AKD EMULSION AND METHOD OF MAKING
20240158991 ยท 2024-05-16
Assignee
Inventors
Cpc classification
International classification
Abstract
Provided is an alkyl ketone dimer emulsion and the preparation thereof. More particularly, described is a 3-component emulsion, which is easy to prepare using low emulsification abilityhigh shear speed capability equipment to prepare the AKD emulsion with excellent quality, high efficiency, and less preparation time.
Claims
1. A composition for treating a paper product comprising: a) a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, or combinations thereof; b) a second component chosen from an alkyl ketene dime (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, or combinations thereof,. and c) a dispersant; wherein the composition is in the form of an emulsion.
2. The composition according to claim 1, wherein the first component of the composition is a polyDADMAC and/or polyDADMAC derivative.
3. The composition according to claim 1, wherein the second component of the composition is an alkyl ketene dimer.
4. The composition according to claim 1, wherein the dispersant in the composition is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, copolymer of acrylamide, sulfonic acid, and combinations thereof.
5. The composition according to claim 1, wherein the first component in the composition is present in an amount of from about 0.1 wt. % to about 30 wt. %, about 0.1 wt. % to about 20 wt. %, about 0.5 wt. % to about 15 wt. %, based on the total weight of the composition.
6. The composition according to claim 1, wherein the second component in the composition is present in an amount of from about 0.1 wt. % to about 60 wt. %, or about 1 wt. % to about 50 wt. %, or about 5 wt. % to about 40 wt. %, based on the total weight of the composition.
7. The composition according claim 1, wherein the dispersant in the composition is present in amount of from about 0.1 wt. % to about 10.0 wt. %, or about 0.1 wt. % to about 1 wt. %, or about 025 wt. % to about 0.75 wt. %, based on the total weight of the composition.
8. The composition according to claim 1, further comprising a saturated or unsaturated fatty acid.
9. The composition according to claim 8, wherein the fatty acid in the composition is present an amount of from about 0.1 to about 10 wt. %, or about I wt. % to about 10 wt. %, based on the total weight of the composition.
10. The composition according to claim 1, wherein a paper product treated with the composition has higher water resistance compared with an untreated paper product.
11. A method of preparing an oil in water emulsion, wherein the method comprises: providing a composition comprising a. a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide, a polyamine, a polyethyleneimine, a. polyvinyl alcohol, and combinations thereof; b. a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and c. a dispersant; and homogenizing the composition to produce the emulsion.
12. The method according to claim 11, wherein the first component in the composition is chosen from a polyDADMAC and/or a polyDADMAC derivative.
13. The method according to claim 12, wherein the polyDADMAC derivative is a copolymer of acrylamide and diallyl dimethyl ammonium chloride.
14. The method according to claim 11, herein the second component in the composition is an alkyl ketene dimer.
15. The method according to claim 11, wherein the dispersant in the composition is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, a copolymer of acrylamide and sulfonic acid, and combinations thereof
16. The method according to claim 11, wherein the first component in the composition is present in an amount of from about 0.1 wt. % to about 30 wt. %, or about 0.5 wt. % to about 15 wt. % based on the total weight of the composition.
17. The method according to claim 11, wherein the second component in the composition is present in an amount of from about 1 wt. % to about 60 wt. %, or about 1 wt. % to about 50 wt. %, or about 5 wt. % to about 40 wt. % based on the total weight of the composition.
18. The method according to claim 11, wherein the dispersant in the composition is present in amount of from about 1.0 wt. % to about 10 wt. %, or about 0.1 wt../i) to about 1 wt. %, or about 0.25 wt. % to about 0.75 wt. %, based on the total weight of the composition.
19. The method according to claim 11, wherein the composition further comprises a fatty acid in an amount of from about 0.1 to about 10 wt. %, or about 1 wt. % to about 5 wt. %, based on the total weight of the composition.
20. A method of producing a paper product comprising; providing an emulsion composition according to claim 1; and treating paper with the emulsion composition to form the paper product.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION
[0025] The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. As used herein, the word exemplary means serving as an example, instance, or illustration. Thus, any embodiment described herein as exemplary is not necessarily to be construed as preferred or advantageous over other embodiments. All of the embodiments described herein are exemplary embodiments provided to enable persons skilled in the art to make or use the invention and not to limit the scope of the invention which is defined by the claims. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary, or the following detailed description.
[0026] Provided is an emulsion composition that can be added to the wet end of a papermaking process or applied to the surface of the formed paper to provide resistance to aqueous liquids. The emulsion composition contains a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, or any combination thereof; a second component chosen from an alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, and combinations thereof; and a dispersant.
[0027] The emulsion composition is based upon a coacervate concept, wherein two oppositely charged polymers (anionic and cationic) are mixed in such a proportion to produce a stabilized colloidal coacervate which functions as an emulsifier or dispersant and stabilizes the emulsified or dispersed sizing agents.
[0028] In some aspects, the anionic component is an anionic polyelectrolyte selected from the group consisting of a polycarboxylate, polysulfate and polysulfonate, such as a lignosulfonate. The cationic component can be chosen from a cationic polyamine, a polysulfonium, a polyamidoainine, or combinations thereof.
[0029] In some aspects of the emulsion composition, a first component is chosen from a polymer which could be anionic, cationic, or non-anionic. The polyamines may be primary amines, secondary amines, tertiary amines, or quaternary amines or may contain a mixture of different strength amine groups such as polyethyleneimine. The polymers which are particularly useful in these compositions include homopolymers and copolymers having a molecular weight (Mw) of about 10,000 or higher, as determined by size exclusion chromatography.
[0030] In some aspects of the emulsion composition, a quaternaty polyamine, such as poly (diallyldialkylammonium chloride) is used wherein the alkyl moiety has I to about 6 carbons; a polyvinylamine; and their derivatives. Other cationic components can be a quaternary polyamine such as a poly(diallyldialkylammonium chloride), wherein the alkyl moiety has I to about 6 carbons.
[0031] In the context of the present application the term a polyacrylamide denotes a polyacrylamide where both cationic and anionic units are present in an aqueous solution. Amphoteric polyacrylamide is obtained by copolymerization of acrylamide or methactylamide together with both anionic and cationic monomers. The amphoteric polyacrylamide can be obtained by copolymerization of acrylamide together with both anionic and cationic monomers. In some aspects of the emulsion composition, alley ketene dimers having general formula (I)
##STR00001##
wherein R.sup.1 and R.sup.2 represent saturated or unsaturated hydrocarbon groups, the hydrocarbon groups having from 8 to 36 carbon atoms and can be straight or branched and having 6 chain alkyl groups and 12 to 20 carbon atoms, such as hexadecyl and octadecyl groups.
[0032] The alkenyl succinic anhydrides (ASA) used in this invention are well known and are composed of unsaturated hydrocarbon chains containing pendant succinic anhydride groups.
[0033] ASA, which are preferred in this invention, are usually made in a two-step process starting with an alpha olefin. The olefin is first isomerized by randomly moving the double bond from the alpha position, in the second step the isomerized olefin is reacted with an excess of maleic anhydride to give the final ASA structure as indicated in the following reaction scheme.
##STR00002##
[0034] Isomerized Olefin, Maleic Anhydride, or Alkenyl Succinic Anhydride (ASA) results if the isomerization step is omitted. ASA's that are solid at room temperature may be produced if the chain length of the starting alpha olefin is in the C-14 to C-22 range and may be linear or branched. For the purpose of current compositions, the ASA's were prepared by reaction of maleic anhydride: with olefins containing 14-18 carbon atoms, Typical ASA's are commercially available fr?m Albemarle Corporation, Baton Rouge, La. Representative starting olefins for reaction with maleic anhydride to prepare ASAs for use in the present formulation include: octadecene, tetradecene, hexadecene, eicodecene, 2-nhexyl-1-octene, 2-n-octyl-1-dodecene, 2-n-octyl-l-decene, 2-n-dodecyl-l-octene, 2-n-octyl-1-octene, 2-n-octyl-1- nonene, 2-n-hexyl-1-decent: and 2-n-heptyl-1-octene.
[0035] The paraffin wax is generally Obtained through separation and extraction of a hydrocarbon of good crystallizability from the oily distillate moiety in reduced-pressure distillation of crude oil. It is a colorless or white transparent solid wax containing a linear hydrocarbon as the main ingredient and has a melting point of about 40? C. to about 90? C. Other exemplary hydrophobic acid anhydrides that may be stabilized with the polymers of this formulation are useful as sizing agents.
[0036] In some aspects of the emulsion composition, the dispersant is an anionic surface-active polyelectrolyte, such as polycarboxylates (e.g., polyaciylates, carboxymethyl cellulose, hydrolyzed polyacrylamides), polysulfates (e.g., polyvinyl sulfate, polyethylene sulfate) or polysulfonates (e.g., polyvinyl sulfonate, lignin sulfonates).
[0037] In some aspects of the emulsion composition, the anionic surfactants can be chosen from alkyl, aryl or alkyl aryl sulfates, alkyl, aryl or alkyl aryl carboxylates, alkyl, aryl or alkyl aryl sulfonates, or combinations thereof
[0038] In some aspects, the alkyl moieties can have from 1 to about 18 carbons, the aryl moieties can have from about 6 to about 12 carbons, and the alkyl aryl moieties can have from about 7 to about 30 carbons. The moieties can be propyl, butyl, hexyl, decyl, dodecyl, phenyl, or benzyl groups, and linear or branched alkyl benzene derivatives of the carboxylates, sulfates, and sulfonates.
[0039] In other aspects, the anionic component can be chosen from polycarboxylates, polysulfates and polysulfonates. These can include a ligno- or lignin sulfonate, such as the sodium salt, calcium salt, ammonium salt, iron salt or chromium salt.
[0040] In one aspect, the anionic component can be sodium lignosulfonate or a naphthalene-sulfonic acid with formaldehyde condensed polymer, for example BASF's Tamol? line of products, such as Tamor? NN9401.
[0041] In some aspects of the emulsion, the composition comprises the first component in an amount of from about 0.1 wt. % to about 30 wt. %, or from about 0.1 wt. % to about 20 wt. %, from about 0.5 wt. % to about 15 wt. % based on the total weight of the composition
[0042] In some aspects of the emulsion, the second component in an amount of from about 0.1 wt. % to about 50 wt. %, or from about 1 wt. % to about 60 wt. %, or from about 5 wt. % to about 40 wt. % based on the total weight of the composition.
[0043] In yet other aspects of the emulsion, the dispersant is present in an amount of from about 0.1 wt. % to about 10 wt. % or from about 0.1 wt. % to about 1 wt. %, or from about 0.25 wt. % to about 0.75 wt. % based on the total weight of the composition.
[0044] In yet other aspects of the emulsion, the composition further contains fatty acid, such as stearic acid. The fatty acid can be present in the composition in an amount of from about 0.1 to about 10 wt. %, or from 1 wt. % to about 5 wt. % based on the total weight of the composition.
[0045] In still other aspects of the emulsion composition, the emulsion is added to a papermaking furnish prior to forming a paper product or the emulsion composition can be applied to the outer surface of the formed paper. This results in higher water resistance to aqueous liquids of the formed product when compared with an untreated paper, in which water resistance studies were conducted using the TAPPI T 441 Cobb Test.
[0046] In some aspects, there is provided a method of preparing an oil-in-water emulsion. The method includes providing an emulsion composition that includes a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), a polyvinyl alcohol, and combinations thereof; a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and a dispersant. The composition is homogenized thereby producing the emulsion.
[0047] In some aspects of the method, the first component is chosen from a polyDADMAC or a polyDADMAC derivative, such as a copolymer of acrylamide and diallyl dimethyl ammonium chloride.
[0048] In some aspects of the method, the second component is an alkyl ketene dimer.
[0049] In some aspects of the method, the dispersant is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, a copolymer of acrylamide and sulfonic acid, and combinations thereof
[0050] In some aspects of the method, the emulsion composition contains the first component in an amount of from about 0.1 wt. % to about 30 wt. %, or from about 0.1 wt. % to about 20 wt. %, from about 0.5 wt. % to about 15 wt. % based on the total weight of the composition.
[0051] In other aspects of the method, the second component is present in an amount of from about 0.1 wt. % to about 50 wt. %, or from about 1 wt. % to about 60 wt. %, or from about 5 wt. % to about 40 wt. % based on the total weight of the composition.
[0052] In yet other aspects of the method, the dispersant is present in an amount of from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 1.0 wt. %, or from about 0.25 wt. % to about 0.75 wt. % based on the total weight of the composition.
[0053] In some aspects of the method, the emulsion composition further includes fatty acids, for example, stearic acid. The fatty acid can be present in the composition in an amount of from about 0.1 to about 10 wt. %, or from about 1 wt. % to about 5 wt. %. based on the total weight of the composition.
[0054] In some aspects of the method, the composition is homogenized using a rotor%stator generator, a high-pressure device, or a sonic disruptor.
[0055] In some aspects of the method, the composition is homogenized using a rotorlstator generator having a linear shear force of at least 23 mls, such as a colloidal mill,
[0056] In other aspects of the method, the composition is homogenized using a high-pressure device, such as piston pump.
[0057] In some aspects of the method, the emulsion has a mean particle size of less than 2 micron and can be less than 1 micron.
[0058] In yet other aspects, provided is a method of forming a paper product that includes providing an emulsion composition containing a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide wAm), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component chosen from an alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, and combinations thereof; and a dispersant.
[0059] The emulsion composition can be added to the furnish at any point of the papermaking process, for example, at the blend chest or other points in the wet-end of the process. The emulsion composition can also be applied to the surface of the paper produced, for example, at the forming section, dryer section or calendar rolls. The emulsion can be applied by spraying, coating, film transferring, soaking, or other known means used in pa.permaking.
[0060] In some aspects of the method, the paper product can be, for example, paperboard, cardboard, and aseptic packaging, copy paper and coated paper among other paper products.
EXAMPLES
Example 1Lab Waring Blender Study
[0061] An AKD emulsification study was accomplished using Waring blender method. The study looked at the emulsification ability of different mill starch with Prequel? products (calcium salts of long chain fatty acids). The following steps were followed:
[0062] Aqueous phase preparationCharge the target water and mix well with Tamol? with overhead stirrer in a 2-liter(?) glass beaker while maintaining a stirring speed of about 500 to 800 rpm. and charge required gram of polymer to homogenize with Tamol? for 5 min. Adjust pH to 4.5. The 2-liter glass beaker with emulsion was placed int? a water bath and heated this phase (aqueous phase) to 70? C.
[0063] Emulsification stepThe aqueous phase (at 70? C.) and melted AKD (the AKD was kept in a pre-heated oven at 85? C.) were combined in a Waring blender equipped four- blades and capable of generating high shear force capable of breaking the oil into small droplets forming an emulsion. The blender was capped and set on the highest speed setting and the contents homogenized for 1 minute producing an AKD oil-in-water emulsion, Based on the % AKD, the emulsion was diluted to 10-15% and screened with 100 mesh paper cone paint strainers. The AKD emulsion properties were obtained and a 32? C. oven stability test was conducted.
[0064] A combination of PolyDADMAC and Hercobond? 1620 (butanedioic acid, 2-methylene-, polymer with 2-(dimethylaminoethyl 2-methyl-2-propenoate, N,N-ditnethyl-2-propenamide, propenamide and sodium 2-methyl-2-propene-l-sulfonate (1:1), sulfate) were studied. In general, PolyDADMAC and Hercobond? 1620 showed good emulsification ability compared with AKD wax as shown in Tables 1 and 2, The AKI) emulsion prepared with PolyDADMAC and Hercobond? 1620 resulted in an emulsion having a smaller average particle size. The results also showed that different percentages of AKI) polymer and Tamol? (naphthalenesulfonic acid, polymer with formaldehyde, sodium salt) with stirring impacted the average particle size of AKD in the final emulsion. It was also observed that better emulsification was accomplished i.e., gave the higher tear force which in turn gave the better emulsification ability, either at higher speeds of the blender or longer stirring times.
TABLE-US-00001 TABLE 1 Waring Blender -AKD emulsification with PolyDADMAC Run Water PolyDADMAC 1865 9401 Order (g) (g) (g) (g) Media 90% 2 um Mean SD 1 68.802 9.217 21.505 0.476 0.8150 1.2288 99.55 0.8573 0.2879 2 73.306 9.820 16.367 0.507 0.8859 1.4238 98.15 0.9545 0.3721 3 78.620 6.897 13.793 0.690 1.1423 2.1681 87.09 1.3005 NA 4 64.819 14.472 20.260 0.449 0.5990 0.8072 100 0.6082 0.1479 5 68.802 15.361 15.361 0.476 0.7197 0.9983 100 0.7398 0.2013 6 74.950 19.231 12.821 0.064 1.1586 3.4128 74.08 1.6990 1.6143 7 61.622 16.216 21.622 0.541 0.5911 0.7829 100 0.5986 0.1394 8 68.199 9.479 22.117 0.205 0.8003 1.2272 99.42 0.8473 0.2967 9 68.199 15.798 15.798 0.205 0.6435 0.8692 100 0.6565 0.1658 10 72.800 10.118 16.863 0.219 0.9054 1.4688 97.76 0.9778 0.3889 11 77.867 7.353 14.706 0.074 1.1116 2.0409 89.32 1.2413 0.6151 12 68.504 12.461 18.692 0.343 0.7087 0.9855 100 0.7255 0.1999
TABLE-US-00002 TABLE 2 Waring Blender -AKD emulsification with Hercobond? 1620 Water 1620 1865 9401 Run (g) (g) (g) (g) Median 90% 2 um Mean SD 1 68.220 13.650 17.804 0.326 0.7335 1.0662 100 0.7592 0.2331 2 61.271 16.575 22.099 0.055 0.6784 0.9491 100 0.6925 0.1939 3 68.543 16.085 15.175 0.197 0.8269 1.2796 100 0.8744 0.3140 4 67.614 9.091 22.727 0.568 0.7730 1.1426 99.847 0.8052 0.2644 5 62.632 15.789 21.053 0.526 0.6228 0.8437 100 0.6330 0.1578 6 70.000 17.647 11.765 0.588 0.7134 1.0184 100 0.7370 0.2205 7 64.620 15.165 20.029 0.1860 0.7760 1.1272 99.839 0.8096 0.2492
[0065] The Lab Waring blender study showed AKD wax can be adequately emulsified using a composition comprising polyDADMAC and Hercobond? 1620.
Example 2Regenerative Turbine Pump Emulsification Study
[0066] In this study, a Hercules Prequel Starch Alkaline Size Emulsifier (HASE) was used, which includes a Burks? regenerative turbine pump. The pump generates high shear force which can emulsify the AKD, ASA and paraffinic wax 1polyDADMAC or Hercobond? 1620. However, unlike ASA, AKD and paraffinic wax is solid and required melting before being pumped into the turbine pump. The HASE was modified by including a blending tank for water phase preparation, a AKD melting tank, a screw pump, and a hot water tank (see
[0067] In addition to the configuration shown in
[0068] The study indicated that emulsification can be accomplished through the use of either version 1 or 2 of the BASE system. The produced emulsions were sampled, evaluated, and diluted for further oven stability testing. As shown in Table 3 and 4 below, the mean particle size of the emulsion produced by the first version system was at range of 900-1200 ?m and the stability of the emulsion was poor.
[0069] However, when using the modified HASE system shown in
TABLE-US-00003 TABLE 3 HASE middle scale trial version 1 - AKD emulsion properties and stability results 45 kg AKD, 45 kg Hercobond? 1620, 60 kg water, 0.45 kg Tamol? Starting Vis: TS %: 60.0 cps 17.8% Final Visc. Original AKD %: 1 Week 1 Week After 1 week; emulsion 14.96% 23? C. 32? C. 82.8 cps Median 1.3247 1.106 1.0100 0.9999 90% 2.2786 2.0282 1.7490 1.9607 2 um 83.669 89.561 94.185 90.632 Mean 1.4672 1.0402 1.1164 1.1429 SD 0.6507 0.6236 0.5053 0.6666
TABLE-US-00004 TABLE 4 HASE middle scale trial version 1 - AKD emulsion properties and stability results 30 kg AKD, 25 kg PolyDADMAC, 0.3 kg Tamol?, 45 kg water Starting Visc: TS %: 36.9 cps 1:1 dilution 18.93% 1 Week Final Visc. Original Assay: 1 Week 32? C. After 1 week emulsion 11.854% 23? C. (Gel) 698.9 cps Median 0.9585 0.9073 0.9630 5.8679 90% 1.4460 1.5141 1.7917 13.0072 2 um 98.511 96.827 93.139 27.903 Mean 1.0155 0.9943 1.1034 6.3428 SD 0.3329 0.4328 0.5703 5.1579
TABLE-US-00005 TABLE 5 HASE middle scale trial version 2-AKD emulsion with Hercobond? 1620 properties and stability results PolyDADMAC 1:1 dilution AKD AKD 14.5%, 1620 15.3%, Stearic 48 kg/h acid 0.73%, Tamol? 0.28% Original 32 C. emulsion 0 day 3 days 15 days 30 days 12 days Median 0.8871 0.8871 0.9899 0.9761 0.9139 1.0414 90% 1.2147 1.2147 1.6921 1.656 1.471 1.8562 2 um 100 100 94.917 95.49 97.713 92.526 Mean 0.9052 0.9052 1.0929 1.0725 0.9868 1.1654 SD 0.2316 0.2316 0.4906 0.4731 0.3861 0.5655 Viscosity 56.3 121.4
TABLE-US-00006 TABLE 6 HASE middle scale trial version 2-AKD emulsion with Hercobond? 1620 properties and stability results 1:1 dilution AKD AKD 16.21%, 1620 13.8%-15%, Stearic 64 kg/h acid 0.81%, Tamol? 0.15% Original 32 C. emulsion 0 day 3 days 15 days 30 days 12 days Median 0.8464 0.8464 0.8894 0.9702 0.9125 1.0058 90% 1.1419 1.1419 1.5282 1.6513 1.4794 1.8213 2 um 100 100 96.572 95.449 97.439 92.868 Mean 0.8619 0.8619 0.9843 1.0697 0.9911 1.1406 SD 0.2156 0.2156 0.458 0.4763 0.4022 0.5854 Vis- 57.1 280.9 cosity
TABLE-US-00007 TABLE 7 AKD emulsion with polyDADMAC properties and stability results PolyDADMAC 1:1 Dilution AKD flow TS % AKD (16.4%), PolyDADMAC (13.6%), PAC 48 kg/h (22.91) Stearic acid (0.76%), Tamol? (0.28%) (2%) Original 32 C. 32 C. emulsion 0 day 3 days 15 days 30 days 12 days 0 day 15 days 30 days 12 days Median 0.8318 0.8318 0.9502 1.1385 1.1775 Gel 0.8007 0.9653 0.9121 1.1107 90% 1.145 1.145 1.5781 2.4373 3.2434 Unstable 1.0962 1.624 1.5009 2.2189 2 um 100 100 96.668 83.167 75.038 Unstable 100 95.875 97.183 86.626 Mean 0.8519 0.8519 1.0338 1.3716 1.6371 Unstable 0.8171 1.0593 0.9952 1.3175 SD 0.2283 0.2283 0.4293 0.8626 1.3981 Unstable 0.2071 0.461 0.4141 0.7827 Viscosity 111 175.4 Unstable 36.7 64.8 66.9
TABLE-US-00008 TABLE 8 AKD emulsion with polyDADMAC properties and stability results PolyDADMAC 1:1 dilution AKD flow TS AKD (19.5%), PolyDADMAC (10.3%), PAC 64 kg/h (25.78%) Stearic acid (0.90%), Tamol? (0.20%) (2%) Original 32 C. 32 C. Emulsion 0 day 3 days 15 days 30 days 12 days 0 day 15 days 30 days 12 days Median 0.776 0.776 0.8972 1.27 1.433 2.2855 0.7239 0.9789 0.9726 1.1925 90% 1.024 1.0242 1.9961 3.0268 4.4441 6.4611 0.9963 1.6931 1.6785 2.715 2 um 100.00 100.000 90.046 74.424 63.217 44.917 100 94.827 95.13 79.459 Mean 0.784 0.7839 1.1011 1.6062 2.1198 3.0663 0.7332 1.0852 1.0773 1.4949 SD 0.184 0.1839 0.7568 1.1565 2.0079 2.8211 0.2043 0.4952 0.4829 1.0521 Viscosity 201.3 378.9 12.7 41.9 60.5 24.3
[0070] A size performance comparison with Hercules PTV? M5083, a typical starch product, was conducted using the process shown in
[0071] In addition, it was found that the particle size of the emulsion was highly dependent on the ratio of AKD and polymer. Using the HASE the polyDADMAC and Hercobond? 1620 produced acceptable emulsions with the polyDADMAC giving a lower average particle size. It was also found that the PAC help the stability of emulsion prepared with polyDADMAC. Results also indicated that adding stearic acid to the formulation resulted in lower PSD.
[0072] While the study indicated that an acceptable PSI) of the produced AKD/polyDADMAC and AKE)/Hercobond? 1620 emulsions, results indicated that the emulsion samples were unstable after 3 days storage at room temperature and an even shorter stability time at 32? C. But for on-site application, the emulsion quality was acceptable.
[0073] Besides, AKD emulsion was prepared through the turbine pump. The ASA was also tried. The table 9, 10 and 11 shows the emulsion results. The ASA was emulsified with good particle size distribution.
TABLE-US-00009 TABLE 9 ASA emulsion with polyDADMAC properties and stability results PolyDADMAC ASA:polyDADMAC:Tamol? ASA flow 64 kg/h 1:1:0.03 Original 30 60 Emulsion min min Median 0.563 0.58 0.573 90% 0.778 0.812 0.79 2 um 100 100 100 Mean 0.576 0.594 0.585 SD 0.154 0.162 0.155
TABLE-US-00010 TABLE 10 ASA emulsion with Hercobond? 1620 properties and stability results Hercobond? 1620 ASA:1620:Tamol? = ASA flow 64 kg/h 1:1:0 Original 30 60 Emulsion min min Median 0.53 0.540 0.536 90% 0.644 0.643 0.660 2 um 100 100.000 100.000 Mean 0.54 0.543 0.550 SD 0.107 0.110 0.108
Example 3Colloidal mill trial
[0074] The following study was done using a colloidal mill CRS 2000/05 from Shanghai SGN Machinery and Equipment Co., Ltd. An emulsification system was designed using the colloidal mill noted above and as shown in
[0075] In this study, water and Tamorim were added into the blending tank and mixed for 10 minutes at which time polymer liquid was added into the tank and pH was adjusted. The temperature of the mixture was raised to 60? C. at which time AKD was added to the blending tank and mixing continued for an additional 20 minutes, the system was started to cycle. After 1 cycle, a sample of the emulsion from the emulsion storage tank was acquired and measured. The process was continued for several cycles and once the mean particle size was measured and found to be about 1000 microns, another emulsion sample was acquired and diluted for fUrther stability testing. The emulsion was diluted by a factor of 4 and the temperature of the sampled emulsion dropped below 30? C. Circulation was continued until the mean particle size of the emulsion was below 800 micron or circulation time was more than 80 minutes. The colloidal mill was stopped, and the emulsion was collected for additional testing.
[0076] The study indicated AKD was easily emulsified when combined with Hercobonem 162.0 or polyDADMAC. The average particle size was between 0.70-0.90 mm after 1 to 6 times cycles. The Tamor to AKD ratio was fixed to 0.03:1. As shown in Table 11, 12, 13 and 14, the average particle size of the emulsion reached below 0.85 mm (850 pm) even when the ratio of AKD to Hercobond? 1620 was increased to 13.3:1, With the exception of Sample V, the emulsions were stable after 28 days in an oven stability test where the oven temperature was set at 32? C.
TABLE-US-00011 TABLE 11 Colloidal mill study - AKD emulsion samples with 15 kg Hercobond? 1620 AKD - 40 kg, Hercobond? 1620 - 15 kg, Stearic acid - 2 kg, Tamol? - 1.2 kg, water - 41.8 kg Sample 1 cycle 6 cycles 7 cylces no. V VI VII Median 1.0206 0.8006 0.7823 90% 1.6132 1.1064 1.0717 2 um 96.627 99.254 100.0000 Mean 1.0953 0.8226 0.8001 SD 0.4087 0.2146 0.2020
TABLE-US-00012 TABLE 12 Colloidal mill study - the diluted AKD emulsion sample from sample V V 4 times 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32 ? C. 32? C. 32? C. RT Median 1.0204 1.0544 1.0896 1.0785 1.1227 0.9916 90% 1.6403 1.8242 2.1299 2.7665 3.1432 1.6138 2 um 96.096 93.064 88.076 81.397 78.597 96.231 Mean 1.102 1.1719 1.2685 1.51 1.7047 1.0773 SD 0.4286 0.5424 0.7318 1.5485 2.0506 0.4369 pH 4.64-3.7 3.67 3.63 Viscosity 7.6 6.7 16.1 35.8 33.5 7.7 TS % 11.40 11.56/9.28 11.26/9.45
TABLE-US-00013 TABLE 13 Colloidal mill study - the diluted AKD emulsion sample from sample VI VI 4 times 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.8121 0.8351 0.8544 0.8415 0.8076 0.7965 90% 1.1246 1.1957 1.3044 1.3301 1.2957 1.1256 2 um 100 99.82 98.792 98.563 98.681 99.904 Mean 0.8357 0.8686 0.9115 0.9031 0.8667 0.8235 SD 0.221 0.2519 0.3325 0.3563 0.3574 0.2355 pH 4.46-3.80 3.93 4.06 Viscosity 8.8 7.9 14.5 14.9 13.3 6.6 TS % 11.44 11.47/ 11.4/ 10.41 10.39
TABLE-US-00014 TABLE 14 Colloidal mill study - the diluted AKD emulsion sample from sample VI VII 4 times 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.7876 0.7879 0.8037 0.7796 0.8328 0.7668 90% 1.0804 1.0965 1.1959 1.2389 1.3586 1.0743 2 um 100 100 99.555 98.857 97.857 100 Mean 0.8073 0.8108 0.8441 0.8341 0.9113 0.7888 SD 0.2053 0.216 0.2794 0.3373 0.4069 0.2165 pH 4.45-3.70 3.89 3.77 Vis- 8.1 6.8 12.8 14.5 10.7 cosity TS % 11.61 11.57/ 11.42/ 10.59 10.41
Example 4AKD emulsion samples with 20 polyDADMAC
[0077] The procedure described in Example 2 was used in this study. In this study two different ratios of AKD to polyDADMAC were evaluated. A ratio was 5:1 AK.D to polyDADMAC enabled the emulsion to reach a particle size below 0.9 mm (900 ?m) within 25 minutes. Results can be seen in Table 15, 16 and 17.
TABLE-US-00015 TABLE 15 Colloidal mill study - AKD with 20 kg polyDADMAC AKD - 40 kg, PolyDADMAC - 20.2 kg, Tamol? - 1.2 kg, water - 38.8 kg Sample 1 cycle 3 cycles no. I II Median 0.8352 0.7750 90% 1.2041 1.0573 2 um 99.797 100 Mean 0.8703 0.7931 SD 0.2561 0.1976
TABLE-US-00016 TABLE 16 Colloidal mill study - the diluted AKD emulsion sample from sample I I Dilution and PAC 3% 4 times 7 days 14 days 21 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.7727 0.766 0.983 2.332 0.764 0.759 0.782 0.7925 0.784 0.7801 0.756 90% 1.0541 1.074 4.237 10.442 1.087 1.031 1.0767 1.0883 1.114 1.1102 1.042 2 um 100 100 78.743 48.33 100 100 100 100 99.89 99.894 100 Mean 0.7905 0.789 1.984 4.239 0.790 0.777 0.803 0.8144 0.812 0.8082 0.777 SD 0.1976 0.217 2.105 4.450 0.226 0.1937 0.206 0.2065 0.235 0.2347 0.207 pH 3.86 3.35 3.97 3.86 3.93 Viscosity 14.5 14.2 142.2 760.8 13.8 10.8 10.2 10.4 10.3 10.5 11 TS % 12.83% 13.42/13.07% 14.32% 14.46/13.42% 14.98/13.95%
TABLE-US-00017 TABLE 17 Colloidal mill study - the diluted AKD emulsion sample from sample II II Dilution and PAC 3% 4 times 7 days 14 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.7941 4.2596 Gel 0.7829 0.7700 0.7854 0.8087 0.7694 0.7773 0.7789 90% 1.1208 10.9244 Unstable 1.0767 1.0679 1.1136 1.1346 1.1018 1.1076 1.1018 2 um 99.903 37.383 Unstable 100 100 99.878 99.875 99.883 99.885 99.905 Mean 0.8221 4.9629 Unstable 0.8041 0.7923 0.8153 0.8389 0.7986 0.8059 0.806 SD 0.232 4.4613 Unstable 0.2058 0.2086 0.2326 0.2334 0.236 0.2351 0.2292 pH 3.1 Unstable 4.01 3.84 3.84 Viscosity 13.4 114.8 Unstable 14.9 10.5 9.3 9.5 9.4 9.9 10.1 TS % 13.33% Unstable 13.90% 13.86/10.83 14.81/12.93
Example 5Colloidal mill studyAKD emulsion samples with 20 kg poivDADMAC and 2 kg stearic acid
[0078] The procedure described in Example 2 was used in this study. in this study a 5% stearic acid solution was added to AKD according to Tables 18, 19 and 20. Results show that the particle size distribution of the produced emulsion was decreased to the desired range in a shorter milling time indicating more efficient emulsification. The diluted emulsion samples were stable over the first week at 32? C. but became unstable after 7 days, As can be seen in Tables 19 and 20, the samples diluted with 3% PAC showed better stability.
TABLE-US-00018 TABLE 18 Colloidal mill study - AKD with 20 kg polyDADMAC and 2 kg stearic acid AKD - 40 kg, PolyDADMAC - 20 kg, Stearic acid - 2 kg, Tamol? - 1.2 kg, water - 36.8 kg Sample 1 cycle 3 cycles no. III IV Median 0.7577 0.7059 90% 1.0452 0.9547 2 um 100 100 Mean 0.7726 0.7137 SD 0.2024 0.1755
TABLE-US-00019 TABLE 19 Colloidal mill study - the diluted AKD emulsion sample from sample III III Dilution and PAC 3% 4 times 7 days 14 days 21 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.765 0.742 0.9606 Gel 0.75 0.748 0.758 0.7549 0.743 0.7675 0.748 90% 1.058 1.033 3.983 Unstable 1.03 1.020 1.041 1.0336 1.035 1.0797 1.045 2 um 100 100 80.80 Unstable 100 100 100 100 100 100 100 Mean 0.785 0.764 1.777 Unstable 0.768 0.767 0.779 0.7746 0.766 0.7944 0.771 SD 0.207 0.208 2.361 Unstable 0.201 0.196 0.199 0.197 0.208 0.216 0.211 pH 3.52 3.21 Unstable 3.79 3.8 3.84 Viscosity 14.1 13.6 315.4 Unstable 14.4 11.7 10 11 10.2 10.1 10.5 TS % 12.72 12.76/11.79 Unstable 13.76 13.67/12.45 13.9/12.7
TABLE-US-00020 TABLE 20 Colloidal mill study - the diluted AKD emulsion sample from sample IV IV Dilution and PAC 3% 4 times 7 days 14 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.7212 0.7175 Gel 0.7406 0.7159 0.7169 0.7259 0.7179 0.7251 0.7312 90% 0.9706 0.9877 Unstable 0.969 0.9639 0.9733 0.989 0.9843 0.9877 1.0221 2 um 100 100 Unstable 100 100 100 100 100 100 100 Mean 0.7355 0.7369 Unstable 0.7273 0.7299 0.7335 0.7444 0.7364 0.7434 0.7549 SD 0.1768 0.194 Unstable 0.1838 0.1752 0.1828 0.1896 0.191 0.1912 0.2101 pH 3.63 Unstable 3.85 3.8 3.78 Viscosity 14.2 14.3 Unstable 9.8 9.9 10.7 9.6 10.1 10.7 TS % 12.58 Unstable 28 days 13.53 13.62/12.13 13.73/13.03 32? C.
Example 6Colloidal studyAKD emulsion samples with 15 kg polyDADMAC,
[0079] The procedure described in Example 2 was used in this study. This study was done using a 7,5:1 ratio (AKD/polyDADMAC). Results can be seen in Tables 21, 22 and 24. The mean particle size of AKD emulsion was about 0.9-1.0 mm (900-1,000 ?m) after 45 minutes of circulation through the system.
TABLE-US-00021 TABLE 21 Colloidal study -AKD with 15 kg polyDADMAC AKD - 45 kg, PolyDADMAC - 15 kg, Tamol? - 1.35 kg, water - 38.65 kg Sample 1 cycle 4 cycles no. X XI Median 0.9798 0.9148 90% 1.4951 1.3159 2 um 97.83 99.345 Mean 1.044 0.9579 SD 0.3838 0.2864
TABLE-US-00022 TABLE 22 Colloidal study - the diluted AKD emulsion sample from sample X X Dilution and PAC 3% 4 times 7 days 14 days 21 days 28 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.948 0.889 0.966 0.949 0.918 0.897 0.944 0.891 0.9243 0.900 0.947 0.821 90% 1.387 1.351 1.596 1.683 1.612 1.401 1.455 1.345 1.4109 1.404 1.463 1.229 2 um 99.04 98.89 96.237 94.76 95.77 98.43 97.89 98.94 98.466 98.34 97.95 99.46 Mean 0.995 0.944 1.056 1.063 1.017 10.958 1.013 0.944 0.9834 0.964 1.013 0.866 SD 0.305 0.325 0.446 0.523 0.487 0.354 0.369 0.320 0.3425 0.354 0.363 0.286 pH 4.1 3.38 3.35 4.04 3.82 3.98 Viscosity 11.1 10.2 23.5 23.6 27.5 11.3 8.3 7.8 7.6 7.6 7.4 10.5 TS % 12.65 12.87/11.75 12.72/12.15 13.57 14.42/10.57 13.92/11.14
TABLE-US-00023 TABLE 23 Colloidal study - the diluted AKD emulsion sample from sample XI XI Dilution and PAC 3% 4 times 7 days 14 days 21 days 28 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.908 0.835 0.916 0.893 0.913 0.871 0.861 0.836 0.876 0.853 0.859 0.864 90% 1.29 1.218 1.468 1.548 1.565 1.303 1.241 1.215 1.276 1.240 1.274 1.273 2 um 99.53 99.66 97.59 96.06 96.18 99.10 99.66 99.67 99.478 99.60 99.40 99.47 Mean 0.946 0.873 0.990 0.999 1.010 0.921 0.899 0.874 0.918 0.892 0.904 0.907 SD 0.270 0.268 0.395 0.492 0.470 0.310 0.264 0.265 0.280 0.27 0.290 0.285 pH 3.96 3.34 3.39 4.01 3.9 3,84 Viscosity 11.1 10.8 16.4 27 29.8 11.7 8.4 7.9 8.1 8.1 8.3 12.3 TS % 12.91 10.00/11.61 11.04/10.89 13.89 14.61/11.40 14.16/11.75
Example 7Colloidal mill studyAKD emulsion samples with 15 kg polyDADMAC and 2.22 kg stearic acid
[0080] The procedure described in Example 2 was used in this study. in this study, stearic acid was added to the polyDADMAC in forming the emulsions, The AKD wax granules were added to the system when the colloid mill began circulation of the mixture. With the heat generated by the emulsification process, the AKD was melted and well emulsified. The temperature of the water phase was such that the AKD wax was added directly to emulsification process, thus eliminating a heating step.
[0081] It was found with the addition of stearic acid to the formulation, the desired mean particle size and particle size distribution was easily achieved. The stability study showed the samples of the diluted emulsion were stable for 2 to 3 weeks at 32? C. The diluted emulsion samples that included PAC were also found to have the desired stability. Results can be seen in Tables 24, 25 and 26.
TABLE-US-00024 TABLE 24 Colloidal mill study - AKD with 15 kg polyDADMAC and 2.22 kg stearic acid AKD - 45 kg, PolyDADMAC - 15 kg, Stearic acid - 2.25 kg, Tamol? 1.35 kg, water - 36.4 kg 15 min recycling and 30 min sampling Sample sampling 6.1 l/min 6.1 l/min no XII XIII Median 0.8252 0.8067 90% 1.2037 1.1406 2 um 99.566 99.852 Mean 0.866 0.8383 SD 0.2682 0.2401
TABLE-US-00025 TABLE 25 Colloidal mill study - the diluted AKD emulsion sample from XII XII Dilution and PAC 3% 4 times 7 days 14 days 21 days 28 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.823 0.755 0.795 0.869 0.839 0.845 0.771 0.766 0.794 0.803 0.791 0.754 90% 1.141 1.059 1.163 2.503 3.664 1.043 1.067 1.079 1.134 1.179 1.152 1.065 2 um 99.90 100 99.65 87.1 83.10 99.79 100 100 99.85 99.61 99.66 100 Mean 0.851 0.778 0.833 1.738 1.657 0.867 0.793 0.791 0.826 0.843 0.829 0.778 SD 0.230 0.214 0.268 1.703 2.502 0.222 0.207 0.219 0.243 0.269 0.265 0.218 pH 3.77 3.38 3.39 3.95 3.68 3.63 Visc. 11.1 11.2 18.8 82 78.9 12.3 10.4 8.9 12.1 14.1 14.8 10.2 TS % 13.55 13.34/12.07 13.57/13.01 14.32 14.21/13.71 14.46/13.69 Assay % 10.07 9.29 9.07 9.53 9.08 9.30
TABLE-US-00026 TABLE 26 Colloidal mill study - the diluted AKD emulsion sample from XIII XIII Dilution and PAC (3%) 4 times 7 days 14 days 21 days 28 days 28 days 7 days 14 days 21 days 28 days 28 days dilution 0 day 32? C. 32? C. 32? C. 32? C. RT 0 day 32? C. 32? C. 32? C. 32? C. RT Median 0.7959 0.77 0.801 0.8959 gel 0.793 0.767 0.762 0.788 0.7758 0.781 0.785 90% 1.0913 1.06 1.195 6.332 Unstable 1.092 1.038 1.059 1.122 1.121 1.130 1.020 2 um 100 100 99.38 75.44 Unstable 100 100 100 99.86 99.84 99.83 100 Mean 0.8176 0.79 0.846 2.226 Unstable 0.829 0.785 0.785 0.819 0.808 0.814 0.785 SD 0.2067 0.21 0.287 3.190 Unstable 0.218 0.192 0.208 0.237 0.246 0.249 0.209 pH 3.8 3.37 Unstable 3.93 3.66 3.68 Viscosity 12.1 11.6 22.3 625.9 Unstable 12.8 8.5 9.3 12.6 18.5 18.7 11.5 TS % 13.74 13.66/13.27 Unstable 14.58 14.67/13.12 14.64/13.67 Assay % 10.16 9.54 Unstable 9.74 9.47 9.32
Example 8Colloidal mill studyparaffinic wax emulsion samples with 15 kg polyDADMAC and 2.22 kg stearin; acid
[0082] In addition to the emulsification of AKD wax, paraffinic wax was emulsified with potyDADMAC and lignin sulfonate through the colloid mill described above. Table 27 shows the physical properties of the emulsions after preparation and after storage for 1 week. The emulsion showed good particle size distribution after going through 2 cycles of the emulsification process.
TABLE-US-00027 TABLE 27 Colloidal mill study - paraffinic wax emulsion prepared with polyDADMAC 20% PolyDADMAC, 40% Wax Dilution, F66H, 1.2% Lignin Sulfonate PAC1460 (1%) 1 2 23? C. cycle cycles 1 week Median 0.8545 0.7939 0.7951 0.8554 90% 1.4567 1.2294 1.229 1.3361 2 um 98.245 99.275 99.409 98.797 Mean 0.9032 0.8439 0.8422 0.915 SD 0.3267 0.308 0.3048 0.337 pH 6.88 6.9 6.98 Viscosity 95.6 120.2 36.4
Example 9Sizing Study
[0083] After the stability test, a number of AKD emulsion samples stored at room temperature were selected and a sizing performance comparison was accomplished comparing the AKD emulsion samples with PTV? M5083 (starch) samples with 1?'&W and OCC furnish, respectively. In general, the AKD emulsion prepared in the trial showed a comparable size performance with PTV? M5083 (see
[0084] In P&W system, PTV? M5083 showed better sizing performance than when the AKD emulsion was prepared at 7.5 kg/ton. When the dosage increased, the AKD prepared with Hercobond? 1620, showed a comparable size performance with PTV' M5083 (typical AKI) emulsion with starch). However, the AKD emulsion prepared with polyDADMAC, showed poorer size performance. Although not to be bound by theory, this is likely caused by the high charge of polyDADMAC.
Example 10Colloidal mill studyAKD wax emulsion samples with 15 kg PAK resin In addition, PolyDADMAC and amphoteric PAM emulsifying AKD wax, PAE
[0085] (polyamide-epichlorohydrin) and Tamol through the colloid mill described above. Table 27 shows the physical properties of the emulsions after preparation and after storage for 2, 4 weeks. The emulsion showed good particle size distribution after going through 2 cycles of the emulsification process.
TABLE-US-00028 TABLE 28 Colloidal mill study - AKD wax emulsified with PAE resin 16.5% PAE, 40% AKD wax, 1.2% Tamol 1 2 32? C. 23? C. cycle cycles 2 weeks 1 week Median 0.8245 0.6134 0.7396 0.7418 90% 1.4367 0.9006 1.13 1.12 2 um 98.245 100 99.284 99.685 Mean 0.8832 0.6187 0.7919 0.7817 SD 0.3276 0.2234 0.3918 0.37 pH 3.65 3.70 3.82 Viscosity 10.3 9.30 10.5
[0086] While at least one exemplary embodiment has been presented in the foregoing detailed description of the inventive subject matter, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the inventive subject matter in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the inventive subject matter. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the inventive subject matter as set forth in the appended claims.