AGRICULTURAL COMPOSITION CONTAINING SI CLAY AND A BASE

Abstract

The invention relates to a process of treating a plant which applies an agricultural composition which contains Si clay granules or powders and a base wherein the composition is applied in an amount from about 150 pounds to about 4,000 pounds per acre. The invention also relates to an agricultural composition containing Si clay granules or powders and a base wherein the composition can be applied in an amount from about 150 pounds to about 4,000 pounds per acre.

Claims

1. An agricultural composition comprising Si clay granules or Si clay powders and a base wherein the composition would be applied in an amount from about 150 pounds to about 4,000 pounds per acre and with the proviso composition does not contain an insecticide.

2. A process of treating a plant which comprises applying an agricultural composition which consisting essentially of Si clay granules or Si clay powders wherein the composition is applied in an amount from about 150 pounds to about 4,000 pounds per acre and said Si clay granules or powders are present in the agricultural composition in an amount from about 10% to about 90% by weight based on the amount of the composition and with the proviso that the composition does not contain a compound of the formula (I) ##STR00003## wherein, A is —CH.sub.2—CH.sub.2— or —CH═CH—; R.sup.1 is halogen; and R.sup.2 is hydrogen, formyl, cyano, hydroxy, NH, C.sub.1-C.sub.6 alkyl (optionally substituted by aryl, aryloxy, heteroaryl or hetero-cyclyl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy), C.sub.1-C.sub.6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C.sub.1-C.sub.4-alkoxy, tri(C.sub.1-C.sub.4 alkyl)silyloxy C.sub.1-C.sub.2 alkylcarbonyloxy, and C.sub.3-C.sub.5 alkenyl), C.sub.1-C.sub.6 cyanoalkyl, C.sub.1-C.sub.6 alkoxy(C.sub.1-C.sub.6) alkyl (optionally substituted by aryl or heteroaryl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, and C.sub.1-C.sub.4 alkoxy), C.sub.1-C.sub.4 alkoxy(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl, C.sub.1-C.sub.6 alkylcarbonyl(C.sub.1-C.sub.6)alkyl, C.sub.1-C.sub.4 alkoxyimino(C.sub.1-C.sub.4)alkyl, C.sub.1-C.sub.4 haloalkoxy(C.sub.1-C.sub.4)alkyl, C.sub.1-C.sub.6 alkoxycarbonyl(C.sub.1-C.sub.6)alkyl, C.sub.1-C.sub.4 alkoxy(C.sub.1-C.sub.4) alkoxycarbonyl(C.sub.1-C.sub.6)alkyl, hydroxycarbonyl(C.sub.1-C.sub.6)alkyl, aryloxycarbonyl(C.sub.1-C.sub.6)alkyl (wherein the aryl group can be optionally substituted by one or two substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy), C.sub.1-C.sub.4 alkylaminocarbonyl(C.sub.1-C.sub.6)alkyl, di(C.sub.1-C.sub.4 alkyl)aminocarbonyl(C.sub.1-C.sub.6)alkyl, C.sub.1-C.sub.4haloalkylaminocarbonyl(C.sub.1-C.sub.6)alkyl, di(C.sub.1-C.sub.4 haloalkyl)aminocarbonyl-C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.2 alkoxy(C.sub.2-C.sub.4)alkylaminocarbonyl(C.sub.1-C.sub.4)alkyl, C.sub.2-C.sub.6 alkenyloxycarbonyl (C.sub.1-C.sub.6) alkyl, C.sub.3-C.sub.6 alkynyloxycarbonyl(C.sub.1-C.sub.6)alkyl, (R.sup.3O).sub.2(O═)P(C.sub.1-C.sub.6)alkyl where R.sup.3 is hydrogen, C.sub.1-C.sub.4 alkyl or benzyl, C.sub.3-C.sub.7 cycloalkyl (optionally substituted by one to three substituents independently selected from C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy and, additionally, one of the ring member units can optionally represent C═O or C═NR.sup.4 where R.sup.4 is hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 cyanoalkyl, C.sub.1-C.sub.4 alkoxy, or C.sub.3-C.sub.6 cycloalkyl), C.sub.3-C.sub.7 halocycloalkyl, C.sub.3-C.sub.7 cycloalkenyl (optionally substituted by one or two substituents independently selected from C.sub.1-C.sub.4 alkyl, and C.sub.1-C.sub.4 haloalkyl, and, additionally, one of the ring member units can optionally represent C═O), C.sub.3-C.sub.7 halocycloalkenyl, C.sub.1-C.sub.6 alkyl-S(═O)n.sup.1(C.sub.1-C.sub.6)alkyl where n.sup.1 is 0, 1 or 2 (optionally substituted by aryl or heteroaryl or heterocyclyl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy), C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl, aryl(C.sub.3-C.sub.6)alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.3-C.sub.6 haloalkynyl, aryl(C.sub.3-C.sub.6)alkynyl, C.sub.3-C.sub.6hydroxyalkynyl, C.sub.1-C.sub.6 alkoxycarbonyl (optionally substituted by one to three substituents independently selected from halogen, hydroxy, cyano, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl, and aryl), aryloxycarbonyl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy), C.sub.3-C.sub.6 alkenyloxycarbonyl, C.sub.3-C.sub.6alkynyloxycarbonyl, C.sub.1-C.sub.6alkylcarbonyl, C.sub.1-C.sub.6haloalkylcarbonyl, aminocarbonyl, C.sub.1-C.sub.6alkylaminocarbonyl, di(C.sub.1-C.sub.6)alkylaminocarbonyl, aminothiocarbonyl, C.sub.1-C.sub.6alkylaminothiocarbonyl, di(C.sub.1-C.sub.6)alkylaminothiocarbonyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6 alkenyloxy, C.sub.3-C.sub.8alkynyloxy, aryloxy (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, and C.sub.1-C.sub.4alkoxy), C.sub.1-C.sub.6alkylamino, di(C.sub.1-C.sub.6)alkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkylsulfonyl, aryl-S(═O)n.sup.2 (optionally substituted by one or two substituents independently selected from halogen, nitro, and C.sub.1-C.sub.4alkyl) where n.sup.2 is 0, 1 or 2, aryl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, and C.sub.1-C.sub.4haloalkoxy), heteroaryl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, and C.sub.1-C.sub.4haloalkoxy), heterocyclyl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, and C.sub.1-C.sub.4haloalkoxy, and, additionally, a ring member unit can optionally represent C═O or C═NR.sup.5 where R.sup.5 is hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 cyanoalkyl, C.sub.1-C.sub.4 alkoxy, or C.sub.3-C.sub.6 cycloalkyl), (C.sub.1-C.sub.6 alkylthio)carbonyl, (C.sub.1-C.sub.6 alkylthio)thiocarbonyl, C—C alkyl-S(═O)n.sup.3 (═NR.sup.6)—C.sub.1-C.sub.4alkyl wherein R.sup.6 is hydrogen, cyano, nitro, C.sub.1-C.sub.4alkyl and n.sup.3 is 0 or 1, or R.sup.2 represents a group “—C(R.sup.7)(R.sup.8)(R.sup.9)” wherein R.sup.7 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, or cyclopropyl, R.sup.8 is hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, or cyclopropyl, preferably hydrogen, R.sup.9 is cyano, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.5 alkynyl, C.sub.2-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkylaminocarbonyl, di(C.sub.1-C.sub.3 alkyl)aminocarbonyl, C.sub.1-C.sub.2haloalkylaminocarbonyl, C.sub.3-C.sub.6alkenyloxycarbonyl, C.sub.3-C.sub.4 alkynyloxycarbonyl, or C.sub.1-C.sub.3 alkylcarbonyl; (arylthio)carbonyl(C.sub.1-C.sub.6)alkyl(wherein aryl can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy), (C.sub.1-C.sub.3 alkylthio) carbonyl (C.sub.1-C.sub.6) alkyl (optionally substituted by aryl or heteroaryl or heterocyclyl, which themselves can be optionally substituted by one to three substituents indepen-dently selected from halogen, cyano, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and C.sub.1-C.sub.4 alkoxy), or an agrochemically acceptable salt, N-oxide or isomer thereof.

3. The process as claimed in claim 2, wherein the composition is applied in an amount from about 250 to about 2000 pounds per acre.

4. The process as claimed in claim 2, wherein the composition is applied in an amount from about 250 to about 700 pounds per acre.

5. The process as claimed in claim 2, wherein the base is selected from the group consisting of potassium hydroxide, potassium thio sulfate, ammonium thio sulfate, calcium chloride, potassium carbonate, Tri potassium phosphate, di-potassium phosphate, di-potassium phosphyte, fulvic acid, carboxylic acid, humic acid, CORON®, SOLUBOR® and Urea.

6. The process as claimed in claim 2, wherein the composition further comprises A) a fertilizer, B) a pH increaser, C) macronutrients or D) micronutrients.

7. The process as claimed in claim 2, wherein the pH increaser is present.

8. The process as claimed in claim 2, wherein the macronutrient is present and is nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium.

9. The process as claimed in claim 2, wherein the micronutrient is present and is a water soluble salt of boron, iron, manganese, magnesium, copper or zinc.

10. The process as claimed in claim 2, wherein composition is applied to the ground by a band application, broadcast application or strip placement application.

11. The process as claimed in claim 2, wherein composition is applied within 30 days after the ground has been fertilized.

12. The process as claimed in claim 2, wherein said Si clay granules or powders are present in the agricultural composition in an amount from about 10% to about 90% by weight based on the amount of the composition.

13. The process as claimed in claim 2, wherein said Si clay granules or powders are present in the agricultural composition in an amount from about 40% to about 60% by weight based on the amount of the composition.

14. The process as claimed in claim 2, wherein said Si clay granules or powders are present in the agricultural composition in an amount from about 40% to about 60% by weight based on the amount of the composition.

15. The process as claimed in claim 2, wherein the Si clay is attapulgite, montmorillonite or aluminosilicate or a mixture thereof.

16. The process as claimed in claim 2, wherein the plant is grass crops, turf crops, cucurbit crops, Brassica crops, solanaceae crops, bush berries, citrus, stone fruits, nuts, ornamental crops, apples, avocado, mangos, lychee or olives.

17. A process of treating a plant which comprises applying an agricultural composition which consisting essentially of Si clay granules or Si clay powders wherein the composition is applied in an amount from about 150 pounds to about 4,000 pounds per acre and with the proviso that the composition does not contain an insecticide.

18. The process as claimed in claim 2, wherein Si clay granules or powders are present in the agricultural composition in an amount from about 10% to about 90% by weight based on the amount of the composition.

Description

A BRIEF DESCRIPTION OF THE FIGURE

[0064] FIG. 1 illustrates the results of a laboratory evaluation using the “5 Day Method,” a laboratory method designed to evaluate calcium silicate slag sources and is the standard for comparing dry Si sources. Wollastonite, a natural source of CaSiO3, is known to have high levels of plant available Si and is often used as a standard with regards to Si sources. In this evaluation, the Wollastonite expressed 4.46% plant available Si. The red dotted line is at 0.2% Si and materials that evaluate below this threshold are not worthwhile as a Si source. The base treatment, “AB” expressed % Si levels approaching the Wollastonite. ACA, citric acid treatment; AMn, nitric acid treatment; AUT, untreated.

[0065] FIG. 2 illustrates the data according to the invention. As shown, the base option (top line) is 5× the CSS, which is calcium silicate slag.

[0066] FIGS. 3 and 4 illustrate the data according to the invention. The reference to first, second, third, fourth fifth and sixth represents the order of sample evaluation shown also in Table 2.

A DETAILED DESCRIPTION OF THE INVENTION

[0067] The invention relates to an agricultural composition comprising Si clay granules and a base which can be applied to the soil in an in an amount from about 150 pounds to about 4,000 pounds per acre, preferably about 250 pounds to about 2,000 pounds per acre and ever more preferably from about 300 pounds to about 750 pounds per acre and most preferably about 400 pounds to about 700 pounds per acre. The agricultural composition can be applied after the soil has been fertilized. Preferably, the first application would be less than 90 days after the soil has been fertilized, preferably less than 60 days, and more preferably less than 30 and most preferably less 15 days. The agricultural composition can be also applied in more than one applications (multiple applications) for the planting cycle. For example, the agricultural composition can be applied in at least 1, 2, 3, 4, 5, 6, 7 or 8 applications.

[0068] The agricultural composition contains a base as described above.

[0069] The agricultural composition can also contain a fertilizer. The agricultural composition also does not require a fertilizer and exclude a fertilizer.

[0070] The invention relates to a fertilizer composition comprising a fertilizer and Si clay granules wherein the Si clay is an amount from about 10 to about 90% by weight based on the total amount of the fertilizer and Si clay.

[0071] The fertilizer composition can be used for plants such as, but not limited to grass crops, turf crops, cucurbit crops, Brassica crops, solanaceae crops, bush berries, citrus, stone fruits, nuts, ornamental plants other crops.

[0072] Grass crops include but are not limited to barley, maize (corn), oats, rice, rye, sorghum, wheat, millet, sugar cane or bamboo.

[0073] Turf crops include but are not limited to Bermuda grass, St. Augustine grass, Zoysia grass, Kentucky bluegrass reed grass, meadow foxtail, pampas grass, sedge, blue fescue, papyrus, fountain grass or Perennial ryegrass.

[0074] Cucurbit crops include but are not limited to pumpkin, squash, zucchini, cucumber, watermelon or gourd.

[0075] Brassica Crops include but are not limited to cabbage, cauliflower, broccoli, mustard, brussel sprouts, turnips/turnip greens, collards, kale or bok choy.

[0076] Solanaceae crops include but are not limited to tomatoes, tomatillos, eggplant, potatoes, goji berries, tobacco, peppers (bell peppers, chili peppers, paprika, tamales, tomatillos, pimentos, cayenne, etc).

[0077] Bush berries, such as, but not limited to, strawberry, blueberry, blackberry, raspberry, mulberry, elderberry, red currants, white currants, and black currents.

[0078] Citrus, such as, but not limited to, citron, clementine, grapefruit, oranges, sudachi, shonan gold, satsuma, tangelo, tangerine, limetta, tangor, lemons, limes, citron, yuzu or ugli fruit.

[0079] Stone fruits, such as, but not limited to peaches, nectarines and plums would also work.

[0080] Nuts, such as, but not limited to peanut and almond would also work.

[0081] Ornamental plants include but are not limited to rose bushes, tree roses, climbing roses, miniature roses and shrub roses in any color, lilies, tulips, daffodils and onion plants. Japanese maple, along with many other varieties of maple, weeping willow, birch magnolia, pear, cherry, apple and lilac. Conifers which include evergreen trees and shrubs that remain green throughout the season. Weigela, barberry, camellia, lilac maple, dogwood, holly, aromatic herbs such as but not limited to mint, sage, lavender, marigold, thyme, basil and rosemary.

[0082] Other crops such as, but not limited to apples, avocado, mangos, lychee and olives.

[0083] The fertilizer can be any fertilizer such as a fertilizer containing Nitrogen, Phosphorous and potassium (K) referred to as “NPK” or a fertilizer which does not contain any nitrogen referred to as a XPK. The fertilizer can contain boron, zinc, copper, and iron, blends of nitrogen phosphorous and potash or mixtures thereof.

[0084] The fertilizer can be ammonia sulfate, an ammonia salt of a carboxylic acid, mono- or di-potassium phosphate, a micronutrient, ammonia nitrate, urea, ammonia citrate or ammonia acetate.

[0085] The Si clay can be any Si clay. The Si clay is preferably, Agsorb® which is granules that include Montmorillonite from Ripley Miss. or from Mounds Ill., Attapulgite from Ochlocknee Ga., Hydrous Aluminosilicate from Taft, Calif. and Verge™ also from Oil-Dri.

[0086] Prior to the invention it was known to use a conditioner such as Si clay up to 100 pounds per ton fertilizer. I have found that it is much better to increase the amount of Si clay and it should be in an amount from about 200 to about 1800 pounds to the ton fertilizer. Another words the amount of the Si clay is from about 10% by weight to about 90% by weight, and preferably from 20 to 60% by weight and most preferably 40 to 60% weight of the total weight of fertilizer and Si.

[0087] Optional components can be pH increaser and micronutrients.

[0088] The composition can contain micronutrients such as, but not limited to a water soluble salt of boron, iron, manganese, magnesium, copper or zinc.

[0089] The fertilizer composition according to the invention should be applied to the soil in an amount from about 150 pounds to about 4,000 pounds per acre, preferably about 250 pounds to about 2,000 pounds per acre and ever more preferably from about 300 pounds to about 750 pounds per acre and most preferably about 400 pounds to about 700 pounds per acre.

[0090] Sugarcane fertilization requires around 600 pounds of custom fertilizer at planting and 200-300 pounds 3-5 times through the crop cycle (12 months). I was able to incorporate this SiO.sub.2 product with the fertilizer blend in any of these application slots and therefore take advantage of the timing and rate piece of the input strategy.

Examples

[0091] I had the following ingredients mixed as shown in Table 4 below:

TABLE-US-00004 TABLE 4 Ingredients AB AMn ACA AUT water 415 877 1113 1965 0-0-41 1480 205 500 0 Mn EDTA 50 883 332 0 Asset RS 20 20 20 0 AdSpray 101 35 35 35 35 Total pounds 2000 2000 2000 2000

[0092] Agricultural silicon (AgSi)=400 pounds treatment+1600 pounds of Agsorb

[0093] AB=base (potassium hydroxide); potassium hydroxide and carboxylic acid were mixed into a solution and impregnated to the AgSorb to result in a treated granular product with a pH of 10-11, resulting in AgSi B.

[0094] AMn=nitric acid; nitric acid and carboxylic acid were mixed into a solution and impregnated to the AgSorb to result in treated granular product with a pH of 3-4, resulting in AgSi IA.

[0095] ACA=citric acid; citric acid and carboxylic acid were mixed into a solution and impregnated to the AgSorb to result in treated granular product with a pH of 3-4, resulting in AgSi OA.

[0096] AUT=untreated.

[0097] Field trials (data) clearly suggest that the plant tissue silicon levels track similarly in sugarcane with either calcium silicate slag (grower standard) at 3 tons per acre, or AgSi, an acid treated montmorillonite or attapulgite granule, at 750 pounds per acre. Even so, when evaluated with the most accepted method determining plant available Si, (SiO2), in dry products, the “5 Day Method” renders results inconsistent with the field trials.

[0098] The field trial data is shown in the Figure.

[0099] Wollastonite=standard;

[0100] The AgSi treated with KOH extracted levels of Si similar to the Wollastonite (see FIG. 1).

[0101] The procedure of the Dis-solution Trial (DSS) trial was to take 50 grams of the treated material and add 200 ml of distilled water and allow hydrolysis to act upon the material over time with agitation. As a part of the procedure, all treatments were shaken regularly and consistently across several days between samples. All samples treated the same. Solution samples (50 ml) were drawn from the clear solution part of the treatment for evaluation, then replaced with 50 ml of distilled water in order to initiate the next step of the DSS. This is shown in FIG. 2.

[0102] As shown in FIGS. 2-4, the reference to first, second, third, fourth fifth and sixth represents the order of sample evaluation. Samples were evaluated for SiO2 (available Silicon), pH, Manganese and Potassium. There are four treatments, untreated (UT), base (B), nitric acid (NA) and calcium silicate slag (CSS), which is the grower standard.

[0103] All treatments were significantly higher than the (CSS), with the (B) results average 5 times the extracted Si from the grower standard (CSS).

[0104] It is important to note that the base source has potassium derived from potassium hydroxide. Not only does this source in the planting environment serve to release available Si from the AgSorb granule, but also serve to map the effect of the treatment on the Ag Sorb granule with respect to Si release, (which is the primary component of AgSorb, 70.8% SiO2). Potassium is not present in raw AgSorb from Georgia. So when considering these FIGS. 2-4, the trend of the release of Si to mirror the release of K.sub.2O, indicating the base treatment serves to render available Si from a source thought not to have available (Si).

[0105] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “10% to 90%, is inclusive of the endpoints and all intermediate values of the ranges of “10 to 90” etc.). Again, when ranges are listed in the specification and in the claims, it is understood that all the numbers including decimals within the range are included whether specifically disclosed. For example, if the range is from 1 to 10, the range would include every number within the range, such as 1; 1.1; 1.2; 1.3; 1.4; 1.5; 1.6; 1.7; 1.8; 1.9; 2; 2.1; 2.2; 2.3; 2.4; 2.5; 2.6; 2.7; 2.8; 2.9; 3; 3.1; 3.2; 3.3; 3.4; 3.5; 3.6; 3.7; 3.8; 3.9; 4; 4.1; 4.2; 4.3; 4.4; 4.5; 4.6; 4.7; 4.8; 4.9; 5; 5.1; 5.2; 5.3; 5.4; 5.5; 5.6; 5.7; 5.8; 5.9; 6; 6.1; 6.2; 6.3; 6.4; 6.5; 6.6; 6.7; 6.8; 6.9; 7; 7.1; 7.2; 7.3; 7.4; 7.5; 7.6; 7.7; 7.8; 7.9; 8; 8.1; 8.2; 8.3; 8.4; 8.5; 8.6; 8.7; 8.8; 8.9; 9; 9.1; 9.2; 9.3; 9.4; 9.5; 9.6; 9.7; 9.8; 9.9 and 10.

[0106] “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “a” and “an” and “the” herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the film(s) includes one or more films). Reference throughout the specification to “one embodiment”, “another embodiment”, “an embodiment”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0107] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0108] Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes.

[0109] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

[0110] All the references described above are incorporated by reference for all useful purposes.