ELECTROCHEMICAL CHLORINE GAS SENSOR AND FABRICATION THEREOF

Abstract

An electrochemical chlorine gas sensor is disclosed with a working electrode, a counter electrode, and a reference electrode. The working electrode may be coated with a nanoporous gold layer, a first solution comprising an ionic liquid, and a second solution that may be selected from a Nation solution, a chitosan solution, an agar solution, or combinations thereof. The reference and counter electrodes may be further coated with the ionic liquid.

Claims

1. An electrochemical chlorine gas sensor, comprising: a working electrode coated with a nanoporous gold layer, the working electrode being coated with a first solution and a second solution, the first solution comprising an ionic liquid and the second solution being selected from a group consisting of a nafion solution, a chitosan solution, an agar solution, and combinations thereof, a reference electrode coated with the first solution; and a counter electrode coated with the first solution.

2. The gas sensor according to claim 1, wherein the ionic liquid is [Emim][PF6].

3. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of Tris(2-hydroxyethyl)methylammonium methylsulfate, Benzyldimethyltetradecylammonium chloride anhydrous, Tetrahexylammonium hydrogensulfate, and combinations thereof.

4. The gas sensor according to claim 1, wherein the ionic liquid is Cholin acetate.

5. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of 1-Allyl-3-methylirnidazolium bis(trifluorornethylsulfonyl)imide, 1-Benzyl-3-methylimidazolium hexafluorophosphate, 1,3-Bis(cyanomethyl)imidazolium bis(trifluoromethylsulfonyl)imide, 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-Butyl-3-methylimidazolium methanesulfonate, and combinations thereof.

6. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of 1-Butyl-3-methylimidazolium acetate, 1-Butyl-3-methylimidazolium hydrogen sulfate, 1-Butyl-3-methylimidazolium tetrafluoroborate, 1,2,3-Trimethylimidazolium methyl sulfate, and combinations thereof.

7. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of Tetrabutylphosphonium methanesulfonate, Tributylmethylphosphonium methyl sulfate, Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, Trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide, and combinations thereof.

8. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of 1-Butyl-3-methylpyridinium bis(trifluormethylsulfonyl)imide, 1-Butyl-4-methylpyridinium chloride, 1-Butyl-4-methylpyridinium hexafluorophosphate, 3-Methyl-1-propylpyridinium bis(trifluormethylsulfonyl)imide, and combinations thereof.

9. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-Butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide, 1-Butyl-1-methylpyrrolidinium hexafluorophosphate, 1-Butyl-1-methylpyrrolidinium trifluoromethanesulfonate, and combinations thereof.

10. The gas sensor according to claim 1, wherein the ionic liquid is Triethylsulfonium bis(trifluoromethylsulfonyl)imide.

11. The gas sensor according to claim 1, wherein the ionic liquid is selected from a group consisting of 1-Butyl-1-methylpiperidinium tetrafluoroborate, 1-Butyl-1-methylpiperidinium tetrafluoroborate, 1-Butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 1-Butyl-1-methylpiperidinium hexafluorophosphate, 4-Ethyl-4-methylmorpholinium methyl carbonate solution ˜50% in methanol:water, 1,2,3-Tris(diethylamino)cyclopropenylium bis(trifluoromethanesulfonyl)imide, 1,2,3-Tris(diethylamino)cyclopropenylium dicyanamide, and combinations thereof.

12. A method of fabricating an electrochemical chlorine gas sensor with a working electrode, the method comprising: electrodepositing an alloy film of gold and silver onto a surface of the working electrode to obtain an Ag/Au-coated electrode; removing the silver from the alloy film, thereby obtaining a nanoporous gold film on the surface of the working electrode; coating the nanoporous gold film with a solidified ionic liquid layer, thereby obtaining an ionic liquid-modified working electrode; and coating the ionic liquid-modified working electrode with a layer of Nafion, thereby obtaining a Nafion-ionic liquid/nanoporous gold coated working electrode.

13. The method according to claim 12, wherein electrodepositing the alloy film of gold and silver onto the surface of the working electrode further includes: placing the working electrode in an electrochemical cell for use as a cathode electrode, the electrochemical cell comprising an anode electrode, the cathode electrode, and an electrolyte solution; and applying a voltage between the anode electrode and the cathode electrode for a predetermined amount of time, wherein the electrolyte solution includes a silver salt, a gold salt, and an inert electrolyte.

14. The method according to claim 13, wherein the voltage is between −250 mV and −750 mV.

15. The method according to claim 13, wherein the predetermined amount of time is between 300 seconds and 600 seconds.

16. The method according to claim 13, wherein the silver salt is AgNO3.

17. The method according to claim 13, wherein the gold salt is selected from the group consisting of NaAuCl4, HAuCl4, and combinations thereof.

18. The method according to claim 13, wherein the inert electrolyte is selected from the group consisting of NaNO3, Na2SO4, and combinations thereof.

19. The method according to claim 12, wherein removing the silver from the alloy film further includes washing the Ag/Au-coated electrode with a solvent, wherein the solvent is selected from the group consisting of hydrogen peroxide, nitric acid, and combinations thereof.

20. The method according to claim 19, wherein the solvent is a hydrogen peroxide solution with a concentration between 2.5 M and 5 M.

21. The method according to claim 19, wherein the solvent is a nitric acid solution with a concentration of at most 1 M.

22. The method according to claim 12, wherein coating the nanoporous gold film with a solidified ionic liquid layer further includes: drop-casting a first solution comprising ionic liquid onto the nanoporous gold film; and heating the drop-casted first solution to obtain a substantially uniform, solidified ionic liquid layer on the nanoporous gold film.

23. The method according to claim 22, wherein heating the drop-casted first solution further includes heating the drop-casted first solution to a temperature above the melting point of the ionic liquid.

24. The method according to claim 12, wherein coating the ionic liquid-modified working electrode with a layer of Nafion further includes: drop-casting a second solution comprising Nafion in a solvent onto the ionic liquid-modified working electrode; and heating the drop-casted second solution to remove the solvent.

25. The method according to claim 24, wherein the solution of Nation has a concentration of between 0.5 vol % and 2.5 vol %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The drawing figures depict one or more implementations in accord with the present teachings, by way of example only, not by way of limitation. In the figures, like reference numerals refer to the same or similar elements.

[0013] FIG. 1 illustrates a schematic representation of an electrochemical gas detection sensor;

[0014] FIG. 2 illustrates a flowchart of a method for fabricating a chlorine sensor, according to one or more implementations of the present disclosure;

[0015] FIG. 3 illustrates a scanning electron microscope (SEM) image of a nanoporous gold-coated working electrode, according to an implementation of the present disclosure;

[0016] FIG. 4 illustrates an energy-dispersive X-ray (EDX) spectrum of the surface of a nanoporous gold-coated working electrode, according to an implementation of the present disclosure;

[0017] FIG. 5 illustrates cyclic voltammograms of a gold-based screen printed electrode and a nanoporous gold film coated working electrode in a 1M H.sub.2SO.sub.4 solution, according to an implementation of the present disclosure;

[0018] FIG. 6 illustrates the amperometric responses of a Nafion-IL/gold-based screen printed electrode and Nafion-IL/nanoporous gold coated working electrode to 0.01 ppm chlorine gas, according to an implementation of the present disclosure;

[0019] FIG. 7 illustrates a plot of the applied potentials in a range of +0.1V to −0.2V versus the amperometric responses of a gold-based screen printed electrode and a nanoporous gold film coated working electrode to 1.0 ppm chlorine gas, according to an implementation of the present disclosure;

[0020] FIG. 8 illustrates a typical current-time plot for a Nafion-IL/nanoporous gold-coated working electrode at various chlorine concentrations, according to an implementation of the present disclosure; and

[0021] FIG. 9 illustrates a chart of amperometric response of an electrochemical chlorine sensor with a Nafion-IL/nanoporous gold-coated working electrode to different gases with similar concentrations, according to an implementation of the present disclosure.

DETAILED DESCRIPTION

[0022] In the following detailed description, numerous specific details are set forth by way of examples in order to provide a thorough understanding of the relevant teachings. However, it should be apparent that the present teachings may be practiced without such details. In other instances, well known methods, procedures, components, and/or circuitry have been described at a relatively high-level, without detail, in order to avoid unnecessarily obscuring aspects of the present teachings.

[0023] Generally, electrochemical gas detection sensors are gas detectors that are configured to measure the concentration of a target gas by oxidizing or reducing the target gas at an electrode and measuring the resulting current. For example, in FIG. 1, a schematic representation of an electrochemical gas detection sensor (“sensor”) 100 is depicted. In different implementations, electrochemical gas detection sensors may typically include a working electrode 101, a reference electrode 102, a counter electrode 103, and an electrolyte solution 104.

[0024] As illustrated schematically in FIG. 1, once a target gas 105 reaches the sensor 100, it undergoes an electrochemical reaction. The electrons involved in the electrochemical reaction can flow from the working electrode 101 through the external circuit, producing an output signal 106 for the sensor. The reference electrode 102 may help provide a stable electrochemical potential in the electrolyte solution 104. The counter-electrode 103 can be configured to complete the circuit of the electrochemical gas detection sensor. The counter electrode 103 may function as a second half-cell, and can allow electrons to enter or leave the electrolyte solution 104.

[0025] The present disclosure is directed to a novel electrochemical chlorine gas sensor that comprises a Nafion-IL/nanoporous gold electrode for detecting the presence of chlorine gas. In different implementations, this chlorine gas sensor includes provisions to detect chlorine at very low concentrations. In addition to the components comprising sensor 100 described above with reference to FIG. 1, in some implementations of the present electrochemical chlorine gas sensor, the working electrode may be made of a conductive material (for example, carbon or other conductive materials), and may further be coated with a nanoporous gold layer, a solidified ionic liquid layer, and/or a layer of for example Nafion. In addition, in some implementations, the reference electrode and the counter electrode may be coated with a solidified ionic liquid layer. Benefits from these features include, but are not limited to providing a simple and sensitive electrochemical chlorine gas sensor that may be capable of detecting the presence of chlorine gas even at very low concentrations.

Fabrication of a Novel Electrochemical Chlorine Gas Sensor

[0026] For purposes of clarity, FIG. 2 illustrates a method 200 of fabricating an electrochemical chlorine gas sensor according to one or more implementations of the present disclosure. As shown in FIG. 2, in one implementation, the method 200 includes a first step 201 of electrodepositing an alloy film of gold and silver onto a surface of a working electrode to obtain an Ag/Au-coated electrode. A second step 202 can involve removing the silver from the alloy film to obtain a nanoporous gold film on the surface of the working electrode. In a third step 203, the nanoporous gold film can be coated with a solidified ionic liquid layer to obtain an ionic liquid-modified (IL-modified) working electrode. A fourth step 204 may include coating the IL-modified working electrode with a layer of Nafion to obtain a Nafion-IL/nanoporous gold coated working electrode.

[0027] Further details regarding the method of fabrication are provided herein. In some implementations, first step 201 may involve washing the working electrode with water and providing the washed electrode as a cathode electrode in an electrochemical cell. In one implementation, the electrochemical cell may further include an anode electrode and an electrolyte solution. In some implementations, the electrolyte solution of the electrochemical cell may include a silver salt, for example AgNO.sub.3; a gold salt, which may be selected from NaAuCl.sub.4, HAuCl.sub.4, or combinations thereof; and/or an inert electrolyte, for example an NaNO.sub.3 solution, an Na.sub.2SO.sub.4 solution, or combinations thereof.

[0028] In different implementations, by applying a predetermined voltage between the anode and cathode electrodes for a predetermined amount of time, a thin film of silver and gold may be coated on the working electrode to obtain an Ag/Au-coated working electrode. In some exemplary implementations, the predetermined voltage can range from −250 mV to −750 mV; however, in other implementations, the predetermined voltage can range from −200 mV to −800 mV. In addition, in some exemplary implementations, the predetermined amount of time can range from 300 s to 600 s, while in other implementations, the predetermined amount of time can range from 100 s to 800 s.

[0029] Referring to second step 202, in one implementation, the Ag/Au-coated working electrode may be washed with a solvent. For example, a hydrogen peroxide solution with a molarity of 2.5M to 5M, or a nitric acid solution with a molarity of at most 1M, can be used to remove the silver from the alloy film and obtain a nanoporous gold film on the surface of the working electrode.

[0030] With reference to third step 203, in some implementations, a first solution comprising an ionic liquid may be casted onto the working electrode that is coated with a layer of nanoporous gold. In one implementation, the casting may be performed by drop-casting the ionic liquid onto the working electrode. Moreover, in some implementations, the reference electrodes and/or counter electrodes may further be coated with the solidified ionic liquid layer as well. In one implementation, the drop-casted ionic liquid (IL) solution may be heated in order to obtain a uniform solidified ionic liquid layer for coating on the electrodes (such ionic liquid coated electrodes will be hereinafter referred to as IL-modified electrodes).

[0031] According to some implementations, the ionic liquid may be for example an ammonium based ionic liquid, such as Tris(2-hydroxyethyl)methylammonium methylsulfate, Benzyldimethyltetradecylammonium chloride anhydrous, Tetrahexylammonium hydrogensulfate; a Choline based ionic liquid, such as Choline acetate; an Imidazolium based ionic liquid, such as 1-Allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-Benzyl-3-methylimidazolium hexafluorophosphate, 1,3-Bis(cyanomethyl)imidazolium bis(trifluoromethylsulfonyl)imide, 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-Butyl-3-methylimidazolium methanesulfonate; a Basionics based ionic liquid, such as 1-Butyl-3-methylimidazolium acetate, 1-Butyl-3-methylimidazolium hydrogen sulfate, 1-Butyl-3-methylimidazolium tetrafluoroborate, 1,2,3-Trimethylimidazolium methyl sulfate; a Phosphonium based ionic liquid such as Tetrabutylphosphonium methanesulfonate, Tributylmethylphosphonium methyl sulfate, Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, Trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide; a Pyridinium based ionic liquid, such as 1-Butyl-3-methylpyridinium bis(trifluormethylsulfonyl)imide, 1-Butyl-4-methylpyridinium chloride, 1-Butyl-4-methylpyridinium hexafluorophosphate, 3-Methyl-1-propylpyridinium bis(trifluormethylsulfonyl)imide; a Pyrrolidinium based ionic liquid, such as 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-Butyl-1-methylpyrrolidinium hexafluorophosphate, 1-Butyl-1-methylpyrrolidinium trifluoromethanesulfonate; a sulfonium based ionic liquid, such as Triethylsulfonium bis(trifluoromethylsulfonyl)imide; or other ionic liquids, such as 1-Butyl-1-methylpiperidinium tetrafluoroborate, 1-Butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 1-Butyl-1-methylpiperidinium hexafluorophosphate, 4-Ethyl-4-methylmorpholinium methyl carbonate solution ˜50% in methanol water, 1,2,3-Tris(diethylamino)cyclopropenylium bis(trifluoromethanesulfonyl)imide, 1,2,3-Tris(diethylamino)cyclopropenylium dicyanamide, [Emim][PF6], or combinations thereof.

[0032] Furthermore, referring to FIG. 2, in some implementations, fourth step 204 may involve coating the IL-modified working electrode with a second solution. In some implementations, the second solution may be a nafion solution, a chitosan solution, an agar solution, or combinations thereof. In different implementations, in order to coat the IL-modified working electrode with the second solution, a solution of (for example, Nafion) with a concentration of for example between 0.5 vol % and 2.5 vol % in a suitable solvent may first be drop-casted onto the IL-modified working electrode. The drop-casted solution may then be heated to remove the solvent and obtain a Nafion-IL/nanoporous gold-coated working electrode.

Example 1: Fabrication of a Modified Electrochemical Chlorine Sensor

[0033] For purposes of clarity, one example is provided in which an electrochemical chlorine gas sensor is fabricated pursuant to the teachings of the present disclosure. However, it should be understood that in other implementations, one or more of the steps disclosed herein can be omitted as desired, or additional steps may be included. As described above, in one implementation, the electrochemical gas sensor includes a reference electrode, a working electrode, and a counter electrode. Furthermore, the working electrode may be coated with a layer of nanoporous gold. The working electrode is washed thoroughly with water and then disposed in an electrochemical cell for use as a cathode electrode. In one implementation, a solution comprising approximately 5 mM NaAuCl.sub.4 solution, approximately 0.5 mM AgNO.sub.3 solution, and approximately 0.5M NaNO.sub.3 solution is used as the electrolyte solution in the electrochemical cell. In addition, a voltage of approximately −500 mV potential is then applied for approximately 600 seconds to the electrochemical cell. In some implementations, the working electrode may be coated with a thin film of silver and gold as the electrochemical reaction occurs in the electrochemical cell, thereby producing an Ag/Au-coated working electrode.

[0034] In some implementations, the Ag/Au-coated electrode is immersed in an approximately 5M hydrogen peroxide solution for about 12 hours to remove the silver from the alloy film and obtain a nanoporous gold film on the surface of the working electrode. The nanoporous gold film may then be washed thoroughly with water.

[0035] In some implementations, the nanoporous gold film coated working electrode, the counter electrode, and the reference electrode are each coated with a solidified ionic liquid layer. To this end, in one implementation, approximately 0.2 g of [Emim][PF.sub.6] is drop-casted on the electrode surface and heated to a temperature above the melting point of the ionic liquid (58-62° C.). This process melts the [Emim][PF.sub.6] and produces a substantially uniform solidified ionic liquid layer on the electrode surfaces, hereinafter referred to as the IL-modified electrodes.

[0036] In some implementations, the IL-modified working electrode is further coated with a Nafion layer to obtain a Nafion-IL/nanoporous gold coated working electrode. To coat the IL-modified working electrode with a Nafion layer, approximately 10 μL of nafion (1%) is drop-casted onto the IL-modified working electrode. The drop-casted solution may then be heated at approximately 50° C. for around 10 minutes to remove the solvent and obtain a Nafion-IL/nanoporous gold-coated working electrode. The Nafion-IL/nanoporous gold-coated working electrode along with the IL-modified reference and counter electrodes are utilized to form the electrochemical chlorine gas sensor as disclosed herein.

Example 2: Characterization Tests

[0037] In this example, the results of some characterization tests performed on the electrochemical chlorine gas sensor fabricated as described in Example 1, are presented. Referring to FIG. 3, a scanning electron microscope (SEM) image of the nanoporous gold-coated working electrode of the electrochemical chlorine sensor is shown. The porous structure of the surface of the nanoporous gold-coated working electrode is visible in FIG. 3, indicating a successful deposition of a nanoporous gold layer onto the surface of the electrode.

[0038] In order to obtain a chemical characterization of the surface, an energy dispersive X-ray spectroscopy (EDX) method was used. In FIG. 4 an EDX spectrum of the surface of the nanoporous gold coated working electrode. Referring to FIG. 4, two sharp peaks around 2 keV 401 and 10 keV 402 can be seen in the EDX plot, indicating the existence of the nanoporous gold film on the surface of the working electrode.

[0039] Furthermore, a cyclic voltammetry (CV) test was used to obtain anodic and cathodic densities. FIG. 5 depicts the cyclic voltammogram of a commercial electrode 501 (i.e., a gold-based screen printed electrode where the working electrode is coated with a layer of gold) and a nanoporous gold film-coated working electrode 502 in a 1M H.sub.2SO.sub.4 solution. In FIG. 5, the nanoporous gold film-coated working electrode 502 has larger anodic current densities for the formation of Au oxides and cathodic current densities for the reduction of the oxides. In some implementations, this may be attributed to the presence of electro-active sites on the surface of the nanoporous gold film-coated working electrode 502. The roughness factor may be used to express the ratio between the real surface area and the geometrical area of the electrode. By the integration of the charge consumed in the gold oxide reduction, the roughness factor of the nanoporous gold film-coated working electrode is 89.3 and the roughness factor of the commercial electrode is 4.7.

Example 3: Electrochemical Behavior of Nafion-IL/Nanoporous Gold Coated Working Electrode

[0040] FIG. 6 shows the amperometric responses of the Nafion-IL/gold-based screen printed electrode (designated by the letter “a”) and the Nafion-IL/nanoporous gold-coated working electrode (designated by the letter “b”) to 0.01 ppm chlorine gas. It can be seen that the sensitivity of the Nafion-IL/nanoporous gold-coated working electrode is higher than that of the Nafion-IL/gold-based screen printed electrode. In one implementation, the significantly improved performance of the Nafion-IL/nanoporous gold-coated working electrode may be attributed to the presence of more electroactive sites on the surface of a Nafion-IL/nanoporous gold coated working electrode compared to a gold-based screen printed electrode.

[0041] In addition, the effect of applied potentials on the amperometric responses of 1.0 ppm chlorine gas was investigated in a range of +0.1V to −0.2V, and the results are plotted in FIG. 7. As shown in FIG. 7, the sensor response increases rapidly with a decrease in the applied potential from +0.1V to −0.2V, and reaches its maximum at −0.2 V. Therefore, in this case, −0.2 V may be chosen as the optimum detection potential.

[0042] FIG. 8 shows a typical current-time plot of the Nafion-IL/nanoporous gold-coated working electrode for different chlorine gas concentrations at an applied potential of −0.2V. Referring to FIG. 8, once chlorine gas is introduced to the sensor at a point 801, the sensor generates an amperometric response indicating the presence of the chlorine gas. In addition, once the stream of the chlorine gas is cut off at a point 802, the sensor rapidly returns to its reference signal indicating an absence of the chlorine gas.

[0043] The effects of interfering compounds were studied on the determination of chlorine gas by the chlorine gas sensor. For example, FIG. 9 shows a chart of amperometric responses of the disclosed electrochemical chlorine sensor to different gases with similar concentrations. In FIG. 9, no interference is observed with ammonia (NH.sub.3), dimethyl-methane-phososphonate (DMMP), nitrogen dioxide (NO.sub.2) and carbon dioxide (CO.sub.2) for 3-fold (1.0 ppm) quantities of chlorine gas.

[0044] While the foregoing has described what are considered to be the best mode and/or other examples, it is understood that various modifications may be made therein and that the subject matter disclosed herein may be implemented in various forms and examples, and that the teachings may be applied in numerous applications, only some of which have been described herein. It is intended by the following claims to claim any and all applications, modifications and variations that fall within the true scope of the present teachings.

[0045] Unless otherwise stated, all measurements, values, ratings, positions, magnitudes, sizes, and other specifications that are set forth in this specification, including in the claims that follow, are approximate, not exact. They are intended to have a reasonable range that is consistent with the functions to which they relate and with what is customary in the art to which they pertain.

[0046] The scope of protection is limited solely by the claims that now follow. That scope is intended and should be interpreted to be as broad as is consistent with the ordinary meaning of the language that is used in the claims when interpreted in light of this specification and the prosecution history that follows and to encompass all structural and functional equivalents. Notwithstanding, none of the claims are intended to embrace subject matter that fails to satisfy the requirement of Sections 101, 102, or 103 of the Patent Act, nor should they be interpreted in such a way. Any unintended embracement of such subject matter is hereby disclaimed.

[0047] Except as stated immediately above, nothing that has been stated or illustrated is intended or should be interpreted to cause a dedication of any component, step, feature, object, benefit, advantage, or equivalent to the public, regardless of whether it is or is not recited in the claims.

[0048] It will be understood that the terms and expressions used herein have the ordinary meaning as is accorded to such terms and expressions with respect to their corresponding respective areas of inquiry and study except where specific meanings have otherwise been set forth herein. Relational terms such as first and second and the like may be used solely to distinguish one entity or action from another without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms “comprises,” “comprising,” or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by “a” or “an” does not, without further constraints, preclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0049] The Abstract of the Disclosure is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in various implementations. This is for purposes of streamlining the disclosure, and is not to be interpreted as reflecting an intention that the claimed implementations require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed implementation. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separately claimed subject matter.

[0050] While various implementations have been described, the description is intended to be exemplary, rather than limiting and it will be apparent to those of ordinary skill in the art that many more implementations and implementations are possible that are within the scope of the implementations. Although many possible combinations of features are shown in the accompanying figures and discussed in this detailed description, many other combinations of the disclosed features are possible. Any feature of any implementation may be used in combination with or substituted for any other feature or element in any other implementation unless specifically restricted. Therefore, it will be understood that any of the features shown and/or discussed in the present disclosure may be implemented together in any suitable combination. Accordingly, the implementations are not to be restricted except in light of the attached claims and their equivalents. Also, various modifications and changes may be made within the scope of the attached claims.