Composition and Method For Making a Proppant

• US 20080135245A1
• Filed: 06/27/2007
• Published: 06/12/2008
• Est. Priority Date: 02/04/2005
• Status: Active Grant

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Oxane Materials, Inc.
• Inventors: Whitsitt, Elizabeth A., Coker, Christopher E., Barron, Andrew R., Bordia, Rajendra, Costantino, Stephen A., Skala, Robert D., Loscutova, John R., Smith, Russell J., Wiesner, Mark
• Granted Patent: US 7,867,613 B2
• Time in Patent Office: Days
• US Class Current: 166/280.2
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3222 Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
• CPC Class Codes: C04B 2235/3418 Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint glass constituents C04B2235/36
• CPC Class Codes: C04B 2235/5276 Whiskers, spindles, needles or pins
• CPC Class Codes: C04B 2235/528 Spheres
• CPC Class Codes: C04B 2235/5296 with a defined aspect ratio, e.g. indicating sphericity spherical constituents C04B2235/528
• CPC Class Codes: C04B 2235/96 Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/04 based on magnesium oxide
• CPC Class Codes: C04B 35/10 based on aluminium oxide
• CPC Class Codes: C04B 35/14 based on silica
• CPC Class Codes: C04B 35/18 rich in aluminium oxide
• CPC Class Codes: C04B 35/48 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• CPC Class Codes: C04B 35/56 based on carbides or oxycarbides containing free metal binder C22C29/00
• CPC Class Codes: C04B 35/58 based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides containing free binder metal C22C29/00
• CPC Class Codes: C04B 35/62218 obtaining ceramic films, e.g. by using temporary supports
• CPC Class Codes: C04B 35/624 Sol-gel processing
• CPC Class Codes: C04B 35/62655 Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
• CPC Class Codes: C04B 35/62665 Flame, plasma or melting treatment
• CPC Class Codes: C04B 35/628 Coating the powders or the macroscopic reinforcing agents
• CPC Class Codes: C04B 35/62807 Silica or silicates
• CPC Class Codes: C04B 35/6281 : Alkaline earth metal oxides
• CPC Class Codes: C04B 35/62813 : Alumina or aluminates
• CPC Class Codes: C04B 35/62823 : Zirconium or hafnium oxide
• CPC Class Codes: C04B 35/62886 : by wet chemical techniques
• CPC Class Codes: C04B 35/62897 : Coatings characterised by their thickness
• CPC Class Codes: C04B 35/78 : containing non-metallic materials
• CPC Class Codes: C04B 35/80 : Fibres, filaments, whiskers, platelets, or the like
• CPC Class Codes: C04B 38/009 : Porous or hollow ceramic granular materials, e.g. microballoons C04B18/027, C04B20/002 take precedence
• CPC Class Codes: C04B 38/02 : by adding chemical blowing agents
• CPC Class Codes: C04B 38/04 : by dissolving-out added substances
• CPC Class Codes: C04B 38/0655 : Porous materials C04B38/0625 takes precedence
• CPC Class Codes: C04B 38/067 : Macromolecular compounds C04B38/062 takes precedence; polysaccharides C04B38/0645
• CPC Class Codes: C09K 8/80 : Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
• CPC Class Codes: C09K 8/805 : Coated proppants
• CPC Class Codes: Y10T 428/2991 : Coated
• CPC Class Codes: Y10T 428/2993 : Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2995 : Silane, siloxane or silicone coating
• CPC Class Codes: Y10T 428/2998 : including synthetic resin or polymer

Abstract

The present invention relates to proppants which can be used to prop open subterranean formation fractions. Proppant formulations are further disclosed which use one or more proppants of the present invention. Methods to prop open subterranean formation fractions are further disclosed. In addition, other uses for the proppants of the present invention are further disclosed, as well as methods of making the proppants.

Claims

1. A proppant comprising a template sphere having at least one void within the interior of the template sphere and said template sphere having a Krumbein sphericity of at least about 0.3 and a roundness of at least about 0.1, said proppant having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4, and a continuous sintered shell around the entire outer surface of said template sphere, and wherein said shell comprises a ceramic material or oxide thereof and said template sphere comprises a material capable of withstanding sintering.

2. The proppant of claim 1, wherein said continuous shell has a thickness of from about 5 microns to 150 microns, and said template sphere has a specific gravity of 0.01 g/cc to about 1.5 g/cc, and said proppant has a crush strength of about 1,500 psi or greater, and said template sphere has a void volume % of at least 30%.

3. The proppant of claim 1, wherein said template sphere having a sphericity of at least about 0.6, a continuous sintered shell around the entire outer surface of said template sphere, wherein said continuous shell has a substantially uniform thickness, and wherein said template sphere has a specific gravity of 0.01 g/cc to about 1.5 g/cc, and said proppant has a crush strength of about 1,500 psi or greater, and said template sphere has a void volume % of at least 30%.

4. The proppant of claim 2, wherein said crush strength is at least 2,500 psi.

5. The proppant of claim 2, wherein said crush strength is 2,500 psi to 15,000 psi.

6. The proppant of claim 3, wherein said crush strength is at least 2,500 psi.

7. The proppant of claim 3, wherein said crush strength is 2,500 psi to 15,000 psi.

8. The proppant of claim 2, wherein said void volume % is from 30% to 95%.

9. The proppant of claim 2, wherein said void volume % is from 50% to 95%.

10. The proppant of claim 2, wherein said void volume % is from 60% to 90%.

11. The proppant of claim 2, wherein said template sphere has one central void.

12. The proppant of claim 2, wherein said template sphere has one central void and multiple voids throughout said template sphere.

13. The proppant of claim 1, wherein said template sphere comprises a mixture of aluminum oxide and silicon oxide.

14. The proppant of claim 1, wherein said shell comprises aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, or any combination thereof.

15. The proppant of claim 1, wherein said template sphere comprises aerogel, xerogel, pumice, envirospheres, perlite, vermiculite, or fired template spheres.

16. The proppant of claim 1, wherein said shell comprises two or more layers, wherein one of the layers comprises said ceramic material or oxide thereof.

17. The proppant of claim 16, wherein at least one layer of said shell comprises a resin layer or polymer layer.

18. The proppant of claim 17, wherein said resin layer or polymer layer is the outermost layer comprising said shell.

19. The proppant of claim 1, wherein said template sphere has a crush strength of 100 psi to 1,000 psi and said proppant has a crush strength of at least 2,500 psi.

20. The proppant of claim 1, wherein said shell comprises at least one reinforcement material.

21. The proppant of claim 20, wherein said reinforcement material is a fiber, whisker, filler, or any combination thereof.

22. The proppant of claim 20, wherein said reinforcement material is carbon black, fiberglass, carbon fibers, ceramic whiskers, ceramic particulates, hollow spheres, solid spheres, resin material, metallic particles, or any combination thereof.

23. The proppant of claim 1, wherein said shell comprises a metal carbide, metal nitride, or any combination thereof.

24. The proppant of claim 1, wherein said shell comprises a zirconium oxide, a zirconium carbide, a zirconium nitride, or any combination thereof.

25. The proppant of claim 24, wherein said shell further comprises magnesium oxide, calcium oxide, cerium oxide, yttrium oxide, scandium oxide, titanium dioxide, or any combination thereof.

26. The proppant of claim 1, wherein said shell comprises a metal oxide, a metal carbide, a metal nitride, or any combination thereof, derived from a silicon source, titanium source, tungsten source, zirconium source, aluminum source, boron source, or any combination thereof.

27. The proppant of claim 1, wherein said shell is surface modified with the addition of silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, cordierite, spinel, spodumene, steatite, a silicate, a substituted alumino silicate clay or any combination thereof.

28. The proppant of claim 1, wherein said shell is surface modified by applying at least one organic material to said shell.

29. The proppant of claim 1, wherein said shell comprises multiple layers, wherein one of the layers comprises a metal nitride or metal carbide or both.

30. The proppant of claim 1, wherein a glazing layer is present on said template sphere and in immediate contact with said template sphere.

31. The proppant of claim 30, wherein said glazing layer comprises silica, mullite, spodumene, silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, cordierite, spinel, steatite, a silicate, a substituted alumino silicate clay or any combination thereof.

32. The proppant of claim 30, wherein at least a portion of said glazing layer penetrates or infiltrates below the surface of said template sphere.

33. A method of forming the proppant of claim 1, comprising blowing into template spheres with a coaxial blowing nozzle, a suspension or dispersion comprising inorganic or organic solid particles having particle diameters in the range of from 0.001 to 10 microns and heating said template spheres to evaporate any liquid from said suspension or dispersion, and then optionally hardening the template spheres, and further providing a shell around the entire outer surface of said template spheres and then sintering said shell to form a continuous sintered shell.

34. The method of claim 33, further comprising subjecting the template spheres to elevated temperatures to sinter and/or fuse said particles that form the template spheres.

35. The method of claim 33, wherein said suspension or dispersion further comprises a binder material, a film stabilizing agent, a dispersing agent, and a continuous aqueous or non-aqueous liquid phase.

36. The method of claim 33, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

37. A method of forming the proppant of claim 1, comprising:

a) forming template spheres by tumbling together and mixing (1) solidifiable liquid material comprising a thermally fugitive organic binder material and a source of void-forming agent adapted to evolve as a gas and convert the liquid material to a template sphere and (2) a mass of minute discrete free-flowing inorganic heat-sinterable parting agent particles selected from metals, metalloids, metal oxides and metal salts that are wetted by, and at least partially absorbed into, the liquid material during the tumbling action to form liquid spheres;

sufficient parting agent particles being present so that any portion of liquid material uncovered by parting agent particles tumble against discrete unabsorbed parting agent particles;

b) providing conditions during the tumbling action, and tumbling for a sufficient time for the void-forming agent to evolve as a gas and form a central interior space within the liquid spheres and for the thus-hollowed liquid spheres to solidify;

c) collecting the spheres after they have solidified to a shape-retaining condition;

d) optionally firing the hollow spheres to first burn out the organic binder, and to then sinter the parting agent particles to form template spheres; and

e) providing a shell around the entire outer surface of said template spheres and then sintering said shell to form a continuous sintered shell.

38. The method of claim 37, where in step (d) occurs.

39. The method of claim 37, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

40. A method of forming the proppant of claim 1, comprising providing a precursor by forming a mixture of inorganic material and a blowing agent in the shapes of template spheres, optionally drying the mixture and firing the precursor to activate the blowing agent, wherein activation of the blowing agent is controlled such that the blowing agent is activated within a predetermined temperature range, and further providing a shell around the entire outer surface of said template spheres and then sintering said shell to form a continuous sintered shell.

41. The method of claim 40, further comprising firing the precursor to activate the blowing agent.

42. The method of claim 40, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

43. A method of forming the proppant of claim 1, comprising:

a) delivering particles comprising inorganic material to an inlet of a furnace;

b) passing the particles through the furnace;

c) heating the particles as the particles traverse through a heating portion of the furnace to melt at least an outer surface of the particles such that a majority of the particles become substantially spheroidal;

d) cooling the particles as the particles traverse through a cooling portion of the furnace to deter agglomeration and form template spheres; and

e) providing a shell around the entire outer surface of said template sphere and then sintering said shell to form a continuous sintered shell.

44. The method of claim 43, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

45. The method of claim 43, wherein said furnace is a drop tower furnace, a tunnel furnace, a microwave furnace, a drop tube furnace, a rotary kiln, a fluidized bed furnace, or a gravity fed furnace.

46. The method of claim 43, wherein said passing the particles in step b) is achieved by gravity.

47. The method of claim 43, wherein the step of cooling comprises cooling the particles as the particles traverse through a cooling portion of the furnace, wherein, after cooling, the particles have a substantially higher bulk density at room temperature than prior to delivering the particles to the inlet of the furnace.

48. A method of forming the proppant of claim 1, comprising:

a) coating dissolvable beads with a solution comprising an inorganic material;

b) drying the beads so as to form an inorganic coating on the beads;

c) heating the be ads to a first temperature, wherein the first temperature is sufficient to form a continuous inorganic coating and is not sufficient to decompose the beads;

d) dissolving all or some portion of the beads;

e) optionally removing the dissolved beads from within the continuous inorganic coating; and

f) optionally heating the continuous inorganic coating to a second temperature that is sufficient to form said template spheres, and

g) providing a shell around the entire outer surface of said template sphere and then sintering said shell to form a continuous sintered shell.

49. The method of claim 48, wherein step e) and step f) occur.

50. The method of claim 48, wherein said dissolvable beads are polymeric beads.

51. The method of claim 48, wherein said dissolvable beads are inorganic beads.

52. The method of claim 48, wherein said dissolvable beads are geopolymers, ceramic beads, metallic beads, glass beads, ground shells, rust, diatomaceous earth, diatomite, kesselgur, fly ash, gypsum, spent catalyst, clinker, blast furnace slag, or any combination thereof.

53. The method of claim 52, wherein at least 20 volume percent of the dissolvable beads are removed in each template sphere.

54. The method of claim 48, wherein said dissolvable beads are plant seeds;

plant husks;

soil;

crushed nuts;

ground hulls of nuts;

whole nuts;

plant pips;

cells;

coffee grinds;

food products;

algae;

plankton;

animal eggs;

wax;

surfactant-derived liquid beads;

powdered, ground, or crushed agglomerates of wood products;

powdered, ground, or crushed whey;

cellulose;

soap;

bacteria;

rubber;

powdered milk;

animal waste;

unprocessed polymeric resin;

or animal hair.

55. The method of claim 48, wherein said dissolvable bead is spheronized prior to said coating of step a).

56. The method of claim 48, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

57. A method of forming the proppant of claim 1, comprising:

a) coating burnable beads with a solution comprising an inorganic material;

b) drying the burnable beads so as to form an inorganic coating on the beads;

c) heating the coated burnable beads in controlled fashion such that the burnable bead undergoes controlled thermolysis leaving an intact substantially hollow template sphere;

d) providing a shell around the entire outer surface of said template sphere and then sintering said shell to form a continuous sintered shell.

58. The method of claim 57, wherein said beads are polymeric beads.

59. The method of claim 57, wherein said beads are plant seeds;

plant husks;

soils;

crushed nuts;

ground hulls of nuts;

whole nuts;

plant pips;

cells;

coffee grinds;

food products;

algae;

plankton;

animal eggs;

wax;

surfactant-derived liquid beads;

powdered, ground, or crushed agglomerates of wood products;

powdered, ground, or crushed whey;

cellulose;

soap;

bacteria;

rubber;

powdered milk;

animal waste;

unprocessed polymeric resin;

or animal hair.

60. The method of claim 57, wherein said burnable bead is spheronized prior to said coating of step a) by spray drying, rolling, tumbling, or other processes.

61. The method of claim 57, wherein providing said shell comprises introducing said template spheres into a fluidized bed and coating said template spheres with a suspension or dispersion comprising a ceramic material or oxide thereof.

62. A method of forming the proppant of claim 1, comprising forming a template sphere and providing a shell around the entire outer surface of said template sphere, and then sintering said shell to form a continuous sintered shell.

63. The method of claim 62, wherein said sintering comprises liquid phase sintering, reactive phase sintering, solid state sintering, or pressure-assisted sintering.

64. The method of claim 63, wherein said pressure-assisted sintering comprises the application of external gas pressure during heat treatment, with pressures ranging from ambient to 1500 PSIG.

65. The method of claim 62, wherein said sintering comprises indirect radiant heating, direct infrared radiation, direct conduction of heat flux from an environment to said proppant, excitation of molecules of said shell, and consequent heating of said shell by electromagnetic radiation, or inductive coupling of the shell to an external excitation field of alternating current.

66. The method of claim 62, wherein said forming of said template sphere is by a spray drying process, a dehydrating gel process, a sol-gel process, a sol-gel-vibrational dropping process, a drop tower process, a fluidized bed process, a coaxial nozzle gas-bubble process, a thermolysis process, a chemical etching process, or a blowing process.

67. The method of claim 62, wherein said template sphere has a template surface with cracks or flaws, and said method further comprises surface repairing said cracks or flaws with a composition comprising at least one inorganic or ceramic-containing material.

68. The method of claim 67, wherein surface repairing comprises infiltrating said cracks or flaws with a suspension comprising aluminum silicate, ceramic particles (nano-sized) alumoxane, mullite, spinel, zirconia, alumino silicate, magnesium silicate, cordierite, spodumene, steatite, silica, or substituted alumino silicate clay, or a combination thereof.

69. The method of claim 62, wherein said proppant has a proppant surface with cracks or flaws, and said method further comprises surface repairing said cracks or flaws with a composition comprising at least one inorganic or ceramic-containing material.

70. The method of claim 69, wherein surface repairing comprises infiltrating said cracks or flaws with a suspension comprising alumoxane, mullite, or a combination thereof.

71. The proppant of claim 1, wherein said proppant has each of the following characteristics:

(a) an overall diameter of from about 90 microns to about 1,600 microns;

(b) spherical;

(c) said shell has voids or is porous or non-porous;

(d) said proppant has a crush strength of about 1,000 psi or greater;

(e) said coating has a wall thickness of from about 15 to about 120 microns; and

(f) said proppant has a specific gravity of from about 0.9 to about 1.5 g/cc.

72. A proppant formulation comprising the proppant of claim 1 and a carrier.

73. A method to prop open subterranean formation fractions comprising introducing the proppant formulation of claim 72 into said subterranean formation.

74. A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of:

(a) preparing or providing a treating fluid that comprises a fluid, energized fluid, foam, or a gas carrier having the proppant of claim 1 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

75. The method of claim 74, wherein said treating fluid is a fracturing fluid and said particles are deposited in fractures formed in said subterranean producing zone.

76. The method of claim 74, wherein said treating fluid is a gravel packing fluid and said particles are deposited in said well bore adjacent to said subterranean producing zone.

129. The proppant of claim 1, wherein said shell comprises one or more layers and said one or more layers comprises a fugitive phase or hollow material or both.

130. The proppant of claim 129, wherein said fugitive phase or hollow material or both is present uniformly throughout said layer.

131. The proppant of claim 1, wherein said shell comprises Steatite.

132. The proppant of claim 1, wherein said shell comprises two or more layers and wherein at least two layers contain a fugitive phase material or a hollow material or both, wherein the fugitive phase material or hollow material or both are the same or different in each layer.

133. The proppant of claim 132, wherein said two or more layers comprise at least an outer layer and an inner layer, wherein said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said inner layer.

134. The proppant of claim 132, wherein said two or more layers comprise at least an outer layer and an inner layer, wherein said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said inner layer and said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said template sphere.

135. The proppant of claim 129, wherein said layer comprises from about 0.5% to about 15% by volume of said fugitive phase material and/or hollow material.

136. The proppant of claim 129, wherein said layer comprises from about 15% to about 25% by volume of said hollow material when the diameter size of the hollow material is from 0.1 to 0.2 microns.

137. The proppant of claim 129, wherein said layer comprises from about 15 volume % to about 80 volume % of said fugitive phase material and/or hollow material.

138. The proppant of claim 1, wherein said template sphere comprises fugitive phase material and/or hollow material in an amount of from about 0.1 volume % to about 15 volume %.

139. The proppant of claim 1, wherein said template sphere comprises fugitive phase material and/or hollow material in an amount of from about 15 volume % to about 80 volume %.

140. The proppant of claim 1, wherein said shell comprises a coating layer to fill in at least a portion of the pores or voids that are present on a layer comprising a shell or surface of said template sphere.

145. The proppant of claim 20, wherein said reinforcement material is surface treated by a thermal treatment, densification, surface modification, coating, glazing, mechanical treatment, chemical treatment, a direct particle deposition from a slurry containing precursor particles, preferential dissolution of one or more species on the particulates or components, or spark discharge treatment, or any combination thereof.

77. A method of forming a proppant, comprising providing a template sphere wherein said template sphere has one or more flaws on the surface of the template sphere;

removing or diminishing said one or more flaws with one or more chemical treatments, one or more mechanical treatments, one or more thermal treatments, one or more spark discharge treatments, or any combination thereof;

providing a shell around the entire outer surface of said template sphere after said removal or diminishing of one or more flaws, and then sintering said shell to form a continuous sintered shell.

78. The method of claim 77, wherein said chemical treatment is used and comprises treating said template sphere with a chemical that dissolves or otherwise reacts with one or more parts of the surface of the template sphere to remove or reduce said one or more flaws.

79. The method of claim 77, wherein said chemical treatment is used and comprises the preferential dissolution of one or more species contained in and/or on the template sphere.

80. The method of claim 79, wherein said one or more species is silica, iron oxide, free carbon, calcium oxide, sodium oxide, and/or various other contaminant phases that are formed during synthesis of the template system, such that said chemical treatment reduces the overall species content.

81. The method of claim 78, wherein said chemical treatment comprises the application of sodium hydroxide, potassium hydroxide, calcium hydroxide, one or more acids, or any combination thereof to the surface of the template sphere.

82. The method of claim 77, wherein said mechanical treatment is used.

83. The method of claim 82, wherein said mechanical treatment comprises tumbling, tumbling in the presence of abrasive material, impingement, or any combination thereof.

84. The method of claim 77, wherein said thermal treatment is used and comprises a furnace, injection into a high temperature plasma flame, or other high temperature flames.

85. The method of claim 84, wherein said thermal treatment is conducted in the presence of reduced pressure or increased pressure relative to ambient pressure.

86. The method of claim 84, wherein during said thermal treatment, an active phase is present in order to react with one or more phases in the template sphere.

87. The method of claim 77, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 5 or less.

88. The method of claim 77, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 0.1 to 4.

89. The method of claim 77, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 0.5 to 1.3.

90. The method of claim 77, wherein after removing or diminishing one or more flaws, the template sphere has a radius of curvature of from 0.5 microns to 100 microns.

91. The method of claim 77, wherein after removing or diminishing said one or more flaws, the overall surface area of the template sphere is reduced from 1% to 10% compared to the template sphere prior to the surface treatment.

97. The proppant formed by the process of claim 77.

92. A method of forming a proppant comprising providing a template sphere and forming a shell around the entire outer surface of said template sphere by a direct particle deposition from a slurry containing precursor particles that form the shell or coating and then drying or sintering said shell to form a continuous sintered shell.

93. The method of claim 92, wherein one or more sacrificial monolayers are first applied to the template sphere to induce covalent bonding or other attachment mechanisms between the surface of the template and the particles in suspension that form said shell.

94. A method of forming a proppant comprising providing a template sphere and forming a shell around the entire outer surface of said template sphere by direct nucleation and deposition of species onto the template sphere.

95. The method of claim 94, wherein said direct nucleation and deposition comprises a precipitation reaction.

96. The method of claim 95, wherein said precipitation reaction used to form said shell is accomplished through the adjustment of the pH of a solution that contains said template sphere, adjustment of temperature, adjustment of pressure, or any combination thereof.

98. A method of forming a sphere, comprising providing a template sphere wherein said template sphere has one or more flaws on the surface of the template sphere;

removing or diminishing said one or more flaws with one or more chemical treatments, one or more mechanical treatments, one or more thermal treatments, one or more spark discharge treatments, or any combination thereof.

99. The method of claim 98, wherein said chemical treatment is used and comprises treating said template sphere with a chemical that dissolves or otherwise reacts with one or more parts of the surface of the template sphere to remove or reduce said one or more flaws.

100. The method of claim 98, wherein said chemical treatment is used and comprises the preferential dissolution of one or more species contained in and/or on the template sphere.

101. The method of claim 100, wherein said one or more species is silica, iron oxide, free carbon, calcium oxide, sodium oxide, and/or various other contaminant phases that are formed during synthesis of the template system, such that said chemical treatment reduces the overall species content.

102. The method of claim 99, wherein said chemical treatment comprises the application of sodium hydroxide, potassium hydroxide, calcium carbonate, calcium hydroxide, one or more acids, or any combination thereof to the surface of the template sphere.

103. The method of claim 98, wherein said mechanical treatment is used.

104. The method of claim 103, wherein said mechanical treatment comprises tumbling, tumbling in the presence of abrasive material, impingement, or any combination thereof.

105. The method of claim 98, wherein said thermal treatment is used and comprises a furnace, injection into a high temperature plasma flame, or other high temperature flames.

106. The method of claim 105, wherein said thermal treatment is conducted in the presence of reduced pressure or increased pressure relative to ambient pressure.

107. The method of claim 105, wherein during said thermal treatment, an active phase is present in order to react with one or more phases in the template sphere.

108. The method of claim 98, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 5 or less.

109. The method of claim 98, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 0.1 to 4.

110. The method of claim 98, wherein said template sphere after removing or diminishing one or more flaws, has an aspect ratio of 0.5 to 1.3.

111. The method of claim 98, wherein after removing or diminishing one or more flaws, the template sphere has a radius of curvature of from 0.5 microns to 100 microns.

112. The method of claim 98, wherein after removing or diminishing said one or more flaws, the overall surface area of the template sphere is reduced from 1% to 10% compared to the template sphere prior to the surface treatment.

113. The method of claim 98, wherein said template sphere has one central void.

114. The method of claim 98, wherein said template sphere has one central void and multiple voids throughout said template sphere.

115. The method of claim 98, wherein said template sphere comprises a mixture of aluminum oxide and silicon oxide.

116. The method of claim 98, wherein said template sphere comprises aerogel, xerogel, pumice, envirospheres, perlite, vermiculite, or fired template spheres.

117. The method of claim 98, wherein said template sphere is a non-composite material.

118. The method of claim 98, wherein said template sphere is a composite material.

119. The method of claim 98, wherein said template sphere is a cenosphere.

120. The method of claim 98, wherein said template sphere comprises fly ash particles or particles derived from fly ash.

121. The method of claim 98, wherein said template sphere is an aluminate.

122. The method of claim 98, wherein said template sphere is a blown sphere.

123. The method of claim 98, wherein said template sphere is a synthetic ceramic microsphere.

124. Sphere particles formed by the method of claim 98.

125. A concrete product comprising a plurality of the sphere particles of claim 124 and cement.

126. A proppant comprising the sphere particles of claim 124.

127. A matrix comprising a plurality of the sphere particles of claim 124 and at least one matrix material.

128. A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of:

(a) preparing or providing a treating fluid that comprises a fluid, energized fluid, foam or gas carrier having the proppant of claim 126 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

141. A method of forming a reinforced template sphere comprising providing a template sphere and reinforcing around the outer surface of said template sphere by direct nucleation and deposition of species onto the template sphere.

142. The method of claim 141, wherein said direct nucleation and deposition comprises a precipitation reaction.

143. The method of claim 142, wherein said precipitation reaction utilizes a precipitation precursor selected from titanium tetrachloride, titanium oxychloride, titanium chloride, titanium oxysulphate, titanium sulphate, titanium organo-metallic compounds, titanium isopropoxide, calcium chloride, calcium hydroxide, aluminum chloride, aluminum nitrate, aluminum sulphate, aluminum organo-metallics, aluminum isopropoxide, or any combination thereof.

144. A method of forming a proppant comprising providing a template sphere having silica present and reacting a calcium containing species with said silica to form a calcium silicate phase on said template, and optionally coating said calcium silicate phase with at least one layer comprising a ceramic material.