726351 | Apr 2014 | CN |
103741523 | Apr 2014 | CN |
203546404 | Apr 2014 | CN |
104342869 | Feb 2015 | CN |
3906724 | Sep 1990 | DE |
4333221 | Apr 1995 | DE |
4333221 | Apr 1995 | DE |
2004076190 | Mar 2004 | JP |
9314255 | Jul 1993 | WO |
9418264 | Aug 1994 | WO |
9963146 | Dec 1999 | WO |
0233163 | Apr 2002 | WO |
Entry |
---|
U.S. Appl. No. 15/048,634, filed Feb. 19, 2016, Kelly Matt W et al, 115 pages. |
U.S. Appl. No. 15/048,655, filed Feb. 19, 2016, Kelly Matt W et al, 114 pages. |
International Search Report and Written Opinion dated Jun. 1, 2016 in International Patent Application No. PCT/US2016/018668, 12 pages. |
International Preliminary Report on Patentability dated Aug. 31, 2017 in International Patent Application No. PCT/US2016/018668, 8 pages. |
Non-Final Office Action dated Nov. 30, 2017 in U.S. Appl. No. 15/048,634, 8 pages. |
European Office Action and Examination report in application No. 16 708 862.4-1107 dated Jun. 1, 2018, 3 pages. |
European Office Action and Examination report in application No. 16 709 859.9-1107 dated Jun. 1, 2018, 3 pages. |
Final Office Action in related U.S. Appl. No. 15/048,634 dated May 15, 2018, 9 pages. |
International Search Report and Written Opinion dated Jun. 1, 2016 in International Patent Application No. PCT/US2016/018671, 12 pages. |
International Search Report and Written Opinion dated Jun. 3, 2016 in International Patent Application No. PCT/US2016/018673, 11 pages. |
Office Action dated Sep. 25, 2018 in European Patent Application No. 16710359.7, 3 pages. |
Communication pursuant to Article 94(3) dated Dec. 7, 2018 in European Patent Application No. 16709859.9, 3 pages. |
Communication pursuant to Article 94(3) dated Dec. 7, 2018 in European Patent Application No. 16708862.4, 3 pages. |
Non-Final Office Action dated Jan. 8, 2019 in U.S. Appl. No. 15/048,634, 10 pages. |
Non-Final Office Action dated Jan. 29, 2019 in U.S. Appl. No. 15/048,655, 5 pages. |
Communication pursuant to Article 94(3) dated Feb. 1, 2019 in European Patent Application No. 16710359.7, 3 pages. |
Communication pursuant to Article 94(3) dated May 16, 2019 in European Patent Application No. 16708862.4, 3 pages. |
Communication pursuant to Article 94(3) dated May 16, 2019 in European Patent Application No. 16709859.9, 3 pages. |
Communication pursuant to Article 94(3) dated Jun. 7, 2019 in European Patent Application No. 16710359.7, 3 pages. |
Notice of Allowance dated Apr. 25, 2019 in Korean Patent Application No. 10-2017-7026570, 1 page. |
Notice of Allowance dated Jun. 28, 2019 in U.S. Appl. No. 15/048,634, 9 pages. |
Notice of Allowance dated Aug. 23, 2019 in U.S. Appl. No. 15/048,655, 7 pages. |
Communication pursuant to Article 94(3) dated Oct. 22, 2019 in European Patent Application No. 16708862.4, 3 pages. |
Communication pursuant to Article 94(3) dated Nov. 26, 2019 in European Patent Application No. 16710359.7, 3 pages. |
Communication under Rule 71(3) dated Jan. 3, 2020 in European Patent Application No. 16709859.9, 7 pages. |
Non-Final Office Action received for U.S. Appl. No. 16/661,688, dated Apr. 28, 2020, 9 pages. |
Intention to Grant received for European Patent Application No. 16710359.7, dated May 29, 2020, 6 pages. |
Number | Date | Country | |
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20160244912 A1 | Aug 2016 | US |
Number | Date | Country | |
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62296987 | Feb 2016 | US | |
62119015 | Feb 2015 | US | |
62119010 | Feb 2015 | US |