Thermoset nanocomposite particles, processing for their production, and their use in oil and natural gas drilling applications
Thermoset polymer particles are used in many applications requiring lightweight particles possessing high stiffness, strength, temperature resistance, and/or resistance to aggressive environments. The present invention relates to the use of two different methods, either each by itself or in combination, to enhance the stiffness, strength, maximum possible use temperature, and environmental resistance of such particles. One method is the application of post-polymerization process steps (and especially heat treatment) to advance the curing reaction and to thus obtain a more densely crosslinked polymer network. In general, its main benefits are the enhancement of the maximum possible use temperature and the environmental resistance. The other method is the incorporation of nanofillers, resulting in a heterogeneous “nanocomposite” morphology. In general, its main benefits are increased stiffness and strength. Nanofiller incorporation and post-polymerization heat treatment can also be combined to obtain the benefits of both methods simultaneously. The present invention relates to the development of thermoset nanocomposite particles. It also relates to the optional further improvement of the heat resistance and environmental resistance of said particles via post-polymerization heat treatment. Furthermore, it also relates to processes for the manufacture of said particles. Finally, it also relates to the use of said particles in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells; for example, as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.
1. A method for reducing friction in a well penetrating a subterranean formation comprising:
mixing into a drilling fluid formulation as a solid lubricant an effective amount of a polymeric nanocomposite spherical bead comprising:
a thermoset polymer matrix and
from 0.001 to 60 volume percent of nanofiller particles possessing a length that is less than 0.5 microns in at least one principal axis direction, wherein said nanofiller particles comprise at least one of dispersed fine particulate material, fibrous material, discoidal material, or a combination of such materials; and wherein said nanofiller particles are selected from the group of nanofillers consisting of: carbon black, fumed silica, fumed alumina, carbon nanotubes, carbon nanofibers, cellulosic nanofibers, fly ash, polyhedral oligomeric silsesquioxanes, or mixtures thereof, and wherein said nanofiller particles are dispersed throughout said polymeric nanocomposite spherical bead, wherein said spherical bead has a diameter ranging from 0.1 mm to 4 mm; and
introducing said drilling fluid formulation with said effective amount of the polymer nanocomposite spherical bead into said well.
2. A method for reducing friction in a well penetrating a subterranean formation comprising:
mixing into a drilling fluid formulation as a ball bearing an effective amount of a polymeric nanocomposite spherical bead comprising:
a thermoset polymer matrix and
from 0.001 to 60 volume percent of nanofiller particles possessing a length that is less than 0.5 microns in at least one principal axis direction, wherein said nanofiller particles comprise at least one of dispersed fine particulate material, fibrous material, discoidal material, or a combination of such materials; and wherein said nanofiller particles are selected from the group of nanofillers consisting of: carbon black, fumed silica, fumed alumina, carbon nanotubes, carbon nanofibers, cellulosic nanofibers, fly ash, polyhedral oligomeric silsesquioxanes, or mixtures thereof, and wherein said nanofiller particles are dispersed throughout said polymeric nanocomposite spherical bead, wherein said spherical bead has a diameter ranging from 0.1 mm to 4 mm; and
introducing said drilling fluid formulation with said effective amount of the polymer nanocomposite spherical bead into said well.
3. The method of claim 1 , wherein said thermoset polymer matrix comprises at least one of a thermoset epoxy, a thermoset epoxy vinyl ester, a thermoset polyester, a thermoset phenolic, a thermoset polyurethane, a thermoset polyurea, a thermoset polyimide, or mixtures thereof.
4. The method of claim 1 , wherein said thermoset polymer matrix comprises a terpolymer.
5. The method of claim 1 wherein said thermoset polymer matrix comprises a styrene-ethylvinylbenzene-divinylbenzene terpolymer.
6. The method of claim 1 wherein said nanofiller particle has a shape; selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.
7. The method of claim 1 , wherein a largest principal axis dimension of said nanofiller particle does not exceed 10 millimeters.
8. The method of claim 1 , wherein said nanofiller particle comprises carbon black, possessing a length that is less than 0.5 microns in at least one principal axis direction and an amount from 0.1% to 15% of said particle by volume.
9. The method of claim 1 , wherein said polymeric nanocomposite spherical bead is blended with other solid particles including at least one of sand, resin-coated sand, ceramic and resin-coated ceramic.
10. The method of claim 2 wherein said thermoset polymer matrix comprises at least one of a thermoset epoxy, a thermoset epoxy vinyl ester, a thermoset polyester, a thermoset phenolic, a thermoset polyurethane, a thermoset polyurea, a thermoset polyimide, or mixtures thereof.
11. The method of claim 2 , wherein said thermoset polymer matrix comprises a terpolymer.
12. The method of claim 2 , wherein said thermoset polymer matrix comprises a styrene-ethylvinylbenzene-divinylbenzene terpolymer.
13. The method of claim 2 , wherein said nanofiller particle has a shape; selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.
14. The method of claim 2 , wherein a largest principal axis dimension of said nanofiller particle does not exceed 10 millimeters.
15. The method of claim 2 , wherein said nanofiller particle comprises carbon black, possessing a length that is less than 0.5 microns in at least one principal axis direction and an amount from 0.1% to 15% of said particle by volume.
16. The method of claim 2 , wherein said polymeric nanocomposite spherical bead is blended with other solid particles including at least one of sand, resin-coated sand, ceramic and resin-coated ceramic.