This paper describes efforts in an experimental search for polymers that are sufficiently soluble in dense CO 2 that· they could serve as mobility control agents. The operation of the apparatus designed and built for the measurement of solubility in condensed gases is described. A modified version of this apparatus has been used to measure viscosity by timing the fall of a cylinder in a tube.More than a dozen polymers have been found that are soluble at least in the parts-per-thousand (ppt) range in liquid and in dense supercritical CO 2 , As pressures and temperatures are varied, the solubilities of these polymers generally are found to increase with increasing CO 2 density. Certain generalizations have been made concerning the influence of various polymer properties on their solubility in dense CO 2 , These properties include structure, stereochemistry, and molecular weight. Although the viscosity enhancements of the solutions measured thus far are insufficient for purposes of mobility control, they provide clues that point toward those features of polymer molecules that yield greater thickening properties.Also discussed are considerations involved in the application of direct thickeners in the mobility control of CO 2 floods and the advantages in the use of such CO 2 -soluble polymers in place of methods that involve the injection of water.

Summary Polymer residues that stay in the fracture after fracturing can limit the treatment effectiveness. A new and easy-to-prepare, surfactant-based polymer-free fluid, ClearFRAC™, that consists of a quaternary ammonium salt derived from a long-chain fatty acid is described. In brine, it builds fluid viscosity and viscoelasticity due to the formation of highly entangled worm-like micelles. The micelles have a gross structure similar to a polymer chain. Since the viscosity of the fluid depends on the nature of micelles, the fluid can be broken by changing this micellar structure. The breaking occurs when the fluid is exposed to hydrocarbons or diluted with formation water. Therefore, conventional breakers are not required, and the produced oil or gas can act as breakers for this fluid system. The structural characteristics of this viscoelastic surfactant-based fluid to its chemical and physical properties are correlated in this article. Structure, rheology, fluid loss, and conductivity of this surfactant fluid together with its case histories are presented. Introduction Fracturing fluid is a very critical component of a hydraulic fracturing treatment. Selection of the fracturing fluid, job design, and well turnaround procedure all determine the productivity of a well after a stimulation by hydraulic fracturing.1,2 A fracturing fluid should provide sufficient viscosity to suspend and transport proppant into the fracture, and should break into a low-viscosity fluid after the job is completed. This will facilitate the fracture to clean up by allowing rapid flowback of fluid to the surface. Analysis of the fluid returned to the surface (flowback fluid) after hydraulic fracturing indicates that as little as 30 to 45% of the guar-based polymer pumped during the treatment returned from the well during the flowback period.3 Polymer residues that remain in the fracture significantly contribute to lower proppant-pack permeability, leading to a loss in fracture treatment effectiveness.1 The field success of a viscoelastic surfactant-based (VES) polymer-free fluid4–6 in frac-pack applications led to the development of a similar fluid for hydraulic fracturing. This VES fluid, ClearFRAC can be used for the fracturing treatment of potentially all gas and oil wells below 240°F. The principal advantage of this fluid system is its operational simplicity. This fluid is easy to prepare and requires less equipment at the wellsite. This fluid does not require polymer hydration, biocides, buffers, crosslinkers, or breakers. When flowing back, contact with the produced hydrocarbons or dilution with formation brine can also break ClearFRAC. This new fracturing fluid has been used successfully in more than 2,100 fracturing jobs around the world. Case histories from representative treatments are presented. Theory The presence of two structurally dissimilar groups (a hydrophilic and a hydrophobic) within a single molecule is the most fundamental characteristic of all surfactants. These molecules are composed of groups of opposing solubility tendencies, typically an oil-soluble hydrocarbon chain (hydrophobic) and a water-soluble ionic group (hydrophilic). In aqueous solution these molecules self-associate in an attempt to sequester their apolar regions from contact with the aqueous phase. Micelles can have different structures such as small spheres, disks, or long cylinders.7 When dissolved in brine, a small group of surfactants is able to form micellar structures other than the most commonly encountered spheres or disks. This includes the family of quaternary ammonium compounds, which is the subject of this article. The geometry of the micelles is similar to that of polymer molecules. This network of micellar structure resists distortion, whereby the viscosity increases and imparts viscoelastic properties to the fluid. Unlike guar-based fluids for the VES system, no crosslinker is necessary. There is a repulsive interaction in the micelle structure, primarily between the positively charged head groups. This repulsive force make the micelles assume a spherical shape, leading to a fluid of brine-like viscosity. To counteract this repulsive force, the presence of a counter-anion is necessary. The use of some inorganic and organic8 anions is found to enhance the viscosity of this surfactant fluid. When organic and other hydrophobic substances dissolve in the micelle hydrocarbon core, they will swell the rod-shaped micelle structure and ultimately break it into smaller spherical micelles with resultant loss in fluid viscosity (Fig. 1). Hydrocarbons such as oil and gas have this effect, and will readily reduce the viscosity of VES fluids to that of brine. Therefore, no internal chemical or enzyme breaker is required with this fluid system. Results and Discussion Micelle Structure. The micellar structure of the viscoelastic surfactant in brine was examined using cryotransmission electron microscopy (cryo-TEM). For this study a 4% (by vol) VES surfactant was added to a 3% solution of NH4Cl in a Waring blender and mixed for about 3 minutes. The resulting gel was de-aerated by placing it in a hot water bath. The samples for cryo-TEM were prepared in a controlled environmental vitrification9 system (CEVS) using this gel. Cryo-TEM examination of a VES gel in NH4Cl brine showed that it is composed of highly entangled worm-like [Fig. 2(a)] or long cylindrical [Fig. 2(b)] micelles with crossbridges. Rheology. The rheological performance of the VES fluid was investigated by measuring its viscosity on a Fann 50 or Fann 35 viscometer and/or on a Reciprocating Capillary Viscometer (RCV). The rheology of the fluid was examined at temperatures ranging from 80 to 250°F in the presence of different clay stabilizers. Depending on the application temperature, the amount of the surfactant used ranges from 0.5 to 4% (low concentration for low temperatures). In a typical experiment, the required amount of the surfactant is added to 500 mL of a 3% NH4Cl solution in a Waring blender. The mixture is blended until the vortex is closed. The time required for vortex closure (which ranges from 2 to 5 minutes) depends on the amount of surfactant used. The viscosity of the fluid is examined after de-aerating the fluid by heating in a water bath (?80°C) for about 1 hour.

Polymer residues that stay in the fracture after a hydraulic fracturing treatment can limit treatment effectiveness. A new and easy-to-prepare, polymer-free fluid that consists of a quaternary ammonium salt derived from a long-chain fatty acid is described. In brine, it builds viscosity due to the formation of highly entangled worm-like micelles. The micelles have a gross structure similar to a polymer chain. Since the viscosity of the fluid depends on the nature of micelles, the fluid can be broken by changing this micellar structure. The breaking occurs when the fluid is exposed to hydrocarbons or diluted with formation waters. Therefore, conventional breakers are not required, and the produced oil or gas can act as breakers for this fluid system. The structural characteristics of the polymer-free surfactant fluid to its chemical and physical properties are correlated in this paper. Structure, rheology, fluid loss and conductivity of this surfactant fluid together with its production data are presented. Introduction Fracturing fluid is a very critical component of a hydraulic fracturing treatment. Selection of the fracturing fluid, job design, and well turnaround procedure all help to determine the production of a well after a stimulation by hydraulic fracturing. A fracturing fluid should provide sufficient viscosity to suspend and transport proppant into the fracture, and should break into a low-viscosity fluid after the job is completed. This will facilitate the fracture to clean up by allowing rapid flowback of fluid to the surface. Analysis of the fluid returned to the surface (flowback fluid) after hydraulic fracturing indicates that as little as 30 to 45% of the guar-based polymer pumped during the treatment returned from the well during the flowback period. Polymer residues that remain in the fracture significantly contribute to a lowered proppant-pack permeability leading to a loss in fracture treatment effectiveness. The field success of a viscoelastic surfactant-based (VES) polymer-free fluid in frac-pack applications led to the development of a similar fluid for hydraulic fracturing. The VES fluid can be used for the fracturing treatment of potentially all gas and oil wells below 240 F. The principal advantage of this fluid system is its operational simplicity. This fluid is easy to prepare and requires less equipment at the wellsite This fluid does not require polymer hydration, biocides, crosslinkers, or breakers. The hydrocarbons produced, or dilution of VES gel by other formation fluids, can break this fluid. This new fluid has been used for the successful execution of more than 250 fracturing jobs. Results from representative treatments are presented. Theory The presence of two structurally dissimilar groups (a lyophilic and a lyophobic) within a single molecule is the most fundamental characteristic of all surfactants These molecules are composed of groups of opposing solubility tendencies, typically an oil-soluble hydrocarbon chain (hydrophobic) and a water-soluble ionic group (hydrophilic). In aqueous solution these molecules self-associate in an attempt to sequester their apolar regions from contact with the aqueous phase. Micelles can be small spheres, disks, or long cylindrical structures. When dissolved in brine. a small group of surfactants is able to form structures other than the most commonly encountered spheres or disks. This includes the family of quaternary ammonium compounds, which is the subject of this paper. The geometry of the micelles is similar to polymer molecules. This network of micellar structure resists distortion, whereby the viscosity increases and imparts viscoelastic properties to the fluid. In this system. unlike guar-based fluids, no crosslinker is necessary. There is a repulsive interaction in micelle structure, primarily between the positively charged head groups. P. 553^

The woven replication process was used to fabricate lead zirconate titanate (PZT)/polymer composites with 1-3, 2-3, and 3-3 connectivities by starting with novoloid-derived carbon fiber, woven fabric, and nonwoven felt templates, respectively. Activated carbon-fiber template material was impregnated with PZT by soaking it in a solution containing stoichiometric amounts of dissolved lead, zirconium, titanium, and niobium ions. Heat treatment burned out the carbon, leaving a PZT replica with the same form as the template material. Replicas were sintered in a controlled atmosphere and backfilled with an epoxy polymer to form final composites. This method, which is believed to be adaptable for mass production, is capable of producing composites withextremely fine microstructures. Woven composite samples have fiber tow diameters of 200 to 250 pm and spacings between tows of about 150 to 250 pm. Average d33 = 90 pC/N, g33 = 211 mV * m/N, and dhgh hydrophone figure of merit of 2100 X lo-'' m2/N values are reported for woven PZT/polymer composites. [

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