| US7846556B2 | 2010-12-07 | |||
| US20080312111A1 | 2008-12-18 | |||
| US20050064196A1 | 2005-03-24 | |||
| US20110059876A1 | 2011-03-10 | |||
| US20070117244A1 | 2007-05-24 | |||
| US20070134468A1 | 2007-06-14 |
| CLAIMS What is claimed is: 1. A textured surface comprising: (a) a surface with textured features, (b) wherein the features are adapted to enhance the effectiveness of a nano-particle lubricant, and wherein the features are formed by one or more processes selected from the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition, (c) wherein the textured features comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material, (d) a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface, (e) wherein the nano-particle lubricant comprises at least one member selected from the group consisting of: (i) solid nano-particles, (ii) a layered nano-particle macro-composition, (iii) a bonded plurality of layered nano-particle macro-compositions, (iv) nanoparticles having an open-ended architecture and comprising an organic medium intercalated in the nanoparticle, (v) a nanoparticle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer, and (vi) a plurality of nanoparticle inner nuclei, on each nucleus, an outer layer intercalated with the nucleus or encapsulating the nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond, (f) a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface, the tribo-film comprising at least one of a phosphorus- containing compound, a phosphide, a boron-containing compound, and a boride, (g) wherein the tribo-film comprises at least a component of the nano-particle lubricant, (h) wherein the size of one or more of the textured features is a multiple of the size of a unit of the nano-particle lubricant, and (i) wherein the surface comprises a substrate with a layer of material deposited over the substrate, and wherein the textured features expose parts of the substrate. 2. A textured surface comprising: (a) a surface with textured features, and (b) wherein the features are adapted to enhance the effectiveness of a nano-particle lubricant, and (c) a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface. 3. The textured surface in claim 2, wherein the textured features comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material. 4. The textured surface in claim 2, further comprising textured features that are formed by one or more processes selected from the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition. 5. The textured surface in claim 1, wherein the nano-particle lubricant comprises molybdenum disulfide. 6. The textured surface in claim 2, wherein the nano-particle lubricant comprises at least one member selected from the group consisting of: (i) solid nano-particles, (ii) a layered nano-particle macro-composition, (iii) a bonded plurality of layered nano-particle macro-compositions, (iv) nanoparticles having an open-ended architecture and comprising an organic medium intercalated in the nanoparticle, (v) a nanoparticle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer, and (vi) a plurality of nanoparticle inner nuclei, on each nucleus, an outer layer intercalated with the nucleus or encapsulating the nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond. 7. The textured surface in claim 2, further comprising a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface. 8. The textured surface in claim 7, wherein the tribo-film comprises at least one of a phosphorus-containing compound and a phosphide, a boron-containing compound, and a boride. 9. The textured surface in claim 7, wherein the tribo-film comprises at least a component of a nano-particle lubricant. 10. The textured surface in claim 2, wherein the size of one or more of the textured features is a multiple of the size of a unit of a nano-particle lubricant in contact with the textured surface. 11. The textured surface in claim 2, wherein the surface comprises a substrate with a layer of material deposited over the substrate, and wherein the textured features expose parts of the substrate. 12. A method for forming a textured surface with textured features comprising: (a) forming the features to enhance the effectiveness of a nano-particle lubricant, (b) wherein the features are formed by one or more processes belonging to the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition, (c) wherein the textured features comprise at least one feature belonging to the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material, (d) placing a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface, (e) wherein the nano-particle lubricant comprises at least one member belonging to the group consisting of: (i) solid nano-particles, (ii) a layered nano-particle macro-composition, (iii) a bonded plurality of layered nano-particle macro-compositions, (iv) nanoparticles having an open-ended architecture and comprising an organic medium intercalated in the nanoparticle, (v) a nanoparticle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer, and (vi) a plurality of nanoparticle inner nuclei, on each nucleus, an outer layer intercalated with the nucleus or encapsulating the nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond. (f) forming a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface, the tribo-film comprising at least one of a phosphorus- containing compound, a phosphide, a boron-containing compound, and a boride, (g) wherein the tribo-film comprises at least a component of the nano-particle lubricant, (h) wherein the size of one or more of the textured features is a multiple of the size of a unit of the nano-particle lubricant, (i) forming the surface by depositing a layer of material over a substrate, and (j) exposing a part of the substrate by forming the textured features. 13. A method for forming a textured surface with textured features, comprising: (a) forming the features to enhance the effectiveness of a nano-particle lubricant, and (b) placing a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface. 14. The method in claim 13, wherein the textured features comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material. 15. The method in claim 13, further comprising: (a) forming the textured features by one or more processes belonging to the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition,. 16. The method in claim 12, wherein the nano-particle lubricant comprises molybdenum disulfide. 17. The method in claim 13, wherein the nano-particle lubricant comprises at least one member belonging to the group consisting of: (i) solid nano-particles, (ii) a layered nano-particle macro-composition, (iii) a bonded plurality of layered nano-particle macro-compositions, (iv) nanoparticles having an open-ended architecture and comprising an organic medium intercalated in the nanoparticle, (v) a nanoparticle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer, and (vi) a plurality of nanoparticle inner nuclei, on each nucleus, an outer layer intercalated with the nucleus or encapsulating the nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond. 18. The method in claim 13, further comprising: (a) forming a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface. 19. The method in claim 18, wherein the tribo-film comprises at least one of a phosphorus-containing compound, a phosphide, a boron-containing compound, and a boride. 20. The method in claim 18, wherein the tribo-film comprises at least a component of a nano-particle lubricant. 21. The method in claim 13, wherein the size of one or more of the textured features is a multiple of the size of a unit of a nano-particle lubricant in contact with the textured surface. 22. The method in claim 13, further comprising: (a) forming the surface by depositing a layer of material over a substrate, and (b) exposing a part of the substrate by forming the textured features. 23. The method in claim 13, wherein forming the features to enhance the effectiveness of a nano-particle lubricant comprises chemical texturing. 24. The method in claim 23, wherein chemical texturing comprises chemically functionalizing at least a portion of the lubricated surface. 25. The method in claim 23, further comprising: the chemical texturing reacting with and anchoring the nano-particle lubricant. 26. A lubricated surface comprising: a surface with textured features, wherein the textured features are adapted to enhance the effectiveness of a nano-particle lubricant, and a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface, wherein the nano-particle lubricant comprises a suspension, dispersion, or emulsion of nano-particles in a base material. 27. The lubricated surface of claim 26, wherein the nano-particles have an average particle dimension of less than or equal to about 100 nm. 28. The lubricated surface of claim 26, wherein the nano-particles comprise solid nano- particles. 29. The lubricated surface of claim 28, wherein the solid nano-particles comprise at least one material selected from the group consisting of molybdenum disulphide, tungsten disulphide, graphite, intercalated graphite, polytetrafluoroethylene, boron nitride, hexagonal boron nitride, soft metals, silver, lead, nickel, copper, cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron nitrate, borax, fluorinated carbon, zinc phosphide, boron, and combinations of any thereof. 30. The lubricated surface of claim 26, wherein the nano-particles comprise layered nano- particles. 31. The lubricated surface of claim 26, wherein the nano-particles comprise at least one type of layered nano-particles selected from the group consisting of molybdenum disulfide nano-particles, tungsten disulfide nano-particles, graphite nano-particles, boron nitride nano- particles, and combinations of any thereof. 32. The lubricated surface of claim 26, wherein the nano-particles comprise at least one layered material comprising a chalcogenide. 33. The lubricated surface of claim 26, wherein nano-particles comprise molybdenum disulfide nano-particles. 34. The lubricated surface of claim 26, wherein the nano-particles comprise nano-particles having an open architecture. 35. The lubricated surface of claim 26, wherein the nano-particles comprise an organic medium intercalated in the nano-particles. 36. The lubricated surface of claim 35, wherein the organic medium comprises at least one material selected from the group consisting of oil mediums, grease mediums, alcohol mediums, composite oil, canola oil, vegetable oil, soybean oil, corn oil, ethyl and methyl esters of rapeseed oil, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, hydrocarbon oils, n-hexadecane, phospholipids, and combinations of any thereof. 37. The lubricated surface of claim 35, wherein the organic medium comprises an oil medium selected from the group consisting of composite oil, canola oil, vegetable oil, soybean oil, corn oil, hydrocarbon oil, and combinations of any thereof. 38. The lubricated surface of claim 35, wherein the organic medium comprises a vegetable oil. 39. The lubricated surface of claim 35, wherein the organic medium comprises a phospholipid. 40. The lubricated surface of claim 26, wherein the nano-particles comprise nano-particles having an open architecture and an organic medium intercalated in the nano-particles. 41. The lubricated surface of claim 26, wherein the nano-particles are intercalated and encapsulated with an organic medium. 42. The lubricated surface of claim 26, wherein the nano-particles comprise a layered nano-particle macro-composition. 43. The lubricated surface of claim 26, wherein the nano-particles comprise a bonded plurality of layered nano-particle macro-compositions. 44. The lubricated surface of claim 26, wherein the nano-particles comprise a nano- particle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer. 45. The lubricated surface of claim 44, wherein the nanoparticle inner nucleus comprises at least one of molybdenum disulfide, tungsten disulfide, graphite, or boron nitride; and wherein the intermediate layer and the outer layer independently comprise at least one of a lecithin, phospholipid, phosphide, detergent, glyceride, monoglyceride, diglyceride, thiol phosphate, ester of monoglyceride, ester of fatty acid, compound containing phosphorous, compound containing sulfur, compound containing nitrogen, oil, grease, alcohol, composite oil, canola oil, vegetable oil, soybean oil, corn oil, ester of rapeseed oil, hydrocarbon oil, alkane, or combinations of any thereof. 46. The lubricated surface of claim 26, wherein the nano-particles comprise a plurality of nanoparticle inner nuclei and an outer layer intercalated with each nucleus or encapsulating each nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond. 47. The lubricated surface of claim 26, wherein the textured features comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material. 48. The lubricated surface of claim 26, wherein the textured features comprise at least one feature formed by one or more processes selected from the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition. 49. The lubricated surface of claim 26, further comprising a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface. 50. The lubricated surface of claim 49, wherein the tribo-film comprises at least one of a phosphorus-containing compound and a boron-containing compound. 51. The lubricated surface of claim 49, wherein the tribo-film comprises at least one of a phosphide and a boride. 52. The lubricated surface of claim 49, wherein the tribo-film comprises at least a component of the nano-particle lubricant. 53. The lubricated surface of claim 26, wherein the size of one or more of the textured features is a multiple of the size of a nano-particle in contact with the textured surface. 54. The lubricated surface of claim 26, wherein the surface comprises a substrate with a layer of material deposited over at least a portion of the substrate, and wherein the textured features expose at least a portion of the substrate underneath the deposited layer. 55. The lubricated surface of claim 26, wherein the base material comprises at least one material selected from the group consisting of oil, grease, plastic, gel, wax, silicone, hydrocarbon oil, vegetable oil, corn oil, peanut oil, canola oil, soybean oil, mineral oil, paraffin oil, synthetic oil, petroleum gel, petroleum grease, hydrocarbon gel, hydrocarbon grease, lithium based grease, fluoroether based grease, ethylenebistearamide, and combinations of any thereof. 56. The lubricated surface of claim 26, wherein the base material comprises at least one material selected from the group consisting of an oil, a grease, a plastic, a gel, a wax, a silicone, and combinations of any thereof. 57. The lubricated surface of claim 26, wherein the base material comprises an oil or a grease. 58. The lubricated surface of claim 26, wherein the base material comprises at least one material selected from the group consisting of mineral oil, paraffin oil, synthetic oil, petroleum grease, hydrocarbon grease, lithium based grease, and combinations of any thereof. 59. The lubricated surface of claim 26, wherein the nano-particle lubricant further comprises an emulsifier. 60. The lubricated surface of claim 59, wherein the emulsifier comprises at least one material selected from the group consisting of lecithins, phospholipids, soy lecithins, detergents, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, compounds containing phosphorous, compounds containing sulfur, compounds containing nitrogen, and combinations of any thereof. 61. The lubricated surface of claim 59, wherein the emulsifier comprises a compound containing phosphorous. 62. The lubricated surface of claim 59, wherein the emulsifier comprises a phospholipid. 63. The lubricated surface of claim 59, wherein the emulsifier comprises a lecithin. 64. The lubricated surface of claim 26, wherein the nano-particle lubricant comprises a suspension, dispersion, or emulsion of molybdenum disulfide nano-particles in a base material comprising an oil or a grease, wherein the molybdenum disulfide nano-particles are intercalated with an oil medium selected from the group consisting of composite oil, canola oil, vegetable oil, soybean oil, corn oil, hydrocarbon oil, and combinations of any thereof. 65. The lubricated surface of claim 64, wherein the molybdenum disulfide nanoparticles are intercalated with a vegetable oil. 66. The lubricated surface of claim 64, further comprising an emulsifier comprising a phospholipid. 67. The lubricated surface of claim 66, wherein the emulsifier comprises a lecithin. 68. A method for lubricating a surface comprising: forming textured features in the surface to enhance the effectiveness of a nano-particle lubricant; and placing a nano-particle lubricant in contact with the textured features of the textured surface in a position to lubricate the surface, wherein the nano-particle lubricant comprises a suspension, dispersion, or emulsion of nano-particles in a base material. 69. The method of claim 68, wherein forming the textured features to enhance the effectiveness of a nano-particle lubricant comprises chemical texturing. 70. The method of claim 69, wherein chemical texturing comprises chemically functionalizing at least a portion of the lubricated surface. 71. The method of claim 69, wherein chemical texturing comprises chemically anchoring at least a portion of the nano-particle lubricant to the surface. 72. The method of claim 68, wherein the nano-particles have an average particle dimension of less than or equal to about 100 nm. 73. The method of claim 68, wherein the nano-particles comprise solid nano-particles. 74. The method of claim 73, wherein the solid nano-particles comprise at least one material selected from the group consisting of molybdenum disulphide, tungsten disulphide, graphite, intercalated graphite, polytetrafluoroethylene, boron nitride, hexagonal boron nitride, soft metals, silver, lead, nickel, copper, cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron nitrate, borax, fluorinated carbon, zinc phosphide, boron, and combinations of any thereof. 75. The method of claim 68, wherein the nano-particles comprise layered nano-particles. 76. The method of claim 68, wherein the nano-particles comprise at least one type of layered nano-particles selected from the group consisting of molybdenum disulfide nano- particles, tungsten disulfide nano-particles, graphite nano-particles, boron nitride nano- particles, and combinations of any thereof. 77. The method of claim 68, wherein the nano-particles comprise at least one layered material comprising a chalcogenide. 78. The method of claim 68, wherein nano-particles comprise molybdenum disulfide nano-particles. 79. The method of claim 68, wherein the nano-particles comprise nano-particles having an open architecture. 80. The method of claim 68, wherein the nano-particles comprise an organic medium intercalated in the nano-particles. 81. The method of claim 80, wherein the organic medium comprises at least one material selected from the group consisting of oil mediums, grease mediums, alcohol mediums, composite oil, canola oil, vegetable oil, soybean oil, corn oil, ethyl and methyl esters of rapeseed oil, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, hydrocarbon oils, n-hexadecane, phospholipids, and combinations of any thereof. 82. The method of claim 80, wherein the organic medium comprises an oil medium selected from the group consisting of composite oil, canola oil, vegetable oil, soybean oil, corn oil, hydrocarbon oil, and combinations of any thereof. 83. The method of claim 80, wherein the organic medium comprises a vegetable oil. 84. The method of claim 80, wherein the organic medium comprises a phospholipid. 85. The method of claim 68, wherein the nano-particles comprise nano-particles having an open architecture and an organic medium intercalated in the nano-particles. 86. The method of claim 68, wherein the nano-particles are intercalated and encapsulated with an organic medium. 87. The method of claim 68, wherein the nano-particles comprise a layered nano-particle macro-composition. 88. The method of claim 68, wherein the nano-particles comprise a bonded plurality of layered nano-particle macro-compositions. 89. The method of claim 68, wherein the nano-particles comprise a nano-particle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer. 90. The method of claim 89, wherein the nanoparticle inner nucleus comprises at least one of molybdenum disulfide, tungsten disulfide, graphite, or boron nitride; and wherein the intermediate layer and the outer layer independently comprise at least one of a lecithin, phospholipid, phosphide, detergent, glyceride, monoglyceride, diglyceride, thiol phosphate, ester of monoglyceride, ester of fatty acid, compound containing phosphorous, compound containing sulfur, compound containing nitrogen, oil, grease, alcohol, composite oil, canola oil, vegetable oil, soybean oil, corn oil, ester of rapeseed oil, hydrocarbon oil, alkane, or combinations of any thereof. 91. The method of claim 68, wherein the nano-particles comprise a plurality of nanoparticle inner nuclei and an outer layer intercalated with each nucleus or encapsulating each nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond. 92. The method of claim 68, wherein the textured features comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material. 93. The method of claim 68, wherein the textured features are formed by one or more processes selected from the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition. 94. The method of claim 68, further comprising forming a tribo-film in contact with the textured features of the textured surface in a position to lubricate the surface. 95. The method of claim 94, wherein the tribo-film comprises at least one of a phosphorus-containing compound and a boron-containing compound. 96. The method of claim 94, wherein the tribo-film comprises at least one of a phosphide and a boride. 97. The method of claim 94, wherein the tribo-film comprises at least a component of the nano-particle lubricant. 98. The method of claim 68, wherein the size of one or more of the textured features is a multiple of the size of a nano-particle in contact with the textured surface. 99. The method of claim 68, further comprising: depositing a layer of material over a substrate surface; and exposing at least a portion of the substrate by forming the textured features in the deposited layer of material. 100. The method of claim 68, wherein the base material comprises at least one material selected from the group consisting of oil, grease, plastic, gel, wax, silicone, hydrocarbon oil, vegetable oil, corn oil, peanut oil, canola oil, soybean oil, mineral oil, paraffin oil, synthetic oil, petroleum gel, petroleum grease, hydrocarbon gel, hydrocarbon grease, lithium based grease, fluoroether based grease, ethylenebistearamide, and combinations of any thereof. 101. The method of claim 68, wherein the base material comprises at least one material selected from the group consisting of an oil, a grease, a plastic, a gel, a wax, a silicone, and combinations of any thereof. 102. The method of claim 68, wherein the base material comprises an oil or a grease. 103. The method of claim 68, wherein the base material comprises at least one material selected from the group consisting of mineral oil, paraffin oil, synthetic oil, petroleum grease, hydrocarbon grease, lithium based grease, and combinations of any thereof. 104. The method of claim 68, wherein the nano-particle lubricant further comprises an emulsifier. 105. The method of claim 104, wherein the emulsifier comprises at least one material selected from the group consisting of lecithins, phospholipids, soy lecithins, detergents, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, compounds containing phosphorous, compounds containing sulfur, compounds containing nitrogen, and combinations of any thereof. 106. The method of claim 104, wherein the emulsifier comprises a compound containing phosphorous. 107. The method of claim 104, wherein the emulsifier comprises a phospholipid. 108. The method of claim 104, wherein the emulsifier comprises a lecithin. 109. The method of claim 68, wherein the nano-particle lubricant comprises a suspension, dispersion, or emulsion of molybdenum disulfide nano-particles in a base material comprising an oil or a grease, wherein the molybdenum disulfide nano-particles are intercalated with an oil medium selected from the group consisting of composite oil, canola oil, vegetable oil, soybean oil, corn oil, hydrocarbon oil, and combinations of any thereof. 1 10. The method of claim 109, wherein the molybdenum disulfide nanoparticles are intercalated with a vegetable oil. 1 1 1. The method of claim 109, wherein the nano-particle lubricant further comprises an emulsifier comprising a phospholipid. 1 12. The method of claim 1 1 1 , wherein the emulsifier comprises a lecithin. |
BACKGROUND
1. Field of Invention
[0001] Embodiments of the present invention relate generally to nano-lubrication that is lubrication using nano-materials. More specifically, embodiments of the present invention relate to preparation of surfaces to be lubricated to enhance the effectiveness of intended nano-lubrication.
2. Description of Related Art
[0002] Nano-materials have been developed and used for lubrication and other purposes. Nano-materials have also been used with other materials for lubrication and other purposes. However, this knowledge is still in its infancy and a need exists to enhance the effectiveness of nano-lubrication.
SUMMARY OF EMBODIMENTS OF THE INVENTION
[0003] Embodiments of the present invention may provide textured surfaces to be lubricated, the texturing to enhance the effectiveness of the intended nano-lubrication. The word "texture" refers to a physical and/or chemical patterning on the surfaces to be lubricated, also referred to herein as the application surface or the substrate. The texturing may make asperities and depressions in the surface to be lubricated with or without chemical functionalization. This texturing may be executed, for example, by chemical etching, laser etching, mechanical machining or other techniques. This texturing may create locations in the lubricated surface to hold or anchor the intended nano-lubricants, to facilitate the creation of a lubricating tribo-film on the application surface when the surface is used under pressure, temperature and other stress factors, and resulting in delivery of multiple chemistries from the nano-lubricant.
[0004] In non-limiting embodiment, a textured surface and a method of making a textured surface according to the present disclosure comprises a surface with textured features and methods of making the textured features. The textured features are adapted to enhance the effectiveness of a nano-particle lubricant. In a non-limiting embodiment the features are formed by one or more processes selected from the group consisting of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition. The textured features may comprise at least one feature selected from the group consisting of pores, waves, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and chemically functional material.
[0005] A nano-particle lubricant is in contact with the textured features of the textured surface in a position to lubricate the surface. In non-limiting embodiments, the nano-particle lubricant comprises at least one member selected from the group consisting of: (i) solid nano-particles, (ii) a layered nano-particle macro-composition, (iii) a bonded plurality of layered nano-particle macro-compositions, (iv) nanoparticles having an open- ended architecture and comprising an organic medium intercalated in the nanoparticle, (v) a nanoparticle inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer, and (vi) a plurality of nanoparticle inner nuclei, on each nucleus, an outer layer intercalated with the nucleus or encapsulating the nucleus, the layer with the nucleus forming a layered nanoparticle, and a plurality of bonds, each bond bonded to at least two of the layered nanoparticles, such that each layered nanoparticle is bonded to at least one other of the layered nanoparticles by a bond.
[0006] In a non-limiting embodiment according to the present disclosure, a tribo- film is in contact with the textured features of the textured surface in a position to lubricate the surface. In another non-limiting embodiment according to the present disclosure, the tribo-film comprises at least one of a phosphorus-containing compound, a phosphide, a boron containing compound, and a boride. In still another non-limiting embodiment, the tribo-film comprises at least a component of the nano-particle lubricant. According to non-limiting aspects of the present disclosure, the size of one or more of the textured features is a multiple of the size of a unit of the nano-particle lubricant, and the surface comprises a substrate with a layer of material deposited over the substrate, where the textured features expose parts of the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Embodiments of the present invention are described herein, by way of example, in conjunction with the following figures.
[0008] Figure 1 is a schematic diagram illustrating a textured surface and a layer of nano-lubricants located on the surface.
[0009] Figure 2 is a schematic diagram illustrating a nano-lubricant.
[0010] Figure 3 is a schematic diagram illustrating two textured surfaces approaching frictional contact, each textured surface having a layer of nano-lubricants located on the surface.
[0011] Figure 4 is a schematic diagram illustrating two textured surfaces approaching frictional contact and showing plastic deformation of nano-lubricants located on the surfaces.
[0012] Figure 5 is a schematic diagram illustrating two textured surfaces in frictional contact with a tribofilm formed from deformed nano-lubricants located between the surfaces.
[0013] Figure 6 shows an embodiment with materials deposited on a substrate, and then etched exposing portions of the substrate.
EMBODIMENTS OF THE PRESENT INVENTION
[0014] Embodiments of the present invention may provide textured surfaces to be lubricated, the texturing to enhance the effectiveness of the intended nano-lubrication. The texturing may make asperities and depressions in the surface to be lubricated that can mechanically anchor or mechanically interlock the nano-lubricant to the surface. Texturing may also include chemical functionalization of all or a portion of the application surface, and the chemical functionalization may be directed to various patterns on the application surface. The term "chemical functionalization" as used herein refers to the attachment or bonding of various chemical groups to the application surface, wherein the functionalized surface can then form chemical bonds with suitably chemically functionalized nano-lubricants.
[0015] In non-limiting embodiments, this texturing may be executed, for example, by one or more of etching, chemical etching, chemical functionalization, laser etching, laser blasting, sand blasting, physical etching, mechanical etching, top down processes, bottom up processes, chemical texturing, physical texturing, mechanical texturing, stamping, laser texturing, vapor deposition, plasma deposition, electroplating, self assembly, directed assembly, subtractive manufacturing, additive manufacturing, hybrid manufacturing, and other deposition,. This texturing may create locations in the lubricated surface to hold or anchor the intended nano-lubricants, which, in non-limiting embodiments, may be introduced to the application surface as a suspension, dispersion, or emulsion in a medium such as, for example, an oil. As used herein, the terms "anchor" or "anchoring" mean that the nano- lubricant is held to the application surface through various means, including, but not limited to mechanical interlocking; chemical bonding, such as, for example, covalent bonding, ionic bonding, London dispersion forces, electrostatic forces, hydrogen-bonding; and by other biases such as, for example, a magnetic field, until the nano-lubricant is released from the surface as a result of use under pressure to form a tribo-film adjacent to the surface to be lubricated. The anchored nano-lubricant is used to facilitate the creation of a tribo-film on the surface, as a result of releasing the anchored lubricant when the textured surface is used under stress such as pressure and temperature, and results in delivery of multiple chemistries from the nano-lubricant.
[0016] In various embodiments, the nano-lubricant may be a layered or an open architecture nanoparticle, as described in U.S. Patent Application No. 12/160,758 (U.S. Publication No. 2008/03121 1 1 Al), for "Nanoparticle Compositions and Methods of Making and Using The Same," by Malshe et al., which is incorporated by this reference into this specification in its entirety. The nanoparticles may be solid lubricant nanoparticles. The nanoparticles may be made from starting materials or solid lubricant starting materials. Examples of solid lubricants may include, but are not limited to, layered materials, suitably chalcogenides, more suitably, molybdenum disulphide, tungsten disulphide, or a combination thereof. Another suitable layered material is graphite or intercalated graphite. Other solid lubricants that may be used alone or in combination with the layered materials are polytetrafluoroethylene, boron nitride (suitably hexagonal boron nitride), soft metals (such as silver, lead, nickel, copper), cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron nitrate, borax, fluorinated carbon, zinc phosphide, boron, or a combination thereof. Fluorinated carbons may be, without limitation, carbon-based materials such as graphite which has been fluorinated to improve its aesthetic characteristics. Such materials may include, for example, a material such as CF X wherein x ranges from about 0.05 to about 1.2.
[0017] Other nano-lubricants that may be used include, for example, the nanoparticle of macro-compositions described in U.S. Application Patent No. 13/540,235, filed July 2, 2012, for "Nanoparticle Macro-Compositions" by Malshe, which is incorporated by this reference into this specification in its entirety. Non-limiting embodiments of the present invention may include a macro-composition with a special structure. The term "macro-composition", as used herein, is a term to describe embodiments of the present invention. The structure includes a layered macro-composition made of a nanoparticle as an inner nucleus, an intermediate layer around the nucleus, and an outer layer intercalated with the nucleus or encapsulating the nucleus and the intermediate layer. A plurality of the layered macro-compositions is bonded together by bonds, so that each layered macro- composition is bonded to at least one other such layered macro-composition. Embodiments include a macro-composition made of three 3 -layered macro-compositions joined in a chain by two bonds. These macro-composition assemblies may take the shape of layered macro- compositions bonded together in chains, or forming other shapes, such as rings. The layered macro-composition may be about 20 nanometers in size, for example. The bonds of the complex macro-composition may have an average length of no more than about 100 nanometers, for example. Embodiments of a macro-composition, may be available from NanoMech, Inc., in Springdale, Arkansas.
[0018] In various embodiments, the surface to be lubricated may be textured using nanoscale laser etching, for example, in a sub-micron scale. This laser etching is described in a paper by Malshe, et al., entitled "Femtosecond laser-induced periodic structure writing on diamond crystals and microclusters" in Applied Physics Letters, 6 December 1999, Vol. 75, Number 23, pp. 3716-3718, which is incorporated in its entirety into this specification by this reference. Layered Surfaces
[0019] In an alternative embodiment of the present invention, materials may be deposited in layers on the surface to be lubricated, by for example vapor deposition, plasma deposition, electroplating, or otherwise. This surface with deposition layers may then be etched by, for example, laser-etching, chemical etching, or otherwise. This etching may provide a surface texture to expose chemically receptive materials in depressions or other features between asperities in the surface to bond or with nano-particles intended as nano- lubricants, to form tribo-films in the depressions. For example, the textured surface may react with phosphorus-containing compounds or phosphides in layered nano-lubricant particles, which phosphorus-containing compounds or phosphides may be released under pressure during use of the lubricated surface, to form glossy tribo-films in the depressions or other features.
[0020] Figure 6(a) shows an embodiment of a surface to be lubricated with substrate 10. Figure 6(b) shows a layer 62 of material deposited on the substrate 10. Figure 6(c) shows the embodiment after etching of the deposited layer 62, which exposes portions of the substrate 10, while leaving portions of the deposited layer 62. This creates textured features including asperities 14, and low areas 63 between asperities 14. The bottom of the low areas 63 consist of substrate 10, and the tops of the asperities consist of deposited material 62. This may allow, for example, the bottom of the asperity 14, consisting of substrate 10, to react with and bond to the nano-lubricant in a manner different from the top of the asperities 14, consisting of deposited material 62.
Texture, Residence Time, and Anchoring
[0021] In various embodiments, either the nano-lubricant, or the lubricated surface, or both the lubricant and the lubricated surface, may be textured in one or more ways to enhance the effectiveness of the lubrication. The nano -lubricants may be closed architecture and/or open architecture lubricants.
[0022] The texturing may be, for example, physical, chemical, mechanical, by laser, or otherwise, or a combination of these methods. This texturing may facilitate the lubricant being anchored onto the textured surface. The anchoring may comprise at least one or more of a mechanical anchoring, a chemical bond anchoring, or other bias such as magnetic field anchoring.
[0023] In various embodiments, texturing of the surface to be lubricated can provide an open architecture for the surface to be lubricated. As an example, chemical etching of the surface is a form of chemical texturization. Open architecture is a term that is sometimes used to refer to the structure of a material that tends to promote intercalation of other materials, or the bonding, attachment, localization, anchoring, or other attraction of other materials to the open architectured item on the surface and/or inside the core shell.
[0024] The effect of the texturing is to enhance the residence time of the lubricant at the lubricated mated surfaces, and to enhance the efficiency and effectiveness of the lubricant particles. The periodicity or period of the residence time when the lubricant is localized at the lubricated surface may be is defined as short range, medium range, or long range.
A Delivery System
[0025] Texturing mated lubricated surfaces can be viewed as a type of delivery system, where in the components of the layered nanoparticle lubricant are delivered to the surface of the mated lubricated surfaces. This delivery may occur when a multi-layered nano-particle lubricant is deformed and breaks down under use at the textured lubricated surface delivering, for example, its intermediate layer of phosphorus-containing compounds to the surface.
Size and Parameters of Textured Features
[0026] The size of the textured features at the mated lubricated surface, for example, the size of the depressions between neighboring asperities, may be measured as N times the size of the lubricant unit (for example, a multi-layered nano-composition, molecule, or otherwise). For example, if it were intended that a multi-layered nanoparticle composition, with a particle size of about 20 nanometers, would be used as the lubricant, then texturing of the lubricated surfaces may be designed to be about 2 times the size of this nano-lubricant, that is, 40 nanometers across a depression between neighboring asperities. The resulting density of the texturing may be the referred to as the size of the repeating textured features, or for example, the distance to repeating asperities.
[0027] Texturing of the mated lubricated surfaces may have several basic parameters. These may include (1) the size of the textured features (for example, the distance of depressions between neighboring asperities), (2) the primary and secondary order of the texturing (for example, the height of the asperities or the depth of the depressions or the periodicity of the asperities), (3) the density (the number of repeating physical characteristics of the texturing in a given area or distance), (4) a combination of physical and chemical texturing (chemical texturing may include the deposition of functional or molecular groups that would attach nano-lubricants to the lubricated surfaces), and (5) the direction of motion of the mated lubricated parts with respect to the orientation of texture. In a non-limiting embodiment, texturing the surface to form the features to enhance the effectiveness of a nano-particle lubricant comprises chemical texturing. In still another non-limiting embodiment, chemical texturing comprises chemically functionalizing at least a portion of the substrate.
[0028] Texturing of the nano-lubricant particles may include various fundamentals and parameters including (1) a multi-component chemistry of the layered nano- lubricant particles (see, for example, U.S. Patent Application 12/160,758 for "Nanoparticle Compositions and Methods of Making and Using the Same" by Malshe for a description of some possible multi-component chemistries) and the placement of the nano-lubricant particles on a lubricated surface, (2) physical or chemical openness of the texture in the layered nano-particles (chemical openness here refers to the tendency of the lubricant to chemically attach to the lubricated surface), (3) the textured lubricant particle bond or linkage to dispersion media and application media (for example, multi-layered nano-particle lubricants may be intercalated with longer chain hydrocarbon oil molecules to form macro- compositions or macromolecules for lubricants, as described in Patent Application No. 13/540,235, filed July 2, 2012, for "Nano-particle Macro-Compositions" by Malshe), and (4) the texturing of the nanoparticle lubricant to give the nanoparticle chemical and/or physical texture complimentary to the mated lubricated surface. For example, functional chemical groups attached to the nanoparticle lubricants may attach the lubricant particles to the lubricated textured surfaces through covalent bonding, ionic bonding, London dispersion forces, electrostatic forces, hydrogen-bonding and other known forms of chemical bond formation.
Types of Textured Features
[0029] Physical texturing of the nanoparticle lubricants, and/or the mated lubricated surfaces may provide various textured features, including, for example, pores, waviness, striations, channels, protrusions, asperities, depressions, grooves, holes, low points, high points, cracks, low areas, high areas, exposed sandwiched layers, and other features. The physical texturing of the nano-lubricant particles and/or lubricated surfaces may be executed by processes including chemical etching, laser etching, laser blasting, sand blasting, top-down processes, physical etching, mechanical etching, and otherwise.
[0030] Chemical texturing of the nanoparticle lubricants and the lubricated mated surfaces may include features such as, for example, multi-component chemistries (in the nano-particle lubricants) in combination with the preceding physical texturing features or processes. Processes for chemical texturing of the lubricant and lubricated surfaces may include functionalization (e.g. the attachment of chemically active elements or chemical groups), using bottom up chemical processes such as solutions or vapor deposition.
[0031] The processes and features of physical texturing and chemical texturing of the nanoparticle lubricants and the textured surfaces may be integrated for a specific application and a specific design criteria, for a designed custom lubrication application.
Detailed Discussion of the Figures: Figure 1
[0032] Figure 1 is a schematic diagram illustrating a textured surface and a layer of nano-lubricants located on the surface. By way of example, referring to Figure 1, a substrate 10 comprises a textured surface 12. The textured surface 12 comprises asperities 14. The asperities 14 of the textured surface 12 may be formed using a texturing process as described herein. Alternatively, the asperities 14 of the textured surface 12 may form as a result of the general production or processing of the substrate 10. A lubricant layer 20 is located on the textured surface 12 of the substrate 10. The lubricant layer 20 comprises nano- lubricants 30. The nano-lubricant particles 30 are shown for convenience in Figure 1 and other figures herein as round or spherical; however, note that actually the nano-lubricant particles 30 may be irregular shaped, or ovaloid, and in any case have an open architecture facilitating intercalation and other types of attachment and bonding.
[0033] The nano-lubricants 30 may, for example, comprise layered nanoparticle macro-compositions as described in U.S. Patent Application No. 12/160,758 (U.S. Publication No. 2008/031211 1 Al) for "Nanoparticle Compositions and Methods of Making and Using The Same," by Malshe et al. The nano-lubricants 30 may, for example, comprise nanoparticle macro-compositions as described in U.S. Application Patent No. 13/540,235, filed July 2, 2012, for "Nanoparticle Macro-Compositions" by Malshe.
Figure 2
[0034] Figure 2 is a schematic diagram illustrating a solid nano-lubricant. For example, referring to Figure 2, the nano-lubricants 30 may comprise a layered macro- composition comprising an inner nucleus 32, an intermediate layer 36 encapsulating the inner nucleus 32, and an outer layer 38 encapsulating the inner nucleus 32 and the intermediate layer 36. The intermediate layer 36 and the outer layer 36 may independently comprise at least one organic material. The intermediate layer 36 and the outer layer 38 may comprise the same or a different organic material. The inner nucleus 32 may be intercalated with an organic material comprising the intermediate layer 36 and/or the outer layer 38.
[0035] The inner nucleus 32 may comprise at least one solid nanoparticle material selected from the group consisting of chalcogenides, molybdenum disulphide, tungsten disulphide, graphite, boron nitride, polytetrafluoroethylene, hexagonal boron nitride, soft metals, silver, lead, nickel, copper, cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron oxide, borax, fluorinated carbon, zinc phosphide, boron, and combinations thereof.
[0036] The intermediate layer 36 and/or the outer layer 38 may independently comprise at least one organic material selected from the group consisting of lecithins, phospholipids, phosphides, soy lecithins, detergents, glycerides, distilled monoglycerides, monoglycerides, diglycerides, thiol phosphate and related complexes, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, compounds containing phosphorous, compounds containing sulfur, compounds containing nitrogen, oil, grease, alcohol, composite oil, canola oil, vegetable oils, soybean oil, corn oil, ethyl and methyl esters of rapeseed oil, hydrocarbon oils, alkanes such as n-hexadecane, and combinations thereof.
[0037] Referring to Figure 1, the lubricant layer 20 located on the textured surface 12 of the substrate 10 may comprise, consist essentially of, or consist of the nano- lubricants 30. For example, the lubricant layer 20 may comprise the nano-lubricants 30 added as lubrication enhancers to an amount of a base lubricant such as, for example, grease, oil, gear oil, lithium complex grease, paste and protective surface coatings.
Figure 3
[0038] Figure 3 is a schematic diagram illustrating two textured surfaces approaching frictional contact, each textured surface having a layer of nano-lubricants located on the surface. Figure 3 shows two substrates 10, 10' each comprising textured surfaces comprising asperities 14, 14'. Lubricant layers 20, 20' are located on the textured surfaces of the substrates 10, 10', and the lubricant layers 20, 20' each comprise nano-lubricants 30. The substrates 10, 10' are shown as approaching frictional contact between the respective textured surfaces. The nano-lubricants 30 localize into the spaces between the asperities 14, 14' on the respective textured surfaces.
Figure 4
[0039] Figure 4 is a schematic diagram illustrating two textured surfaces approaching frictional contact and showing plastic deformation of nano-lubricants located on the surfaces. As the distance decreases between the respective surfaces of the substrates 10, 10', the mechanical stress (pressure) on the nano-lubricants 30 increases. This plastically deforms the nano-lubricants 30, as shown in Figure 4. The plastic deformation of the nano- lubricants 30 due to applied stress between the two surfaces in frictional contact may disrupt the layered structure of the nano-lubricants (closed as well as open architecture), thereby breaking up the layered nano-lubricant particles and releasing organic materials comprising the intermediate layer 36 and/or the outer layer 38.
Delivery and the Tribo-film: Figure 5
[0040] Figure 5 is a schematic diagram illustrating two textured surfaces in frictional contact with a tribo-film formed from deformed nano-lubricants located between the surfaces. The organic material(s) is(are) released in situ on the lubricated surfaces of the substrates 10, 10' and in the spaces between the asperities 14, 14'. This provides targeted and site-specific delivery of the organic material(s), which may coalesce into a tribofilm 50, as shown in Figure 5. The tribofilm 50 provides enhanced nano-lubrication between the respective surfaces of the substrates 10, 10' in frictional contact. In various embodiments, wherein the nano-lubricants 30 comprise different organic materials, the resulting tribofilm 50 may comprise multiple chemistries that provide enhanced lubricity. For example, the tribofilm 50 may comprise a mixture of phospholipids, phosphides, borates, amides and/or other phosphorus-containing and other compounds and the material comprising the inner nucleus 32, such as, for example, graphite, boron nitride, chalcogenides, molybdenum disulphide, tungsten disulphide, zirconium oxide or other chalcogenides. In a non-limiting embodiment, the tribo-film formed from deformed nano-lubricants includes at least one of a phosphorus-containing compound, a phosphide, a boron-containing compound, and a boride. In a non-limiting embodiment, the tribo-film formed from deformed nano-lubricants includes at least a component of the nano-particle lubricant.
OTHER MATTERS
[0041] It is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the description or illustrated in the drawings herein. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
[0042] Any numerical range recited herein includes all values from the lower value to the upper value. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10%o to 30%>, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
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