TUBULAR ARTICLES WITH ELECTRODEPOSITED COATINGS, AND SYSTEMS AND METHODS FOR PRODUCING THE SAME

• US 20200131658A1
• Filed: 04/20/2018
• Published: 04/30/2020
• Est. Priority Date: 04/21/2017
• Status: Active Grant

• Current Assignee: Modumetal Incorporated
• Original Assignee: Modumetal Incorporated
• Inventors: LOMASNEY, Christina A., LI, Guohua, ANGELO, Nicholas
• Granted Patent: US 11,286,575 B2
• Time in Patent Office: Days
• CPC Class Codes: C25D 17/005 Contacting devices
• CPC Class Codes: C25D 17/06 Suspending or supporting devices for articles to be coated
• CPC Class Codes: C25D 17/08 Supporting racks , i.e. not for suspending
• CPC Class Codes: C25D 17/12 Shape or form C25D17/14 takes precedence
• CPC Class Codes: C25D 7/04 Tubes; Rings; Hollow bodies
• CPC Class Codes: F16L 57/04 against fire or other external sources of extreme heat
• CPC Class Codes: F16L 57/06 against wear F16L57/04 takes precedence
• CPC Class Codes: F16L 58/08 by metal

Abstract

Provided herein are tubular articles comprising electrodeposited nano- or microlaminate coatings, which have improved heat, wear, and corrosion resistance. The present disclosure further provides apparatuses, systems, and methods for the electrodeposition of such coatings on tubular workpieces using fixed or dynamic electrical contact points.

Claims

1. An apparatus comprising:

a rack comprising;

at least one support structure configured to support a tubular workpiece having a substantially cylindrical shape, a hollow cavity defined by an inner surface having a first surface area, an outer surface having a second surface area, and a longitudinal axis; and

a contact point assembly configured to rotate the tubular workpiece, enable electrical contact with the tubular workpiece, or both.

2. The apparatus of claim 1, further comprising a conductive bus supported by the rack, the conductive bus configured to be in electrical contact with the tubular workpiece via the contact point assembly, such that the tubular workpiece is free to rotate while maintaining electrical contact with the conductive bus.

3. The apparatus of claim 2, wherein the contact point assembly comprises a gear, the gear comprising a threaded portion, and the conductive bus being configured to be in electrical contact with the tubular workpiece via the gear.

4. The apparatus of claim 3, further comprising a coupler, the coupler comprising:

a first threaded portion that corresponds to the threaded portion of the gear, such that the threaded portion of the gear and the first threaded portion of the coupler may be joined together; and

a second threaded portion that corresponds to a threaded portion of the tubular workpiece, such that the threaded portion of the tubular workpiece and the second threaded portion of the coupler may be joined together.

5. The apparatus of claim 4, wherein the threaded portion of the gear corresponds to the threaded portion of the tubular workpiece, such that the threaded portion of the gear and the threaded portion of the tubular workpiece may be joined together.

6. The apparatus of any one of claims 1-5, wherein the contact point assembly comprises a conductive article.

7. The apparatus of any one of claims 1-6, wherein the at least one support structure comprises a rod positioned substantially along the longitudinal axis or an axis substantially parallel to the longitudinal axis within the hollow cavity of the tubular workpiece.

15. The apparatus of any one of claims 1-14, further comprising an interior anode having an exterior surface, the interior anode configured to be positioned along the longitudinal axis of the tubular workpiece or an axis substantially parallel to the longitudinal axis within the hollow cavity of the tubular workpiece.

16. The apparatus of claim 15, wherein the exterior surface of the interior anode is positioned a predetermined distance from the inner surface of the tubular workpiece.

17. The apparatus of any one of claims 1-16, wherein the at least one support structure is configured to support a plurality of tubular workpieces that comprises the tubular workpiece.

18. The apparatus of claim 17, wherein the contact point assembly is configured to rotate each tubular workpiece of the plurality of tubular workpieces around a respective longitudinal axis.

19. The apparatus of claim 18, wherein the contact point assembly is configured to rotate each of the plurality of tubular workpieces at the same speed.

20. The apparatus of any one of claims 17-19, wherein the plurality of tubular workpieces is arranged in a planar configuration or a polygonal configuration.

21. The apparatus of any one of claims 17-20, wherein individual workpieces of the plurality of tubular workpieces are coupled in serial with a plurality of couplers.

22. The apparatus of any one of claims 17-21, wherein the plurality of workpieces comprises at least three tubular workpieces.

30. The apparatus of any one of claims 16-29, further comprising a guide coupled to the rack, the guide configured to maintain the interior anode in position.

31. The apparatus of any one of claims 16-30, wherein the interior anode is columnar or tubular, the interior anode having a diameter that is smaller than an inner diameter of the tubular workpiece.

32. The apparatus of any one of claims 16-31, wherein the exterior surface of the interior anode is corrugated.

33. The apparatus of any one of claims 16-32, wherein the interior anode has a hollow cavity.

34. The apparatus of any one of claims 16-33, wherein the interior anode has a plurality of holes that extend laterally through the interior anode.

35. The apparatus of claim 34, wherein a number of a subset of the plurality of holes that is in a predetermined area of the interior anode varies along a length of the interior anode.

36. The apparatus of claim 34 or 35, wherein diameters of individual holes of the plurality holes vary along a length of the interior anode.

37. The apparatus of any one of claims 1-36, further comprising an exterior anode having a length that is less than or equal to a length of the tubular workpiece, the exterior anode being adjacent to the tubular workpiece at a second predetermined distance from an exterior surface of the tubular workpiece

38. The apparatus of claim 37, wherein the exterior anode is positioned substantially parallel to the longitudinal axis at a substantially uniform distance from the exterior surface of the tubular workpiece.

39. The apparatus of any one of claims 1-38, further comprising shielding or thieving positioned adjacent to the tubular workpiece.

40. The apparatus of claim 39 wherein:

the tubular workpiece has a first threaded portion;

at least a portion of the shielding or thieving is positioned adjacent to the first threaded portion between the tubular workpiece and the interior anode or the exterior anode.

41. The apparatus of any one of claims 39-40, wherein at least the portion of the shielding is substantially circular, semi-circular, or rectangular.

42. The apparatus of any one of claims 39-41, wherein at least the portion of the shielding is substantially cuboidal, substantially cylindrical, or substantially semi-cylindrical.

43. The apparatus of any one of claims 39-42, wherein at least the portion of the shielding is positioned between the tubular workpiece and the interior anode, the exterior anode, or both.

44. The apparatus of any one of claims 39-43, wherein the shielding comprises acrylic.

45. The apparatus of any one of claims 1-44, wherein the rack is configured to maintain the tubular workpiece with its longitudinal axis at an incline ranging from about 0.5 degrees to about 2.5 degrees relative to horizontal.

46. The apparatus of any one of claims 1-45, wherein the tubular workpiece has a length ranging from about 0.1 meters (m) to 15 m.

47. The apparatus of any one of claims 17-46, wherein the plurality of tubular workpieces have substantially a same length, substantially a same inner diameter, a same outer diameter, or a combination thereof.

48. An electroplating system comprising:

a tubular workpiece having a substantially cylindrical shape, a hollow cavity defined by an inner surface of the tubular workpiece, and a longitudinal axis; and

an apparatus of any one of claims 1-47.

49. The electroplating system of claim 48, further comprising an interior anode.

50. The electroplating system of claim 48 or 49, further comprising a process tank that, in operation, houses the rack and an electrolyte bath.

51. The electroplating system of any one of claims 48-50, wherein the electroplating system further comprises an electrolyte distribution tube positioned adjacent to the interior anode within the hollow cavity of the tubular workpiece.

52. The electroplating system of claim 51, wherein the electrolyte distribution tube has a plurality of holes that extend laterally through the electrolyte distribution tube.

53. The electroplating system of claim 52, wherein a number of a subset of the plurality of holes that is in a predetermined area of the electrolyte distribution tube varies along a length of the electrolyte distribution tube, wherein diameters of individual holes of the plurality holes vary along a length of the electrolyte distribution tube, or both.

54. The electroplating system of any one of claims 48-53, further comprising a flow control unit to distribute an electrolyte solution through a process tank.

55. The electroplating system of claim 54, wherein the flow control unit, in operation, introduces an electrolyte bath into the hollow cavity of the tubular workpiece.

56. The electroplating system of claim 54 or 55, wherein the flow control unit, in operation, transmits at least a portion of the electrolyte bath through the plurality of holes in the electrolyte distribution tube, the plurality of holes in the interior anode, or both.

57. The electroplating system of any one of claims 48-56, further comprising:

a power supply electrically coupled to the interior anode; and

a power supply controller that, in operation, controls at least one of a current and a voltage applied to the tubular workpiece.

58. The electroplating system of claim 57, wherein the power supply controller, in operation, controls a current density applied to the tubular workpiece, wherein the current density varies over time.

59. The electroplating system of claim 57 or 58, further comprising an exterior anode electrically coupled to the power supply, wherein the power supply controller, in operation, controls at least one of a current and a voltage applied to the tubular workpiece.

60. The electroplating system of any one of claims 57-59, wherein the power supply is a single power supply and wherein the power supply controller, in operation, distributes power supplied by the power supply to the conductive bus.

61. The electroplating system of any one of claims 57-60, wherein the power supply comprises two or more power supply devices;

and the power supply controller, in operation, distributes power supplied by the two or more power supply devices to the conductive bus.

62. The electroplating system of any one of claims 57-61, wherein the power supply controller, in operation, distributes power supplied by the power supply to at least two locations on the conductive bus.

63. The electroplating system of any one of claims 57-62, wherein the interior anode is positioned within a fabric material, the fabric material comprising polypropylene, napped poly, cotton, synel, canton flannel, mono-filament polypropylene, nylon, polypropylene microfilet, cotton duck, felt, or polyester.

64. The electroplating system of any one of claims 57-63, further comprising a motor coupled to the contact point assembly and configured to provide rotational motion to the contact point assembly.

8. An apparatus comprising:

a rack configured to support a tubular workpiece, wherein the tubular workpiece is substantially cylindrical, and comprises;

a hollow cavity defined by an inner surface having a first surface area, a longitudinal axis, and an outer surface having a second surface area, the rack comprising;

a conductive bus;

a dynamic contact point assembly electrically coupled to the conductive bus, such that the tubular workpiece and the conductive bus are in electrical contact via the dynamic contact point assembly during rotation of the tubular workpiece;

a drive roller that is substantially cylindrical in shape, the drive roller configured to maintain physical contact with the tubular workpiece; and

a driven roller that is substantially cylindrical in shape, the driven roller configured to maintain physical contact with the tubular workpiece.

9. The apparatus of claim 8, wherein the dynamic contact point assembly includes a conductive roller assembly comprising a conductive roller that is configured to be in electrical contact with the tubular workpiece.

10. The apparatus of claim 9, wherein the conductive roller assembly further comprises:

a first bearing assembly positioned at a first end of the conductive roller; and

a second bearing assembly positioned at a second end of the conductive roller, the first bearing assembly and the second bearing assembly being arranged such that the conductive roller, in operation, is free to rotate with the tubular workpiece while maintaining electrical contact with the conductive bus.

11. The apparatus of claim 10, wherein the first bearing assembly and the second bearing assembly comprise a first needle roller bearing and a second needle roller bearing, respectively, the first needle roller bearing and the second needle roller bearing each having a plurality of cylindrical rollers that are configured to be in electrical contact with the conductive roller and the first needle roller bearing or the second needle roller bearing, respectively.

12. The apparatus of claim 11, wherein the first needle roller bearing or the second needle roller bearing is sheathed in a bearing housing, the bearing housing joined to the conductive bus via a conductive article.

13. The apparatus of claim 12, wherein the bearing housing is joined to the conductive bus via a flexible material.

14. The apparatus of claim 13, wherein the bearing housing is coupled to the conductive article via a mechanical fastener or an adhesive.

23. The apparatus of any of claims 2-22, wherein the conductive bus is configured to maintain electrical contact with the outer surface of the tubular workpiece.

24. The apparatus of any of claims 2-23, wherein the conductive bus is configured to be in electrical contact with the exterior surface of the tubular workpiece in at least two places.

25. The apparatus of any one of claim 6-8 or 12-24, wherein the conductive bus is configured to be in electrical contact with the tubular workpiece via the conductive article, which is configured to maintain physical contact with the tubular workpiece during rotation of the tubular workpiece.

26. The apparatus of any one of claim 6-8 or 12-25, wherein the conductive article is a flexible sheet, a brush, a rod, or a wire.

27. The apparatus of any one of claim 6-8 or 12-26, wherein the conductive article comprises two or more linkages.

28. The apparatus of any one of claim 6-8 or 12-27, wherein the conductive article comprises two or more threaded portions.

29. The apparatus of any one of claims 2-28, wherein the conductive bus is a bus bar that is positioned substantially parallel to the longitudinal axis

65. A method for producing a nanolaminate coating on a tubular workpiece, the method comprising:

introducing a tubular workpiece that is substantially cylindrical, has a longitudinal axis, a hollow cavity defined by an inner surface, and an outer surface, to a system comprising;

a rack that, in operation, supports the tubular workpiece;

an interior anode; and

an electrolyte bath comprising an electrolyte solution having an electrodepositable species;

rotating the tubular workpiece in the rack at a rotational speed; and

electrodepositing the electrodepositable species onto the tubular workpiece as a first nanolaminate coating and a second nanolaminate coating, the first nanolaminate coating being on at least a portion of the outer surface, the first nanolaminate coating having a first thickness; and

the second nanolaminate coating being on at least a portion of the inner surface, the second nanolaminate coating having a second thickness.

66. The method of claim 65, wherein the first thickness is less than the second thickness.

67. The method of claim 65 or 66, wherein the tubular workpiece has a first threaded portion, and the method further comprises electrodepositing the electrodepositable species as a third nanolaminate coating on the first threaded portion, the third nanolaminate coating having a third thickness that is less than the first thickness and the second thickness.

68. The method of claim 67, wherein the electrodepositing the electrodepositable species as a third nanolaminate coating comprises reducing the current density at the first threaded portion.

69. The method of claim 68, wherein the reducing the current density comprises positioning shielding or thieving adjacent to the first threaded portion.

70. The method of any one of claims 65-69, wherein the electrodepositing comprises applying a voltage or a current to a conductive article in contact with the tubular workpiece.

71. The method of any one of claims 65-70, wherein the electrodepositing comprises applying a voltage or a current to a gear or a coupler in physical contact with the tubular workpiece.

72. The method of any one of claims 65-71, wherein the electrodepositing comprises applying a voltage or a current to a conductive roller in electrical contact with the tubular workpiece.

73. The method of any one of claims 70-72, comprising varying the voltage or current over time.

74. The method of any one of claims 65-73, wherein the rotating the tubular workpiece comprises varying the rotational speed over time, such that a composition of the first nanolaminate coating or the second nanolaminate coating is changed.

75. The method of any one of claims 65-76, wherein the rotational speed ranges from about 0.5 revolutions per minute (rpm) to about 10 rpm.

76. The method of claim 74 or 75, wherein the varying the rotational speed over time comprises:

changing the rotational speed from a first rotational speed to a second rotational speed; and

changing the rotational speed from the second rotational speed to the first rotational speed.

77. The method of any one of claims 65-76, wherein the tubular workpiece is rotated by a driven roller that is substantially cylindrical in shape and is in physical contact with the tubular workpiece.

78. The method of any one of claims 65-76, wherein the tubular workpiece is rotated by a gear or a coupler in physical contact with the tubular workpiece.

79. The method of any one of claims 65-78, wherein introducing the tubular workpiece to the system comprises positioning the interior anode along the longitudinal axis of the tubular workpiece or an axis substantially parallel to the longitudinal axis within the hollow cavity of the tubular workpiece such that an exterior surface of the interior anode is positioned a predetermined distance from the inner surface of the tubular workpiece.

80. The method of any one of claims 65-79, wherein the electrodepositing the electrodepositable species comprises distributing a portion of the electrolyte solution into the hollow cavity of the tubular workpiece via a hollow cavity of the interior anode or a plurality of holes that extend laterally through the interior anode;

wherein the electrodepositing the electrodepositable species comprises distributing a portion of the electrolyte solution into the hollow cavity via an electrolyte distribution tube or a plurality of holes in an electrolyte distribution tube positioned in the hollow cavity of the tubular workpiece;

or

both.

81. The method of any one of claims 65-80, wherein the electrodepositing the electrodepositable species comprises positioning an exterior anode adjacent to the tubular workpiece.

82. The method of any one of claims 67-81, wherein the first nanolaminate coating, the second nanolaminate coating, and the third nanolaminate coating collectively cover substantially all of the inner surface and the outer surface.

83. The method of any one of claims 65-82, wherein the first nanolaminate coating, the second nanolaminate coating, or both comprise a series of alternating layers.

84. The method of claim 83, wherein the series of alternating layers comprises:

a first layer comprising at least one electrodepositable species independently selected from Ag, Al, Au, B, Be, C, Co, (Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn, and Zr; and

a second layer comprising at least one electrodepositable species independently selected from Ag, Al, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn, and Zr.

85. The method of claim 84, wherein the first layer or the second layer comprises Ni in a concentration ranging from about 50% (w/w) to about 99% (w/w).

86. The method of claim 84 or 85, wherein the first layer or the second layer comprises Co in a concentration ranging from about 5% (w/w) to about 35% (w/w).

87. The method of any one of claims 84-86, wherein the first layer or the second layer comprises Cr in a concentration ranging from about 5% (w/w) to about 99% (w/w).

88. The method of any of claims 84-87, wherein the first layer and the second layer comprise Ni and W.

89. The method of claim 88, wherein the first layer and the second layer further comprise Mo.

90. The method of claim 88 or 89, wherein the first layer, the second, layer, or both, independently comprise Ni in a concentration ranging from about 40% (w/w) to about 70% (w/w);

wherein the first layer, the second layer, or both, independently comprise W in a concentration ranging from about 30% (w/w) to about 50% (w/w);

or both.

91. The method of claim 90, wherein the first layer, the second layer, or both, independently comprise Mo in a concentration of up to about 40% (w/w)

92. The method of any one of claims 88-91, wherein the first layer, the second layer, or both, independently comprise Ni in a concentration of about 60% (w/w), and W in a concentration of about 40% (w/w).

93. The method of any one of claims 65-92, wherein the first nanolaminate coating is substantially the same thickness at two or more locations;

and

wherein the second nanolaminate coating is substantially the same thickness at two or more locations.

94. An article produced by the method of any one of claims 65-93.

95. An oil country tubular good (OCTG) produced by the method of any one of claims 65-93.

96. A tubular article, comprising:

a tubular workpiece having an interior surface and an exterior surface; and

nanolaminate coatings comprising;

a first nanolaminate coating on the interior surface; and

a second nanolaminate coating on the exterior surface, the second nanolaminate coating having a thickness that is less than a thickness of the first nanolaminate coating.

97. The tubular article of claim 96, further comprising:

a first threaded portion of the tubular workpiece; and

a third nanolaminate coating on the first threaded portion, the third nanolaminate coating having a thickness that is less than the thickness of the first nanolaminate coating.

98. The tubular article of claim 97, wherein the third nanolaminate coating has a thickness that is less than a thickness of the second nanolaminate coating.

99. The tubular article of any one of claims 96-98, wherein the interior surface and the exterior surface are substantially 100% covered by the nanolaminate coatings.

100. The tubular article of any one of claims 97-99, wherein the thickness of the third nanolaminate coating ranges from about 50 micrometer (μ

m) to about 150 μ

m.

101. The tubular article of any one of claims 97-100, wherein the thickness of the third nanolaminate coating does not prevent joining the first threaded portion of the tubular workpiece with a corresponding threaded portion of a second workpiece, such that the joining does not compromise the third nanolaminate coating.

102. The tubular article of any one of claims 96-101, wherein the tubular workpiece comprises a steel alloy.

103. The tubular article of any one of claims 96-101, wherein the tubular workpiece comprises a plastic, and the tubular article further comprises a strike layer on the plastic.

104. The tubular article of any one of claims 96-103, wherein the tubular workpiece is a connector for joining two oil country tubular goods (OCTG).

105. The tubular article of any one of claims 96-103, wherein the tubular workpiece is an OCTG or a line pipe.

106. The tubular article of any one of claims 96-105, wherein the first nanolaminate coating is substantially the same thickness at two or more locations, wherein the second nanolaminate coating is substantially the same thickness at two or more, or both.

107. The tubular article of any one of claims 96-106, wherein the first nanolaminate coating and the second nanolaminate coating each comprise a series of alternating layers.

108. The tubular article of any one of claims 97-107, wherein the third nanolaminate coating comprises a series of alternating layers.

109. The tubular article of claim 107 or 108, wherein the series of alternating layers comprises:

a first layer comprising at least one electrodepositable species independently selected from Ag, Al, Au, B, Be, C, Co, (Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn, and Zr; and

a second layer comprising at least one electrodepositable species independently selected from Ag, Al, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn, and Zr.

110. The tubular article of claim 109, wherein:

the first layer comprises each electrodepositable species of the at least one electrodepositable species in a concentration of at least 0.01% (w/w); and

the second layer comprises each electrodepositable species of the at least one electrodepositable species in a concentration of at least 0.01% (w/w).

111. The tubular article of claim 109 or 110, wherein the first layer or the second layer comprises Ni in a concentration ranging from about 50% (w/w) to about 99% (w/w).

112. The tubular article of any one of claims 109-111, wherein the first layer or the second layer comprises Co in a concentration ranging from about 5% (w/w) to about 35% (w/w).

113. The tubular article of any one of claims 109-112, wherein the first layer or the second layer comprises Cr in a concentration ranging from about 5% (w/w) to about 99% (w/w).

114. The tubular article of any of claims 109-113, wherein the first layer and the second layer comprise Ni and W.

115. The tubular article of claim 114, wherein the first layer and the second layer further comprise Mo.

116. The tubular article of claim 114 or 115, wherein the first layer, the second, layer, or both, independently comprise Ni in a concentration ranging from about 40% (w/w) to about 70% (w/w);

wherein the first layer, the second layer, or both, independently comprise W in a concentration ranging from about 30% (w/w) to about 50% (w/w);

or both.

117. The tubular article of claim 116, wherein the first layer, the second layer, or both, independently comprise Mo in a concentration of up to about 40% (w/w)

118. The tubular article of any one of claims 114-117, wherein the first layer, the second layer, or both, independently comprise Ni in a concentration of about 60% (w/w), and W in a concentration of about 40% (w/w).

119. The tubular article of any one of claims 97-118, wherein the number of layers in the first nanolaminate coating, the second nanolaminate coating, and the third nanolaminate coating comprise a same number of layers.

120. The tubular article of any one of claims 96-119, wherein the tubular workpiece has a length ranging from about 0.1 meters (m) to 15 m.

121. An anode comprising a substantially cylindrical metal member, the metal member having an exterior surface with a surface area feature that increases a surface area of the anode, the metal member, in use, being in electrical contact with a tubular workpiece.

122. The anode of claim 121, wherein the anode is tubular, such that a hollow cavity is defined by an inner surface of the anode.

123. The anode of claim 121 or 122, wherein the surface area feature is a series of continuous alternating convex and concave portions, such that the exterior surface is corrugated.

124. The anode of any one of claims 121-123, wherein the exterior surface is configured in a polygonal or sawtooth tube configuration, the exterior surface comprising a number of interconnected sides.

125. The anode of claim 124, wherein the number of interconnected sides is three, four, five, or six.

126. The anode of claim 124 or 125, wherein the anode has a length, and the number of interconnected sides varies over the length of the anode.

127. The anode of any one of claims 121-126, wherein the anode has a substantially constant material thickness ranging from about 0.25 mm to about 6.4 mm.

128. The anode of any one of claims 121-127, wherein the anode is substantially solid.

129. The anode of any one of claims 121-128, wherein the anode material is substantially non-porous, wherein the anode comprises a plurality of holes that, in operation, distributes or causes mixing of the solution adjacent the anode.

130. The anode of any one of claims 121-129, wherein the anode is porous, and wherein the anode has a percentage open area ranging from about 45% to about 99%.

131. The anode of any one of claims 121-130, wherein the anode comprises Zn, Ni, Sn, or a combination thereof.

132. The anode of any one of claims 121-131, wherein the anode comprises a precious metal.

133. The anode of any one of claims 121-132, wherein the anode is positioned within a fabric material, the fabric material comprising polypropylene, napped poly, cotton, synel, canton flannel, mono-filament polypropylene, nylon, polypropylene microfilet, cotton duck, felt, or polyester.