US4503170A — Shear thickening fluid

Claim 1

Independent Claim 144 words

A well-control shear thickening composite comprising (1) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising oil and a surfactant and (3) an aqueous phase comprising water and a water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear-thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste.

Claim 2

Dependent Claim 144 words

A well-control shear thickening composite comprising (1) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising oil and a surfactant and (3) an aqueous phase comprising water and a water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear-thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste.

Claim 3

Dependent Claim 35 words

The composite of claim 1 wherein the water swellable clay granules are selected from the group consisting of granular montmorillonite clay and granular attapulgite clay with a particle size of between 10 to 60 mesh.

Claim 4

Dependent Claim 40 words

The composite of claim 1 wherein the oil comprises mineral oil, C 6 to C 1000 paraffinic oil, motor oil, substituted paraffinic oil wherein the substituents are selected from the group consisting of halogens, amines, sulfates, nitrates, carboxylates and hydroxyls.

Claim 5

Dependent Claim 18 words

The composite of claim 2 wherein the oil is a C 6 to C 200 liquid paraffin oil.

Claim 6

Dependent Claim 22 words

The composite of claim 1 wherein the water soluble polymer is polyacrylamide, polymethacrylamide, polystyrene sulfonate, polyvinyl toluene sulfonate, polyethyleneoxide, or polyvinyl alcohol.

Claim 7

Dependent Claim 12 words

The composite of claim 4 wherein the water soluble polymer is polyacrylamide.

Claim 8

Dependent Claim 18 words

The composite of claim 6 wherein the polyacrylamide is hydrolyzed to a degree ranging from 0 to 50%.

Claim 9

Dependent Claim 43 words

The composite of claims 1, 2, 3, 4, 5, 6 or 7 comprising 100 parts by weight (pbw) granular clay, 25 to 400 pbw water, 0.1 to 6.7 pbw water soluble polymer, 25 to 130 pbw oil, and 5.5 to 29 pbw surfactant.

Claim 10

Dependent Claim 98 words

The composite of claim 8 wherein the surfactant is the product obtained by the reaction of the polyamine: ##STR6## wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Y are selected from the group consisting of hydrogen, C 1 to C 20 alkyl, C 6 to C 20 aryl, C 7 to C 20 alkaryl radicals and substituted derivatives thereof and x is an integer of from 1 to 100 with polyalkenyl succinic anhydrides, reaction proceding at the R 3 , R 4 substituted nitrogen.

Claim 11

Dependent Claim 27 words

The composite of claim 9 wherein the polyalkenyl succinic anhydride is selected from the group consisting of polyisobutenyl succinic anhydride, polypropenyl succinic anhydride acid polybutenyl succinic anhydride.

Claim 12

Dependent Claim 94 words

The composite of claim 9 wherein the surfactant is represented by the general formula: ##STR7## wherein n varies from 10 to 60, preferably 10 to 30, most preferably 15 to 17; x varies from 1 to 100, preferably 3 to 10; R 5 , R 6 , R 7 , R 8 , R 9 are hydrogen C 1 to C 20 aryl, C 7 to C 20 alkaryl radical and substituted derivative thereof, and Y is selected from the group consisting of hydrogen and oxygen substituted hydrocarbyl radicals having up to 10 carbons.

Claim 13

Dependent Claim 14 words

The composite of claim 11 wherein the surfactant is represented by the formula: ##STR8##

Claim 14

Dependent Claim 17 words

The composite of claim 8 wherein the clay granules have a grain particle size of 10-40 mesh.

Claim 15

Dependent Claim 17 words

The composite of claim 8 wherein the clay granules have a grain particle size of 20-40 mesh.

Claim 16

Independent Claim 216 words

A method for treating a well penetrating a subterranean formation to block off an unwanted flow path which comprises: (a) forming a well control shear thickening composite comprising (1) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising oil and a surfactant and (3) an aqueous phase comprising water and a water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste; (b) pumping said composite down said well; and (c) subjecting said composite to high shear mixing adjacent to said unwanted flow path sufficient to fragment said clay granules causing them to contact said aqueous phase, so that said composition thickens into said paste blocking off said unwanted flow path.

Claim 17

Independent Claim 216 words

A method for treating a well penetrating a subterranean formation to block off an unwanted flow path which comprises: (a) forming a well control shear thickening composite comprising (1) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising oil and a surfactant and (3) an aqueous phase comprising water and a water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste; (b) pumping said composite down said well; and (c) subjecting said composite to high shear mixing adjacent to said unwanted flow path sufficient to fragment said clay granules causing them to contact said aqueous phase, so that said composition thickens into said paste blocking off said unwanted flow path.

Claim 18

Dependent Claim 29 words

The method of claim 15 wherein the high shear mixing consists of passing the shear thickening fluid through the orifices of a drill bit or nozzle in the well.

Claim 19

Dependent Claim 52 words

The method of claim 15 wherein the shear thickening composite comprises 100 parts by weight (pbw) clay granules, 25 to 400 pbw water, 0.1 to 6.7 pbw water soluble polymer, 25 to 130 pbw oil and 5.5 to 29 pbw surfactant, said clay granules having a grain size ranging from 10-60 mesh.

Claim 20

Dependent Claim 148 words

The method of claim 17 wherein the clay granules are montmorillonite clay or attapulgite clay, the oil is mineral oil, C 6 to C 1000 paraffinic clay, motor oil and substituted paraffinic oil wherein the substituents are selected from the group consisting of halogens, amines, sulfates, nitrates, carboxylates and hydroxyls and the surfactant is the product obtained by the reaction of polyalkenyl succinic anhydrides with a polyamine of the general formula ##STR9## wherein R 3 -R 9 and Y are chosen from the group consisting of hydrogen C 1 to C 20 alkyl, C 6 to C 20 aryl, C 7 to C 20 alkaryl radicals and substituted derivatives thereof, and x is an integer of from 1 to 100, reaction proceeding at the R 3 , R 4 substituted nitrogen, and the water-soluble polymer is polyacrylamide, polymethacrylamide, polystyrene sulfonate, polyvinyl tuluene sulfonate, polyethylene oxide or polyvinyl alcohol.

Claim 21

Dependent Claim 11 words

The method of claim 18 wherein the water-soluble polymer is polyacrylamide.

Claim 22

Dependent Claim 100 words

The method of claim 17 wherein the surfactant is represented by the general formula ##STR10## wherein n varies from 10 to 60, preferably 10 to 30, most preferably 15 to 17; x varies from 1 to 100, preferably 3 to 10; R 5 , R 6 , R 7 , R 8 , R 9 are hydrogen C 1 to C 20 alkyl, C 6 to C 20 aryl, C 7 to C 20 alkaryl radical and substituted derivative thereof, and Y is selected from the group consisting of hydrogen and oxygen substituted hydrocarbyl radicals having up to 10 carbons.

Claim 23

Dependent Claim 13 words

The method of claim 20 wherein the surfactant is of the formula: ##STR11##

Claim 24

Dependent Claim 17 words

The method of claim 17 wherein the clay granules have a grain size range of 10-40 mesh.

Claim 25

Dependent Claim 17 words

The method of claim 17 wherein the clay granules have a grain size range of 20-40 mesh.

Claim 26

Dependent Claim 162 words

A shear thickening composite comprising (1) 100 parts by weight (pbw) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising 25 to 130 pbw oil and 5.5 to 29 pbw surfactant and (3) an aqueous phase comprising 25 to 400 pbw water and 0.1 to 6.7 pbw water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear-thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste.

Claim 27

Dependent Claim 162 words

A shear thickening composite comprising (1) 100 parts by weight (pbw) water swellable clay granules capable of rapidly forming a high strength paste when brought into contact with water, (2) a hydrophobic phase comprising 25 to 130 pbw oil and 5.5 to 29 pbw surfactant and (3) an aqueous phase comprising 25 to 400 pbw water and 0.1 to 6.7 pbw water soluble polymer wherein the clay granules, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft 2 , are suspended in the hydrophobic phase as discrete particles, and the aqueous phase is also suspended as discrete droplets in the hydrophobic phase, the hydrophobic continuous phase maintaining the water swellable clay granules and aqueous phase droplets separated during low shear pumping of the composite, the clay granules fragmenting during the application of high shear to the shear-thickening composite causing the aqueous phase to contact the fragmented clay granules to form said paste.

Claim 28

Dependent Claim 35 words

The composite of claim 24 wherein the water swellable clay granules are selected from the group consisting of granular montmorillonite clay and granular attapulgite clay with a particle size of between 10 to 60 mesh.

Claim 29

Dependent Claim 40 words

The composite of claim 24 wherein the oil comprises mineral oil, C 6 to C 1000 paraffinic oil, motor oil, substituted paraffinic oil wherein the substituents are selected from the group consisting of halogens, amines, sulfates, nitrates, carboxylates and hydroxyls.

Claim 30

Dependent Claim 17 words

The composite of claim 26 wherein the oil is C 6 to C 200 liquid paraffin oil.

Claim 31

Dependent Claim 22 words

The composite of claim 24 wherein the water soluble polymer is polyacrylamide, polymethacrylamide, polystyrene sulfonate, polyvinyl toluene sulfonate, polyethyleneoxide, or polyvinyl alcohol.

Claim 32

Dependent Claim 12 words

The composite of claim 27 wherein the water soluble polymer is polyacrylamide.

Claim 33

Dependent Claim 18 words

The composite of claim 29 wherein the polyacrylamide is hydrolyzed to a degree ranging from 0 to 50%.

Claim 34

Dependent Claim 100 words

The composite of claim 24 wherein the surfactant is the product obtained by the reaction of the polyamine: ##STR12## wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and Y are selected from the group consisting of hydrogen, C 1 , to C 20 alkyl, C 6 to C 20 aryl, C 7 to C 20 alkaryl radicals and substituted derivatives thereof and x is an integer of from 1 to 100 with polyalkenyl succinic anhydrides, reaction proceeding at the R 3 , R 4 substituted nitrogen.

Claim 35

Dependent Claim 27 words

The composite of claim 31 wherein the polyalkenyl succinic anhydride is selected from the group consisting of polyisobutenyl succinic anhydride, polypropenyl succinic anhydride and polybutenyl succinic anhydride.

Claim 36

Dependent Claim 89 words

The composite of claim 32 wherein the surfactant is represented by the general formula: ##STR13## wherein n varies from 10 to 60, preferably 10 to 30, most preferably 15 to 17; x varies from 1 to 100, preferably 3 to 10; R 5 , R 6 , R 7 , R 8 , R 9 are hydrogen C 1 to C 20 alkyl, C 6 to C 20 aryl, C 7 is selected from the group consisting of hydrogen and oxygen substituted hydrocarbyl radicals having up to 10 carbons.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-03-04	1988-09-03	1989-03-05	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-03-04	1992-09-03	1993-03-05	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-03-04	1996-09-03	1997-03-05	$7700.00	Window Closed / Lapsed

Shear thickening fluid

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