Source: http://www.google.com/patents/US7828998?dq=6,332,126
Timestamp: 2017-08-20 06:48:27
Document Index: 439633237

Matched Legal Cases: ['Application No. 200800008', 'Application No. 200700583', 'Application No. 200701830', 'Application No. 200700583', 'Application No. 200700296', 'Application No. 200700583', 'Application No. 200680038963', 'Application No. 200580030660']

Patent US7828998 - Material having a controlled microstructure, core-shell macrostructure, and ... - Google Patents
Disclosed is a method for making a material having a controlled microstructure, the method including providing particles of a ceramic mineral material, the particles having a metal oxide dopant therein. The particles of the ceramic mineral material are consolidated into larger aggregates of a size relevant...http://www.google.com/patents/US7828998?utm_source=gb-gplus-sharePatent US7828998 - Material having a controlled microstructure, core-shell macrostructure, and method for its fabrication
Publication number US7828998 B2
Application number US 11/775,671
Also published as US20080015103, WO2008008828A2, WO2008008828A3
Publication number 11775671, 775671, US 7828998 B2, US 7828998B2, US-B2-7828998, US7828998 B2, US7828998B2
Inventors Walter G. Luscher, John R. Hellmann, Barry E. Scheetz, Brett A. Wilson
Original Assignee Carbo Ceramics, Inc.
Patent Citations (253), Non-Patent Citations (79), Referenced by (3), Classifications (18), Legal Events (6)
Material having a controlled microstructure, core-shell macrostructure, and method for its fabrication
US 7828998 B2
Disclosed is a method for making a material having a controlled microstructure, the method including providing particles of a ceramic mineral material, the particles having a metal oxide dopant therein. The particles of the ceramic mineral material are consolidated into larger aggregates of a size relevant to the desired application using standard industrial mixing and pelletizing technology. The aggregates are heated under reducing conditions so that at least part of the dopant is reduced to form a transient, metastable liquid phase among the particles. The liquid phase includes at least part of the reduced dopant and promotes sintering of the particles and forms islands of reduced metal within the material and on the surface of the aggregates. Following heating of the aggregates under reducing conditions, the aggregates are heated under oxidizing conditions such that the islands of reduced metal are oxidized and/or go into solid solution within the particles, thereby creating voids within and form a shell thereon the particles.
1. A method for making a material having a controlled microstructure comprising:
providing ceramic mineral material particles comprising a metal oxide dopant;
consolidating a plurality of said particles into aggregates comprising a plurality of said particles;
heating said aggregated particles in a reducing atmosphere under conditions of controlled oxygen fugacity so as to at least partially reduce said dopant to at least one of a lower metal oxide and free metal and form a metastable, transient liquid phase amongst said particles, said liquid phase comprising said at least one of a lower metal oxide and free metal; whereby said liquid phase promotes sintering of said aggregated particles and forms islands comprising said free metal in the interior of and on the surface of said aggregated particles; and
heating in an oxidizing atmosphere said aggregated particles having said islands comprising said metal formed therein, so as to cause at least a portion of the material comprising said islands in the interior of said aggregated particles to be taken up by said aggregated particles, the talking up of the material comprising said islands forming an inner region of said aggregated particles with a plurality of voids and forming an outer shell region with fewer voids than said inner region.
2. The method of claim 1, wherein said ceramic mineral material comprises an oxygen-containing mineral material selected from the group consisting of oxides of aluminum, oxides of silicon, aluminosilicates and combinations thereof.
3. The method of claim 2 wherein said oxygen-containing mineral material is selected from the group consisting of kaolinite, bauxite, fly ash and combinations thereof.
4. The method of claim 1 wherein said metal oxide dopant includes an oxide of a polyvalent transition metal.
5. The method of claim 4 wherein said metal oxide dopant comprises Fe2O3.
6. The method of claim 1 wherein said ceramic mineral material particles comprise 0.1-10 percent by weight of said metal oxide dopant.
7. The method of claim 1 wherein said aggregated particles have a sieve size in the range of 12-20 to 20-40 mesh.
8. The method of claim 1 wherein said aggregated particles are heated in said reducing atmosphere to a temperature in the range of 800-1800° C.
9. The method of claim 1 wherein said liquid phase forms a metastable eutectic with the ceramic mineral material.
10. The method of claim 1 wherein said reducing atmosphere has a partial pressure of oxygen of less than 0.005 atm.
11. The method of claim 1 wherein said oxidizing atmosphere comprises air.
12. The method of claim 1 wherein said aggregated particles are heated in said oxidizing atmosphere at atmospheric pressure.
13. The method of claim 1 comprising spheroidizing said particles into aggregates prior to heating said aggregated particles in said reducing atmosphere.
14. The method of claim 1 wherein said aggregated particles are stirred during heating so as to prevent further agglomeration thereof.
15. The method of claim 1 wherein said metal oxide dopant comprises Fe2O3, and wherein when said aggregated particles are heated in said reducing atmosphere, said metal oxide dopant is initially reduced to FeO which forms a metastable eutectic mixture with the ceramic mineral material of said aggregated particles, and wherein said FeO is subsequently at least partially reduced to Fe and said islands include said Fe.
16. A method for making a material having a controlled microstructure comprising:
providing particles comprising a ceramic mineral material and a metal oxide dopant wherein said ceramic mineral material is selected from the group consisting of kaolinite, bauxite, fly ash and combinations thereof and wherein said metal oxide dopant is selected from the group consisting of oxides of polyvalent transition metals;
heating said aggregated particles in a reducing atmosphere having a partial pressure of oxygen of less than 0.005 atm and so as to at least partially reduce said metal oxide dopant and form a metastable transient liquid phase in said particles, said liquid phase comprising said at least partially reduced metal oxide dopant; whereby said liquid phase promotes sintering of said aggregated particles and forms islands of reduced metal in the interior and on the surface of said aggregated particles; and
heating said aggregated particles having said islands formed therein in air, so as to cause at least a portion of the reduced metal forming said islands in the interior of said aggregated particles to be taken up by said aggregated particles creating voids therein and to consolidate the islands of said metal on the surface of said aggregated particles so as to at least partially form a shell thereupon.
This application claims priority of U.S. Provisional Patent Application Ser. No. 60/807,012, filed Jul. 11, 2006, entitled “Dopant Enhanced Densification of Aluminosilicate Aggregate” which is incorporated herein by reference.
The inventions disclosed herein relate to materials and to methods for their fabrication. Certain embodiments of the invention relate to a microstructured material having a core/shell structure. Certain other embodiments relate to a material having a ceramic-based core structure with tailored porosity surrounded by a dense metal or metal-oxide based shell.
Ceramic type mineral materials generally combine high strength with chemical and thermal stability. Hence they have significant utility in many products and processes. For example, ceramic-based materials are often used as supports for catalysts and as casting sands and mold materials used for the fabrication of a variety of articles in high temperature fabrication processes. Particulate ceramic materials also have significant utility as proppants in hydrocarbon recovery processes. Such materials are injected, under very high pressures, into geological structures, together with carrier fluids in a process called hydrofracturing. The injected fluid opens cracks in rock structures allowing for the passage of hydrocarbon products therethrough. The proppant materials wedge into these opened cracks and serve to maintain the integrity and permeability of the cracked structure during the extraction process. Such materials need to have high strength and chemical inertness, and should also have densities comparable to that of the carrier fluid. In addition, since these materials are used in very large amounts, their cost should be low.
The present invention relates to ceramic-based, tailored microstructure materials comprising a ceramic core having a plurality of voids therein, and further including a metal or metal-oxide shell on the outer surface thereof. According to embodiments of the present invention, the ceramic-based, tailored microstructure materials are prepared by a dopant induced transient liquid phase sintering process under controlled oxygen fugacity. The methods of such embodiments may be utilized to prepare a variety of materials having selectably controllable properties such as density, chemical reactivity, thermal reactivity, strength and the like.
According to certain embodiments of the method of the present invention for making a material having a controlled microstructure, the method includes providing particles of a ceramic mineral material the particles having a metal oxide dopant therein. The particles of the ceramic mineral material are consolidated into larger aggregates of a desired size. The aggregates of the ceramic mineral particulates are heated initially under reducing conditions so that at least part of the metal oxide dopant is reduced to form a metastable, transient liquid phase among the particles. The liquid phase includes at least part of the reduced metal oxide dopant, promotes sintering among the particles and forms islands of reduced metal oxide dopant within and on the surface of the aggregates. Following heating under reducing conditions, the aggregates are heated under oxidizing conditions such that the islands of reduced metal oxide are oxidized and/or go into solid solution within the particles, thereby creating voids within and forming a shell on the aggregates.
According to certain embodiments of the present invention, the ceramic mineral material can include oxides of aluminum, oxides of silicon, aluminosilicates and combinations thereof. In some embodiments, the ceramic mineral material can include kaolinite, bauxite, fly ash and combinations thereof. In some embodiments, the metal oxide dopant can include an oxide of a polyvalent transition metal and in some embodiments can include oxides of iron, and/or oxides of titanium, chromium, manganese, or others, and combinations thereof. In one embodiment, the dopant includes hematite. In some embodiments, the amount of metal oxide dopant can range from approximately 0.1 to 30 weight percent of the particles. In some embodiments, the aggregates can have a sieve size in the range of 12-20 to 20-40 mesh and at least one of the heating steps includes a temperature in the range of 1100-1800° C. In some embodiments, larger or smaller aggregate size ranges are used. When heated within this temperature range under a controlled oxygen fugacity, the liquid phase forms a metastable eutectic with the ceramic mineral material, thereby promoting sintering. Post sintering thermal treatment under an alternative oxygen fugacity causes the formation of voids within the aggregates.
In an exemplary embodiment of the present invention, the reducing conditions include a reducing atmosphere with a partial pressure of oxygen of less than 0.005 atm. The oxidizing conditions include an oxidizing atmosphere made from air and can be carried out at atmospheric pressure. Alternative oxidizing conditions can be selected to promote the evolution of the metastable transient liquid phase, as well as to alter the subsequent phase stability of the dopant oxides to promote pore evolution. The aggregates can be stirred during at least one of the heating steps so as to prevent sticking and agglomeration thereof.
FIG. 1 is a scanning electron image of the cross-section of an aggregate of the present invention after being heated under reducing conditions;
FIG. 2 is a scanning electron image of the circle region shown in FIG. 1;
FIG. 3 is a scanning electron image of the cross-section of an aggregate of the present invention after being heated under oxidizing conditions; and
FIG. 4 is a higher magnification of the aggregate shown in FIG. 3.
In general, the methods of the present invention may be implemented utilizing a variety of mineral materials. Typically, the materials used in the various embodiments of the present invention comprise ceramics, and in specific instances, they may comprise oxide and/or silicate-based ceramics such as alumina, aluminosilicates, silicates, and the like. These minerals may include natural products such as kaolin or bentonites, or they may comprise specifically synthesized ceramic materials, or they may comprise industrial byproducts such as fly ash. A dopant material comprising a metal oxide is incorporated into the ceramic material in an amount sufficient so as to facilitate the reactions described hereinbelow. In specific instances, the ceramic material may naturally include some amount of the dopant species therein, and an additional amount of metal oxide dopant can be added so as to raise the total concentration of the dopant material in the ceramic material to between approximately 0.1-30 percent by weight of the ceramic material. In some instances, the as-obtained mineral material will include relatively large amounts of the dopant species therein, while in other instances, the concentration will be low to negligible. Appropriate supplementation may be made by one of skill in the art.
Following the incorporation of the dopant, the mineral material is prepared for further processing, typically by forming it into aggregates having a size and shape consistent with the intended end use of the resultant product. Typically, the starting materials are ground or otherwise pulverized, together with the dopant material. In some instances, the resultant particles are pelletized into substantially larger aggregates so as to provide the resultant product with a desired texture, geometry and size. The specific size of particles employed will depend upon particular applications; however, for many typical applications, including applications as hydrocarbon recovery proppants, particle sizes in the range of 12-20 mesh to 20-40 mesh will be employed. As is known to those of ordinary skill in the art, particles having a size range of 12-20 mesh will pass through a sieve having a 12 mesh size, but be retained by a sieve having a 20 mesh size. A similar relationship holds true for particles having a 20-40 mesh size, It should be understood that in other applications, larger or smaller particle sizes may be employed.
Following the formation of the aggregates, the dopant-containing particles are heated under reducing conditions. Heating may, for example, be carried out in a kiln or furnace, and in specific instances, a rotary kiln is employed to assure that particle-particle adhesion during heating is minimized. The reducing conditions are typically supplied by introducing a reducing atmosphere into the vessel in which the heating is taking place. This atmosphere may comprise a forming gas (N2/H2 mixture) as is known in the art, or it may comprise other reducing atmospheres such as a hydrogen atmosphere, a hydrocarbon-containing atmosphere or the like. In this heating step, the reducing atmosphere at least partially reduces the metal oxide dopant and assists in the formation of a metastable transient liquid phase. This reduction of the metal oxide dopant produces a reduced species comprising lower oxides, a free metal, or a combination of the foregoing. Heating is carried out at a temperature sufficient to liquefy the at least partially reduced dopant material, and this liquid phase serves to facilitate sintering of the mineral material. In some embodiments, the liquid phase forms a metastable eutectic with the mineral material and thereby causes sintering to occur at a lower temperature than would be the case if the liquid phase was not present. This liquid phase migrates through the mineral material, and in general, is further reduced in the course of the heating under reducing conditions. In many instances, the further reduction increases the amount of free metal in the liquid phase, and since the free metal is less likely to wet the mineral material, it thereby aggregates to produce metallic islands both in the bulk of the material also known as the matrix material and on the surface of the particles. The net result of the heating under reducing conditions is the production of a sintered particulate material having islands of a metal and/or a metal-containing species disposed both in the matrix material and on the surface thereof. The matrix material includes polycrystalline ceramic material with glassy grain boundaries, the glassy grain boundaries having an amorphous and/or non-amorphous structure.
The sintered particulate material prepared by heating under reducing conditions is then subjected to heating under oxidizing conditions. In particular embodiments, the heating tinder oxidizing conditions is implemented by heating the sintered particulate material in ambient air, at atmospheric pressure; although, in other instances, more or less vigorous oxidation conditions may be found to be beneficial. When the sintered particulate material is heated under oxidizing conditions, the islands of metal in the matrix material interact with the matrix material and the oxidizing atmosphere and are at least partially reabsorbed back into the matrix material either as oxidized metal or as a component of a complex with the matrix material. The oxidizing conditions can be judiciously selected to tailor the resulting stability of selected crystalline and/or amorphous constituents to promote pore evolution via oxidative decomposition. The net result is that a plurality of voids are formed in the matrix material. The metallic material disposed on the outer surface of the sintered particulate material is not reabsorbed into the matrix material, or is at least reabsorbed to a lesser degree and typically consolidates and disperses so as to form a relatively voidless shell-like structure surrounding the inner structure of the particle having a plurality of voids therein. It is to be understood that this shell may comprise a continuous or a discontinuous body. In some instances, the metallic material on the surface of the particle interacts to some degree with the oxidizing atmosphere so as to form an at least partially oxidized metallic material.
The net result of the process is the production of an aggregate comprised of sintered primary particles, resulting in a relatively high strength ceramic body having a plurality of voids therein and further including a relatively voidless outer shell of a metal or metal-oxide based material. These aggregates have high strength and relatively low density owing to the void structure therein. It will be appreciated by those of ordinary skill in the art that by the appropriate selection of materials and reaction conditions, properties of the aggregate comprised of sintered primary particles may be readily controlled over a wide range of compositional and processing parameters (e.g. temperature, time, oxygen fugacity, etc.).
In one specific group of embodiments of the process of the present invention, starting mineral ores of kaolinite and bauxite were ground to a fine powder (approximately 30 micron) and doped with up to ten weight percent of hematite (Fe2O3) each. The powders were spheroidized in an industrial mixer and size classified by sieving to isolate aggregates in the size range of 12-20 to 20-40 mesh. The resultant mixtures were then heated in a rotary kiln at a temperature in the nominal range of 1400-1600° C. under a forming gas atmosphere (N2/H2 mixture). The oxygen partial pressure was below 0.05 atm, and it was noted that during the sintering process the Fe2O3 was initially reduced to FeO, which forms a metastable eutectic mixture with alumina, silica, and aluminosilicates at a temperature of approximately 1148° C. The formation of this eutectic mixture promoted the sintering of the mineral material at a relatively low temperature. Capillary forces aided in the passage of the iron-rich aluminosilicate liquid through the particulate material, thereby redistributing solids and minimizing porosity through solution precipitation reactions between the liquid and the solid.
As the reduction process proceeded, the iron-rich aluminosilicate liquid was further reduced to form elemental iron. Elemental iron does not readily wet ceramic materials, and hence the liquid phase in the interior portions of the aggregate formed pockets or islands while the liquid phase at the exterior segregated to the surface to form islands thereupon. This process resulted in formation of a ceramic sphere having islands of metal dispersed on the outer surface thereof, and further containing metal islands therein. This material could be used as is for a catalyst, and appropriate catalytic activity could be selected by an appropriate choice of metal oxide dopants. FIG. 1 shows a scanning electron micrograph of a cross section of a bauxite-derived aggregate doped with 10% hematite after being heated in the nominal range of 1400-1600° C. under the forming gas. FIG. 2 is a higher magnification of the circled region in FIG. 1. As shown in these two figures, the aggregate is relatively dense and includes significant amounts of iron on the surface thereof.
Next, the thus-produced particles were heated in an oxidizing atmosphere, which in this embodiment was comprised of air at atmospheric pressure. Heating was again carried out in a rotary kiln at temperatures in the nominal range of 1400-1600° C. This heating process caused the internal islands of elemental iron to be taken back up by the solid matrix material. The iron dissolved into the matrix and/or reacted with surrounding crystal phases, as for example to produce iron titanates. The take-up of the metal produced a number of voids in the sintered aggregate via oxidative decomposition of less stable metal oxides and further served to densify and consolidate the outer metal shell/layer, as shown in FIGS. 3 and 4.
The materials thus produced exhibited a structure which combined high strength together with a controlled density. An example of the experimental parameters used in the above-described process are listed below in Table 1. In addition, Table 2 provides properties of particles produced according to the present invention wherein the characteristic strength, specific gravity and specific strength are compared with current state of the art materials CARBOHSP® and CARBOPROP® with a 20-40 mesh size, manufactured by CARBO Ceramics of Irving, Tex. As shown by Table 2, particles of this type have improved properties in terms of a reduction of specific gravity while maintaining strength and an increase in specific strength (i.e. the ratio of strength to density). compared to current state of the art materials and have significant utility as proppant materials.
Rate Temperature Dwell Time Oxygen Partial
Step # (° C./min) (° C.) (min) Pressure (atm)
Step 1 16 1450 30 1.00 × 10−8
Step 2 16 1450 30 0.21 (air)
Ceramic Iron Oxide Alumina Characteristic Specific Specific
Mineral Content Sintering Content Strength Gravity Strength
Material (wt %) Stage (wt %) (MPa) (g/cc) (MPa/(g/cc))
Bauxite 5 Reducing 72
Bauxite 5 Oxidizing 72 193 3.16 61
Bauxite 10 Reducing 72
Bauxite 10 Oxidizing 72 166 3.43 48
Kaoilnite 5 Reducing 48 236 2.68 88
Kaolinite 5 Oxidizing 48 147 2.51 59
Kaolinite 10 Reducing 48 136 2.75 49
Kaolinite 10 Oxidizing 48 102 2.85 36
CARBOHSP ® 80 250 4.00 63
CARBOPROP ® 72 210 3.70 57
It will be appreciated that by appropriate control of reaction conditions, dopant materials, dopant quantities and the like, the ultimate microstructure of the aggregate may be selectably determined.
While the foregoing has described the preparation of microstructured particles utilizing an iron-based dopant, it is to be understood that other dopant species may be similarly employed. For example, other polyvalent transition metals such as titanium, tin, chromium, manganese and the like may be employed singly or in combination so as to produce composites which include those specified metals. Such materials may have particular utility as catalysts, electro- and/or magnetically-active materials or the like. It is also to be understood that the thus-prepared particles may be subjected to further reactions. For example, the metal-containing particles may be subjected to other reactive atmospheres such as carburizing atmospheres, nitriding atmospheres and the like so as to produce particles having coatings of metal carbides, nitrides and the like on their surfaces. Such particles and/or aggregates can exhibit enhanced hardness and may have utility as high-strength materials, abrasives and the like.
According to certain embodiments, the dopant materials used in the present invention will be present in a range of between 0.1-30 weight percent of the ceramic material. In some embodiments, the dopant materials will be present in a range of between 0.1-10 weight percent of the ceramic material, and in other embodiments in a range of between 5-10 weight percent of the ceramic material.
Typical reduction reactions will be carried out at a temperature range sufficiently high to promote the formation of the transient: metastable liquid phase, and this range will typically be 800-1800° C. In some embodiments, the temperature range will be 1100-1800° C., and in other embodiments the temperature range will be 1400-1600° C. Reaction times will depend upon the temperature and the nature of the materials employed, but it is anticipated that most commercially feasible processes will utilize reaction times for the reduction step in the range of 20-120 minutes. The oxidation reaction will typically be carried out under time and temperature conditions similar to those for the reduction step.
While the foregoing has described the use of rotary kilns for the heating step, it is to be understood that other heating systems may be employed. These can include fluidized bed reactors, stirred bed reactors, tube furnaces, microwave heating, and other such heating systems. The heating may be carried out in a single reactor by varying the atmosphere therein or by using different atmospheric zones. The process may also be carried out using separate reactors.
In view of the foregoing, it will be understood that numerous modifications and variations of the inventions presented herein will be apparent to those of skill in the art. The forgoing is illustrative of particular embodiments of the invention, but is not meant to be a limitation upon the practice thereof. It is the following claims, including all equivalents, which define the scope of these inventions.
US1942431 Nov 18, 1931 Jan 9, 1934 Refractory brick and process of
US2566117 Jun 14, 1947 Aug 28, 1951 Babcock & Wilcox Co Refractory heat transfer bodies and process of manufacture
US2699212 Sep 1, 1948 Jan 11, 1955 Dismukes Newton B Method of forming passageways extending from well bores
US2799074 Jan 24, 1952 Jul 16, 1957 qarloni
US2950247 May 16, 1957 Aug 23, 1960 Atlantic Refining Co Increasing permeability of subsurface formations
US2966457 May 8, 1956 Dec 27, 1960 Swift & Co Gelled fracturing fluids
US3026938 Sep 2, 1958 Mar 27, 1962 Gulf Research Development Co Propping agent for a fracturing process
US3075581 Jun 13, 1960 Jan 29, 1963 Atlantic Retining Company Increasing permeability of subsurface formations
US3126056 Apr 11, 1962 Mar 24, 1964 Hydraulic fracturing of earth formations
US3241613 Feb 19, 1962 Mar 22, 1966 Atlantic Refining Co Shutting off water in vertical fractures
US3242032 Nov 24, 1961 Mar 22, 1966 Charles W Schott Glass spheres and underground proppants and methods of making the same
US3245866 Nov 24, 1961 Apr 12, 1966 Charles W Schott Vitreous spheres of slag and slag-like materials and underground propplants
US3347798 Jun 10, 1964 Oct 17, 1967 Basf Ag Production of catalysts or catalyst carriers in the form of hollow beads
US3350482 Apr 18, 1962 Oct 31, 1967 Sun Oil Co Method of producing spherical solids
US3399727 Sep 16, 1966 Sep 3, 1968 Exxon Production Research Co Method for propping a fracture
US3437148 Jan 6, 1967 Apr 8, 1969 Union Carbide Corp Method and article for increasing the permeability of earth formations
US3486706 Feb 10, 1967 Dec 30, 1969 Minnesota Mining & Mfg Ceramic grinding media
US3497008 Mar 5, 1968 Feb 24, 1970 Exxon Production Research Co Method of propping fractures with ceramic particles
US3598373 Mar 26, 1970 Aug 10, 1971 Coors Porcelanin Co Method and apparatus for making small ceramic spheres
US3663165 Feb 9, 1970 May 16, 1972 Engelhard Min & Chem Zeolitic catalyst and preparation
US3690622 Feb 26, 1970 Sep 12, 1972 Joseph Moritz Hugo Brunner Processing and mixing machine
US3758318 Mar 29, 1971 Sep 11, 1973 Kaiser Aluminium Chem Corp Production of mullite refractory
US3810768 Apr 6, 1972 May 14, 1974 Chicago Fire Brick Co Refractory composition comprising coarse particles of clay or bauxite and carbon
US3856441 Nov 3, 1972 Dec 24, 1974 Ube Industries Apparatus for pelletizing powdered solid substance in a fluidized bed
US3890072 Sep 4, 1973 Jun 17, 1975 Norton Co Apparatus for forming solid spherical pellets
US3939246 Mar 29, 1974 Feb 17, 1976 Mobil Oil Corporation Manufacture of crystalline aluminosilicate zeolites
US3976138 Oct 15, 1975 Aug 24, 1976 Union Carbide Corporation Method of increasing permeability in subsurface earth formation
US4051603 Jul 15, 1974 Oct 4, 1977 Struthers Scientific And International Corporation Fluidized bed apparatus
US4052794 Feb 24, 1976 Oct 11, 1977 Struthers Scientific And International Corporation Fluidized bed process
US4053375 Jul 16, 1976 Oct 11, 1977 Dorr-Oliver Incorporated Process for recovery of alumina-cryolite waste in aluminum production
US4061596 Dec 2, 1975 Dec 6, 1977 Mitsubishi Chemical Industries Ltd. Process for preparing titanium oxide shaped carrier
US4072193 Mar 19, 1976 Feb 7, 1978 Institut Francais Du Petrole Propping agent and method of propping open fractures in the walls of a bored well
US4077908 Sep 3, 1976 Mar 7, 1978 Hoechst Aktiengesellschaft Production of material consisting of solid hollow spheroids
US4104342 Aug 29, 1972 Aug 1, 1978 Mannesmann Aktiengesellschaft Method for making metal powder of low oxygen content
US4113660 Dec 22, 1976 Sep 12, 1978 Sakai Chemical Industry Co., Ltd. Production of shaped catalysts or carriers comprising titanium oxides
US4140773 Feb 24, 1978 Feb 20, 1979 Continental Oil Company Production of high pore volume alumina spheres
US4191720 * Oct 6, 1977 Mar 4, 1980 General Electric Company Method for making porous, crushable core having an integral outer barrier layer
US4195010 Jul 6, 1977 Mar 25, 1980 Burns & Russell Company of Baltimore City Ceramic coated quartz particles
US4268311 Nov 1, 1979 May 19, 1981 Anchor Hocking Corporation High strength cordierite ceramic
US4296051 Oct 22, 1979 Oct 20, 1981 Shikoku Kasei Kogyo Co., Ltd. Method of producing granular sodium dichloroisocyanurate
US4303204 Oct 27, 1980 Dec 1, 1981 Reynolds Metals Company Upgrading of bauxites, bauxitic clays, and aluminum mineral bearing clays
US4343751 Sep 15, 1980 Aug 10, 1982 Lowe's, Inc. Clay agglomeration process
US4371481 Nov 24, 1980 Feb 1, 1983 Phillips Petroleum Company Iron-containing refractory balls for retorting oil shale
US4396595 Feb 8, 1982 Aug 2, 1983 North American Philips Electric Corp. Method of enhancing the optical transmissivity of polycrystalline alumina bodies, and article produced by such method
US4427068 Aug 4, 1982 Mar 24, 1992 Carbo Ceramics Inc Title not available
US4442897 May 13, 1982 Apr 17, 1984 Standard Oil Company Formation fracturing method
US4450184 Feb 16, 1982 May 22, 1984 Metco Incorporated Hollow sphere ceramic particles for abradable coatings
US4462466 Mar 29, 1982 Jul 31, 1984 Kachnik Joseph E Method of propping fractures in subterranean formations
US4521475 Dec 20, 1983 Jun 4, 1985 Riccio Louis M Method and apparatus for applying metal cladding on surfaces and products formed thereby
US4522731 Oct 28, 1982 Jun 11, 1985 Dresser Industries, Inc. Hydraulic fracturing propping agent
US4547468 Jun 30, 1983 Oct 15, 1985 Terra Tek, Inc. Hollow proppants and a process for their manufacture
US4555493 Dec 7, 1983 Nov 26, 1985 Reynolds Metals Company Aluminosilicate ceramic proppant for gas and oil well fracturing and method of forming same
US4601997 Dec 14, 1984 Jul 22, 1986 Engelhard Corporation Porous mullite
US4618504 Feb 28, 1985 Oct 21, 1986 Bosna Alexander A Method and apparatus for applying metal cladding on surfaces and products formed thereby
US4623630 Sep 30, 1983 Nov 18, 1986 Standard Oil Proppants Company Use of uncalcined/partially calcined ingredients in the manufacture of sintered pellets useful for gas and oil well proppants
US4639427 Jun 28, 1985 Jan 27, 1987 Norton Company Stress-corrosion resistant proppant for oil and gas wells
US4652411 May 23, 1984 Mar 24, 1987 The United States Of America As Represented By The United States Department Of Energy Method of preparing thin porous sheets of ceramic material
US4658899 Apr 22, 1985 Apr 21, 1987 Standard Oil Proppants Company, L.P. Use of uncalcined/partially calcined ingredients in the manufacture of sintered pellets useful for gas and oil well proppants
US4668645 Jan 10, 1986 May 26, 1987 Arup Khaund Sintered low density gas and oil well proppants from a low cost unblended clay material of selected composition
US4680153 * May 29, 1984 Jul 14, 1987 Institut For Energetik - Zentralstelle Fur Rationelle Energieanwendung Process for manufacturing highly porous mineralic bodies of polymorphic structure
US4680230 Jan 18, 1984 Jul 14, 1987 Minnesota Mining And Manufacturing Company Particulate ceramic useful as a proppant
US4714623 Feb 13, 1986 Dec 22, 1987 Riccio Louis M Method and apparatus for applying metal cladding on surfaces and products formed thereby
US4732920 Apr 23, 1986 Mar 22, 1988 Graham John W High strength particulates
US4744831 Jul 30, 1984 May 17, 1988 Minnesota Mining And Manufacturing Company Hollow inorganic spheres and methods for making such spheres
US4840729 Feb 12, 1988 Jun 20, 1989 Atlantic Richfield Company Oil spill recovery apparatus
US4894189 Apr 28, 1988 Jan 16, 1990 The British Petroleum Company P.L.C. Process for the production of spherical particles
US4911987 Aug 1, 1989 Mar 27, 1990 National Research Institute For Metals Metal/ceramic or ceramic/ceramic bonded structure
US4993491 Apr 24, 1989 Feb 19, 1991 Amoco Corporation Fracture stimulation of coal degasification wells
US5175133 Dec 21, 1990 Dec 29, 1992 Comalco Aluminium Limited Ceramic microspheres
US5266243 Jul 16, 1992 Nov 30, 1993 Kneller James F Method for preparing a ceramic oxide material
US5443633 Oct 22, 1993 Aug 22, 1995 Nestec S.A. Soil treatment with polymeric hydrogen siloxane
US5656568 Aug 11, 1995 Aug 12, 1997 Advanced Minerals Corporation Highly purified biogenic silica product
US5972835 Sep 12, 1996 Oct 26, 1999 Research Triangle Institute Fluidizable particulate materials and methods of making same
US5993988 May 26, 1997 Nov 30, 1999 Japan Fine Ceramics Center Composite ceramic powder, method for manufacturing the powder, electrode for solid electrolytic fuel cell, and method for manufacturing the electrode
US6074754 Nov 14, 1997 Jun 13, 2000 Degussa Aktiengesellschaft Spherical pigments, process for producing them and use thereof
US6080232 Nov 14, 1997 Jun 27, 2000 Degussa Aktiengesellschaft Spherical color pigments, process for their production and use thereof
US6217646 Apr 26, 1999 Apr 17, 2001 Daubois Inc. Sculptable and breathable wall coating mortar compound
US6319870 Nov 19, 1999 Nov 20, 2001 Corning Incorporated Fabrication of low thermal expansion, high strength cordierite structures
US6503676 Apr 26, 2001 Jan 7, 2003 Ricoh Company, Ltd. Toner, external additive therefor and image forming method using the toner
US7036591 Oct 10, 2002 May 2, 2006 Carbo Ceramics Inc. Low density proppant
US7041250 Aug 22, 2002 May 9, 2006 Powdermet, Inc. Combined liquid phase and activated sintering of refractory metals
US7135231 Jul 1, 2003 Nov 14, 2006 Fairmont Minerals, Ltd. Process for incremental coating of proppants for hydraulic fracturing and proppants produced therefrom
US7270879 Apr 15, 2004 Sep 18, 2007 Hexion Specialty Chemicals, Inc. Particulate material containing thermoplastics and methods for making and using the same
US7569199 May 9, 2007 Aug 4, 2009 Oxane Materials, Inc. Method to remove sulfur or sulfur-containing species from a source
US20030039573 Aug 22, 2002 Feb 27, 2003 Sherman Andrew J. Combined liquid phase and activated sintering of refractory metals
US20040023818 Aug 5, 2002 Feb 5, 2004 Nguyen Philip D. Method and product for enhancing the clean-up of hydrocarbon-producing well
US20040200617 Apr 14, 2004 Oct 14, 2004 Stephenson Christopher John Method of treating subterranean formations with porous ceramic particulate materials
US20050077044 Oct 8, 2004 Apr 14, 2005 Bj Services Company Low residue well treatment fluids and methods of use
US20050244641 Apr 12, 2005 Nov 3, 2005 Carbo Ceramics Inc. Coating and/or treating hydraulic fracturing proppants to improve wettability, proppant lubrication, and/or to reduce damage by fracturing fluids and reservoir fluids
US20060078682 Sep 20, 2005 Apr 13, 2006 Mcdaniel Robert R Particles for use as proppants or in gravel packs, methods for making and using the same
US20060081371 Sep 14, 2005 Apr 20, 2006 Carbo Ceramics Inc. Sintered spherical pellets
US20060135809 Nov 21, 2005 Jun 22, 2006 Celanese International Corporation Modified support materials for catalysts
US20060147369 Feb 17, 2006 Jul 6, 2006 Neophotonics Corporation Nanoparticle production and corresponding structures
US20060162929 Jan 26, 2005 Jul 27, 2006 Global Synfrac Inc. Lightweight proppant and method of making same
US20060175059 Jan 20, 2006 Aug 10, 2006 Sinclair A R Soluble deverting agents
US20060219600 Mar 1, 2006 Oct 5, 2006 Carbo Ceramics Inc. Methods for producing sintered particles from a slurry of an alumina-containing raw material
US20070023187 Jul 29, 2005 Feb 1, 2007 Carbo Ceramics Inc. Sintered spherical pellets useful for gas and oil well proppants
US20070212281 May 9, 2007 Sep 13, 2007 Ecolab, Inc. Deodorizing and sanitizing employing a wicking device
US20080015531 Jul 12, 2006 Jan 17, 2008 The Procter & Gamble Company Disposable absorbent articles comprising non-biopersistent inorganic vitreous microfibers
US20080058228 Aug 30, 2007 Mar 6, 2008 Carbo Ceramics Inc. Low bulk density proppant and methods for producing the same
US20080135245 Jun 27, 2007 Jun 12, 2008 Oxane Materials, Inc. Composition and Method For Making a Proppant
US20080135246 Feb 15, 2008 Jun 12, 2008 Carbo Ceramics Inc. Sintered spherical pellets useful for gas and oil well proppants
US20080220996 May 19, 2008 Sep 11, 2008 Carbo Ceramics Inc. Sintered spherical pellets
US20080241540 Jun 9, 2008 Oct 2, 2008 Carbo Ceramics Inc. Method for producing solid ceramic particles using a spray drying process
US20090008093 Jul 2, 2008 Jan 8, 2009 Carbo Ceramics Inc. Proppants for gel clean-up
US20090032253 Oct 16, 2008 Feb 5, 2009 Oxane Materials, Inc. Composition and Method For Making A Proppant
US20090032254 Oct 16, 2008 Feb 5, 2009 Oxane Materials, Inc. Composition and Method For Making A Proppant
US20090038797 Jul 18, 2008 Feb 12, 2009 Oxane Materials, Inc. Proppants With Carbide and/or Nitride Phases
US20090038798 Oct 16, 2008 Feb 12, 2009 Oxane Materials, Inc. Composition and Method For Making A Proppant
US20090065208 Oct 16, 2008 Mar 12, 2009 Oxane Materials, Inc. Composition and Method For Making A Proppant
US20090118145 Oct 17, 2008 May 7, 2009 Carbo Ceramics Inc. Method for producing proppant using a dopant
US20090137433 Jan 27, 2009 May 28, 2009 Oxane Materials, Inc. Composition And Method For Making A Proppant
US20090205825 Jan 22, 2009 Aug 20, 2009 Carbo Ceramics Inc. Method of logging a well using a thermal neutron absorbing material
US20090288820 May 19, 2009 Nov 26, 2009 Oxane Materials, Inc. Method Of Manufacture And The Use Of A Functional Proppant For Determination Of Subterranean Fracture Geometries
US20100059224 Sep 21, 2009 Mar 11, 2010 Carbo Ceramics Inc. Methods for producing sintered particles from a slurry of an alumina-containing raw material
US20100126728 Jan 25, 2010 May 27, 2010 Carbo Ceramics Inc. Sintered spherical pellets
AR241543A1 Title not available
AR243222A1 Title not available
AU551409B2 Title not available
CA1045027A1 Title not available
CA1117987A1 Title not available
CA1172837A1 Title not available
CA1191020A1 Title not available
CA1194685A1 Title not available
CA1232751A1 Title not available
CA2444826C Oct 10, 2003 May 11, 2010 Chad D. Cannan Low density proppant
CH647689A5 Title not available
CN1189475C Jan 26, 1999 Feb 16, 2005 Ibsa生物化学研究股份有限公司 Process for separating and purifying FSH and corpus luteum hormone
DE2948584A1 Dec 3, 1979 Jun 26, 1980 Carborundum Co Sphaerische sinterkeramische pellets und verfahren zu ihrer herstellung
DK168099C Title not available
EA006953B1 Title not available
EA007864B1 Title not available
EA008825B1 Title not available
EA010944B1 Title not available
EA011732B1 Title not available
EA012824B1 Title not available
EP0083974B1 Jan 6, 1983 Oct 30, 1985 A/S Niro Atomizer A process for the production of sintered spheres
EP0087852B1 Jan 6, 1983 Apr 2, 1986 Dresser Industries, Inc. Hydraulic fracturing propping agent
EP0101855A1 Jul 12, 1983 Mar 7, 1984 Norton Company Low density proppant for oil and gas wells
EP0116369A3 Feb 7, 1984 Jul 3, 1985 Norton Company Proppant for fractured wells
EP0169412A1 Jul 2, 1985 Jan 29, 1986 Norton Company Proppant for oil and gas wells
FR2486930B1 Title not available
GB578424A Title not available
GB715354A Title not available
GB715882A Title not available
GB886342A Title not available
GB992237A Title not available
GB1033143A Title not available
GB1411135A Title not available
GB1421531A Title not available
GB2037727B Title not available
GB2079261B Title not available
GB2092561B Title not available
PH18450A Title not available
RU2014281C1 Title not available
RU2079471C1 Title not available
RU2083528C1 Title not available
RU2090537C1 Title not available
RU2098387C1 Title not available
RU2098618C1 Title not available
RU2107674C1 Title not available
RU2112189C1 Title not available
RU2112761C1 Title not available
RU2121988C1 Title not available
RU2129985C1 Title not available
RU2129987C1 Title not available
RU2133716C1 Title not available
RU2140874C1 Title not available
RU2140875C1 Title not available
RU2147564C1 Title not available
RU2147565C1 Title not available
RU2147717C1 Title not available
RU2150442C1 Title not available
RU2151124C1 Title not available
RU2151125C1 Title not available
RU2151987C1 Title not available
RU2154042C1 Title not available
RU2155735C1 Title not available
RU2163227C1 Title not available
RU2166079C1 Title not available
RU2168484C2 Title not available
RU2178924C1 Title not available
RU2180397C1 Title not available
RU2183370C1 Title not available
RU2183739C2 Title not available
RU2191167C1 Title not available
RU2191169C1 Title not available
RU2191436C1 Title not available
RU2192053C1 Title not available
RU2196675C2 Title not available
RU2196889C1 Title not available
RU2198860C2 Title not available
RU2203248C1 Title not available
RU2206930C1 Title not available
RU2211198C2 Title not available
RU2212719C2 Title not available
RU2215712C1 Title not available
RU2229456C2 Title not available
RU2229458C2 Title not available
RU99107936A Title not available
RU2002117351A Title not available
1 "rock." Encyclopedia Britannica 2007. Encyclopedia Britannica Article. Jun. 27, 2007.
2 Bauxite and Alumina, Luke H. Baumgardner, et al., Minerals Yearbook, 1987, vol. I.
3 Bauxite, Cyril S. Fox, 1927.
4 Chemical Abstracts, vol. 85, No. 24, Dec. 13, 1976.
5 Coors Porcelain Company letter to B. J. Hughes, Inc. dated Aug. 24, 1978 with Proposal to Supply Proppant.
6 Coors Porcelain Company letter to Halliburton Services, Inc. dated Aug. 4, 1978 with Proposal to Supply Proppant.
7 Correspondence from foreign counsel dated Aug. 25, 2008, regarding Office Action issued in connection with Eurasian Patent Application No. 200800008.
8 Correspondence from foreign counsel dated Feb. 29, 2008, regarding Office Action issued in connection with Eurasian Patent Application No. 200700583.
9 Correspondence from foreign counsel dated Jul. 10, 2008, regarding Office Action issued in connection with Eurasian Patent Application No. 200701830.
10 Correspondence from foreign counsel dated May 9, 2008, regarding Office Action issued in connection with Eurasian Patent Application No. 200700583.
11 Correspondence from foreign counsel dated Nov. 29, 2007, regarding Office Action issued in connection with Eurasian Patent Application No. 200700296.
12 Correspondence from foreign counsel dated Sep. 15, 2008, regarding Office Action issued in connection with Eurasian Patent Application No. 200700583.
13 Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation, Progress Report 10, DOE Contract DE-AC19-79BC10038, Submitted by Terra Tek, Inc., TR 80-77, Jul. 1980.
14 Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation, Progress Report 2, DOE Contract DE-AC19-79BC10038, Submitted by Terra Tek, Inc., TR 79-77, Oct. 1979.
15 Didion International, Inc.; Mold & Core Consumables; http://www.moderncasting.com/Morelnfo/0602/FMI-Article-08.asp; Dec. 27, 2002.
16 Didion International, Inc.; Mold & Core Consumables; http://www.moderncasting.com/Morelnfo/0602/FMI—Article—08.asp; Dec. 27, 2002.
17 Document entitled "Feb., Mar., Apr. 1998: Commercial Activity", with Exhibits A-D.
18 Document entitled "Jul. 1998: Commercial Activity", with Exhibit E.
19 Document entitled "Sep. 2001: Commercial Activity", with Exhibit F.
20 DOE Progress Review No. 21 for reporting period Oct. 1-Dec. 31, 1979, Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation.
21 DOE Progress Review No. 22 for reporting period Jan. 1-Mar. 31, 1980, Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation.
22 DOE Progress Review No. 23 for reporting period Apr. 1-Jun. 30, 1980, Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation.
23 DOE Progress Review No. 24 for reporting period Jul. 1-Sep. 31, 1980, Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation.
24 DOE Progress Review No. 26 for reporting period Jan. 1-Mar. 31, 1981, Determine Feasibility of Fabricated Light Weight Proppants for Application in Gas and Oil Well Stimulation.
25 DOE Progress Review No. 27 for reporting period Apr. 1-Jun. 30, 1981, Determining Feasibility of Fabricating Light Weight Proppants for Application in Gas and Oil Well Stimulation.
26 Effect of Grinding and Firing Treatment on the Crystalline and Glass Content and the Physical Properties of Whiteware Bodies; S. C. Sane, et al., 1951.
27 Engineering Properties of Ceramics, Databook to Guide Materials Selection for Structural Applications, J. F. Lynch, et al., TR 66-52, Jun. 1966.
28 Enprotech Corp; About Enprotech; http:www.enprotech.com/aboutus.html; Copyright 2004.
29 Environmental Conservation-Oriented Businesses; Itochu Corporation; pp. 11-16; Jul. 2004.
30 Hydraulic Fracturing with a High-Strength Proppant, Claude E. Cooke, Society of Petroleum Engineers of AIME, SPE 6213, 1976.
31 International Preliminary Examination Report mailed Feb. 20, 2009, by the IB regarding International Application No. PCT/US2007/077290.
32 International Preliminary Report on Patentability mailed Apr. 20, 2007, regarding International Application No. PCT/US2005/033092.
33 International Preliminary Report on Patentability mailed Feb. 7, 2008, by the IB regarding International Application No. PCT/US2006/029234.
34 International Preliminary Report on Patentability mailed Jan. 13, 2009, by the IB regarding International Application No. PCT/US2007/073247.
35 International Preliminary Report on Patentability mailed Jan. 18, 2007, by the IB regarding International Application No. PCT/US2005/024339.
36 International Preliminary Report on Patentability mailed Sep. 20, 2007, by the IB regarding International Application No. PCT/US2006/007308.
37 International Search Report issued by the ISA/US on Mar. 14, 2006 in connection with International Application No. PCT/US2005/012256.
38 International Search Report mailed Aug. 29, 2006, by the ISA/US regarding International Application No. PCT/US2005/024339.
39 International Search Report mailed Dec. 27, 2007, by the ISA/US regarding International Application No. PCT/US2007/073247.
40 International Search Report mailed Feb. 22, 2008, by the ISA/US regarding International Application No. PCT/US2007/077290.
41 International Search Report mailed Jul. 13, 2007, by the ISA/US regarding International Application No. PCT/US2006/007308.
42 International Search Report mailed Jun. 8, 2007, by the ISA/US regarding International Application No. PCT/US2006/029234.
43 International Search Report mailed Oct. 4, 2006, by the ISA/US regarding International Application No. PCT/US2005/033092.
44 International Search Report mailed Oct. 6, 2008, by the ISA/US regarding International Application No. PCT/US2008/069012.
45 International Search Report, mailed Dec. 27, 2007, by the U.S. International Searching Authority, in connection with International Application No. PCT/US2007/073247.
46 Itochu Ceratech Corp.; Ceramics and Minerals Department; http://www.itc-cera.co.jp/english/cera.htm; Jun. 8, 2002.
47 Itochu Ceratech Corporation; CERABEADS-Spherical Ceramic Sand; http://exhibits.gifa.de/exh/GMTN2003/e/3231240; Mar. 13, 2005.
48 Itochu Ceratech Corporation; CERABEADS—Spherical Ceramic Sand; http://exhibits.gifa.de/exh/GMTN2003/e/3231240; Mar. 13, 2005.
49 Light Weight Proppants for Deep Gas Well Stimulation, 2nd Annual Report, Jul. 1, 1980-Jun. 30, 1981, published Apr. 1982, DOE Contract AC19-79BC10038, by R.A. Cutler et al, Terra Tek, Inc.
50 Light Weight Proppants for Deep Gas Well Stimulation, A. H. Jones et al, Terra Tek, Inc., Jun. 1980, TR Report 80-47.
51 Naigai Ceramics Co., Ltd.; Naigai Cerabeads 60; Aug. 1986.
52 Nepheline Syenite-Talc Mixtures as a Flux in Low-Temperature Vitrified Bodies; E. D. Lynch, et al., Apr. 1950.
53 New Proppants for Deep Gas Well Stimulation, SPE 9869, by Raymond A. Cutler, et al., 1977.
54 Office Action issued Aug. 21, 2009, by the State Intellectual Property Office, P.R. China, regarding Chinese Patent Application No. 200680038963.4.
55 Office Action issued Jun. 12, 2008, by the State Intellectual Property Office, P.R. China, regarding GCC Patent Application No. GCC/P/2005/4586.
56 Office Action issued Jun. 19, 2009, by the State Intellectual Property Office, P.R. China, regarding Chinese Patent Application No. 200580030660.3.
57 Oxide Ceramic Proppants for Treatment of Deep Well Fractures, SPE 6816, by E.A. Neel, J.L. Parmley, and P.J. Colpoys, Jr. (1977).
58 Perry's Chemical Engineers' Handbook Section 12, 7th Edition, 1997, pp. 12-81 to 12-90.
59 Reactions in Silica-Alumina Mixtures, Richard R. West, et al., Apr. 1958.
60 Rickards, A. R., et al.; "High Strength, Ultra Lightweight Proppant Development Lends New Dimensions to Hydraulic Fracturing Applications", SPE 84308, Oct. 7, 2003.
61 Role of Impurities on Formation of Mullite from Kaolinite and Al2O3-S1O2 Mixtures, Johnson, Sylvia M. et al., Ceramic Bulletin, vol. 61, No. 8 (1982), pp. 838-842.
62 ScalePROP brochure, Schlumberger, Jan. 2002.
63 Spraying Systems Co.; Air Atomizing Nozzles 1/2J Pressure Spray Set-ups Internal Mix; Air Atomizing Nozzles 1/2J Series External Mix Set-ups; Air Atomizing Nozzles 1/2J Siphon/Gravity-Fed Spray Set-ups; pp. 358-362; Copyright 2003.
64 Spraying Systems Co.; Air Atomizing Nozzles 1/8J and 1/4J Set-ups External Mix; pp. 282-285; Copyright 2003.
65 Spraying Systems Co.; Air Atomizing Nozzles Basic Information; pp. 268-269; Copyright 2003.
66 Spraying Systems Co.; Engineer's Guide to Spray Technology; Copyright 2000.
67 Synthesis and Mechanical Properties of Stoichiometric Aluminum Silicate (Mullite), K. S. Mazdiyasni, et al., Dec. 1972.
68 The Effect of Various Proppants and Proppant Mixtures on Fracture Permeability, Robert R. McDaniel, et al., SPE 7573, 1978.
69 The Industrial Uses of Bauxite, N. V. S. Knibbs, D.Sc., 1928.
70 Unimin Brochure, Unimin Canada Ltd., Mar. 1991.
71 Written Opinion mailed Aug. 29, 2006, by the ISA/US regarding International Application No. PCT/US2005/024339.
72 Written Opinion mailed Dec. 27, 2007, by the ISA/US regarding International Application No. PCT/US2007/073247.
73 Written Opinion mailed Feb. 22, 2008, by the ISA/US regarding International Application No. PCT/US2007/077290.
74 Written Opinion mailed Jul. 13, 2007, by the ISA/US regarding International Application No. PCT/US2006/007308.
75 Written Opinion mailed Jun. 8, 2007, by the ISA/US regarding International Application No. PCT/US2006/029234.
76 Written Opinion mailed Oct. 4, 2006, by the ISA/US regarding International Application No. PCT/US2005/033092.
77 Written Opinion mailed Oct. 6, 2008, by the ISA/US regarding International Application No. PCT/US2008/069012.
78 Written Opinion of the International Searching Authority issued by the ISA/US on Mar. 14, 2006 in connection with International Application No. PCT/US2005/012256.
79 Written Opinion, mailed Dec. 27, 2007, by the U.S. International Searching Authority, in connection with International Application No. PCT/US2007/073247.
US9587170 Aug 20, 2013 Mar 7, 2017 Epropp, Llc Proppant material incorporating fly ash and method of manufacture
US20130307201 * May 18, 2012 Nov 21, 2013 Bryan William McEnerney Ceramic article and additive processing method therefor
U.S. Classification 264/41, 264/49, 264/46.6, 264/42, 264/43
International Classification B29C67/20, B29C65/02
Cooperative Classification C04B35/10, C04B2111/343, C04B35/14, C04B38/0645, C04B38/0025, C04B35/18
European Classification C04B35/14, C04B38/06F2D, C04B38/00C2, C04B35/10, C04B35/18
Owner name: CARBO CERAMICS, INC., TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WILSON, BRETT A.;REEL/FRAME:019871/0883
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LUSCHER, WALTER G.;HELLMANN, JOHN R.;SCHEETZ, BARRY E.;REEL/FRAME:020559/0973;SIGNING DATES FROM 20070717 TO 20070920