CA1154945A

CA1154945A - Thickener from water-swellable material, oil surfactant and water

Info

Publication number: CA1154945A
Application number: CA000360286A
Authority: CA
Inventors: Charles R. Dawson, Jr.; Dennis E. O'brien; Norman N. Li
Original assignee: Exxon Production Research Co; Exxon Research and Engineering Co
Current assignee: ExxonMobil Upstream Research Co; ExxonMobil Technology and Engineering Co
Priority date: 1979-09-28
Filing date: 1980-09-16
Publication date: 1983-10-11
Also published as: EP0036019A1; GB2075088A; SE8103040L; US4397354A; DE3049883A1; WO1981000851A1; EP0036019A4; GB2075088B; SE442534B

Abstract

WELL TREATING FLUID (C-845) ABSTRACT OF THE DISCLOSURE
The instant invention is directed to shear thick-ening fluids which comprise a water-swellable material (clay), present in a sufficient concentration so as to be capable of forming a stiff paste upon interaction with the water used, and water wherein the clay and water are kept separated by an intervening hydrocarbon-surfactant compo-sition. The intervening oil phase prevents the interaction between the water and the clay phases and results in a stable, nonreacting, pumpable composite until such time as the oil envelope is ruptured by application of a sufficiently high shear force. Upon such rupture, the materials inter-act rapidly forming a semi-rigid stiff paste.
Various well-control problems, such as oil and gas with blowouts, can be controlled by use of the above-described composite. The composite is pumped down the well pipe.
Exiting the orifices of the drill bit or a nozzle supplies the shear force needed to rupture the oil envelope thereby permitting the interaction between the clay and the water resulting in the formation of a stiff paste which can stop or prevent unwanted flow in or near the wellbore.

Description

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WELL TREATING FLUID (C-845) The instant invention is clirected to well treating fluids/ particularly blowout control fluids, which are shear thickening fluids. The fluid composites comprise a water swellable material phase (clay for short) present in sufficient quantity so as to form a stiff past:e upon interaction with the water used, which can constittlte any of the known hydratable clays such as bentonite or attapulgite, a nonaqueous hydrophobic phase (oil for short) which comprises a hydrocarbonaceous component and a surfactant-strengthening agent component, and water which, when permitted to interact with the clay, results in a semi~rigid high strength paste.
In one particular embodiment, the clay is encapsulated in the oil phase and this encapsulated clay is suspended in the water resulting in a composite which is identified as a clay in oil in aqueous phase material, an aqueous continuous phase system.
Alternatively~ the water can itsel~ ba encapsulated as discrete d~oplets in the oil phase whereby the oil phase becomes the continuous phase, the system being identified as an oil con-tinuous system.
In either embodiment, the clay and the water are kept separate from each other by the intervening oil phase until such time as their interaction is desired. Such interaction is effected by rupturing the oil phase envelope by the application of a shear-force sufficient to rip apart the oil phase envelope and thereby mix the clay a~d water componen~s.
In drilling operations, this fluid is pumped down the drill pipe only when necessary for the specific purpose of block-ing unwanted flow channels either in or immediate~y adjacent tothe wellboreO This material is not to be confused with typical well circulation-drilling fluids containing clay and water components.

~5~ 5 The material of the instant invention is stable to the forces exerted upon it during pumping down the well pipe. Exit-ing the ori~ices of the drill bit, Ihowever, applies a sufficient force to rupture ~he oil envelope and mix the clay and water components in a semi-rigid, high strength gel capable of, for example, plugging a wellbore to stop a blowout or sealing a lost circulation zone.
A particular achievement O.e the instant invention is its ability to stop pre-existing unwanted flows provided that the past is injected into the unwanted flow at an approximately high rate and provided that the unwanted flow is exiting through a flow channel long enough for a paste plug to be formed.
The exact placement of a paste plug in or near a wellbore will depend on the problem to be treated. For example, if un-wanted fluid was entering the wellbore at the bottom and flowing uphole, the paste plug would be ~ormed as close to the bottom of the hole as possible. On the other hand, if fluid was flowing downhole from and departing the wellbore undesireably into a thie formationt the composite would be pumped into the wellbore just above the thief zone so that the paste would be formed at the flow channels in that zone and plug them. Other possible uses of the present invention can also be envisioned, such as blocking channels in cement behind casing, repairing leaks in ; casing or ~ubing, placing temporary plug in vari~us places, etc.
BACKGROUND OF THE` INtlENTION
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During drilling, or production of an oil or gas well, there are occasionally unwanted fluid flows in or near the well-bore, and there are also oc~asionally unwanted channels open downhole where unwanted flow could take place. On these occasionsj it may be necessary to introduce fluids into the well to kill the well, or at the very least, terminate the unwanted ~low or seal the unwanted channels~

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Examples o~ these problems are:
Unwanted influx of formation fluid into the wellbore (blowout) Loss of drilling fluid into fractures or vugs in the formation (lost circulation).
Channels in cement behind casing.
Holes in casing.
Improperly sealing linear hangers.
A typical scenerio involves formation 1uid influx which cannot be contained by closing the blowout preventers or by cir-culating the high density, drilling mud. For example, when an unusually high pressure formation is encountered, it may be necessary to emply drilling mud at such high weight that a forma-tion above the high pressure zone is fractured. This fractured xone then becomes a "lost zone" into which mud flows at such a high rate that "lost circulation" occurs. The lost circulation may be so severe that it ultimately becomes impossible to main-tain a column of mud above the high pressure zone sufficient to impart the necessary hydros~atic head to offset the high pressures in the high pressure zoneO As this occurs, the well becomes in-creasingly susceptible to blowout into the lost zone or to the surface.
There are a number of techniques which have been employed when one or another of these problems are encountered. A common solution is to force a cement slurry into the unwanted flow channel. This procedure is often successful, although sometimes multiple treatments are necessary, as long as there is no signi-ficant flow presen~ in the unwanted channel. Cement is useless against a pre-established flow because cement has almost no flow ; 30 resistance unt:il it is set. Thus it is always necessary to stop the flow before using cement to plug the flow channel.
The hydrostatic head of various fluids is often employed to prevent or stop unwanted movement of fluids up the wellbore.
In particular, most blowouts involve the uncontrolled flow of î~

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1: L54~45 formation fluids into the wellbore and then upwards in the well-bore. This type of blowout can he controlled by injecting fluid at the proper density and rate into the wellbore at or near the point of influxO In practice, the required density and rate may be difficult to obtain.
One technique involves placing a high density barite slurry (barium sulfate) in the annulus adjacent the high pressure zone to provide ~he extra hydrostatic head needed to ~top or pre-vent formation fluid influx. If the barite slurry remains defloc-culated after placement at the bo~tom of the well and relatively ~ndisturbed, the barite settles uniformly to form a hard plug.
O~e problem with using barite to form a plug is that the barite's ability to form a plug varies greatly depending upon the ~orma-tion temperature, the operating conditions, and the quality of barite used. For example, it is sometimes difficult to plug a well in the presence of a significant flow movement in the well-bore. If the fluid influx is not killed immediately by the hydro-static head of the barite slurry, the settling barite will usually not stop the unwanted flow.
The unwanted loss of fluids from the wellboxe is often treated by injecting a slurry of fiberous, lumpy, or flakey material into the wellbore at the region of the loss. These "lost circulation materials" are intended to plug or form a mat over the channels through which the fluid is entering the rock.
A pasty material known as "gunk" is sometimes used as a lost circulation material and occasionally to form temporary plugs in the wellbore. Gunk is a slurry of dry powdered bentonite in diesel oil. ~ typical gunk recipe is 350 lb of bentonite in of bbl of diesel oil. This slurry is quite fluid when mixed and remains fluid as long as it is kept anhydrous. Mixing gunk slurry with an approximately equal volume of water causes the clay to ~` hydrate into a stiff paste. I~ formed at the right time :
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~ 5 1 and at the right place, this gunk paste is an effQctive lost 2 circulation and plugging material. ~oweve~, since the gunk

3 slurry will hydrate and thic~en im~ediately upon contacting

4 water, i~ must be kept dry until it has been pumpet downhole S to the place where a plug is desired. The mixing of the gunk 6 slurry with water takes place downhole as the two fluids are 7 commingled. In some cases, there is some control over the 8 ratio of gunk slurry to water; in other cases, even this con-9 trol cannot be achieved. Since o~unk only achieves ade~uace flow resistance to for~ a plug within a certain range of 11 gunk/water ratios, the per~onmance of gunk as a pLugging agent 12 has been erratic. In particular, gunk i9 seldom useful for 13 ~lowout control because the re~uirement of having the proper 14 gunk/water ratio is difficult to satisfy.
~ISCIOSUR~
16 The composites ~f the instant invention solve a 17 multitude of well control problems, in particular, the prob-18 lems of thie~ zone control and blowout control or prevention.
19 A low viscosity material, stable to pumping, is pumped town a well pipe and rorced through the orifices of the trill bit 2I or out a nozzle. Upon exiting the drill bit or nozzle or be-22 inO subjec~ed to any other perturbationsuf~icient to generate 23 a hioh enough applied shear~ the oil envelope separating the 24 clay from t~e water is ruptured, permitting the clay and water to mi~ and set up into a high s~rength part at the point in 26 ~he well at which such a paste is required.
27 ~he shear thickening well treating fluids o~ the 28 instant invention are a multi-component composite comprising 29 a wa~er swellable material, present in sufficient quantity to react with the water used and set up into a hi~h strength 31 paste, (for t~e purposes of this speci~ication, the term 32 "clay" shall be employed) preferably a bentonite or attapul-33 gite clay, which can broadly be described as any layered or 34 chair configuration materlal which, in che presence of wacer, swells into a high viscosity solid mass; a hydrophobic phase 36 comprising a hydrocarbonaceous component and , :: :
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, ' 99~5 a surfactant component and water, preferably fresh water, but any water is satisfactory so long clS it does not contain any materials in a high enough concen~ration to interfere with the gelling of the water swellable material.
In general, the hydrophobic phase comprises a liquid oil, preferably any low aromatic content: oil, typically mineral oil, paraffinic oils of from 6 to 1000 carbons (provided they are liquid at the temperature at which they are employed) motor oils such as diesel fuel or kerosene, substituted paraffinic oils wherein the substituents are selected from the group consisting of halogens, amines, sulfates, ni~ra~es, carboxylates, hydroxyls, etc. Pre~erred oils are the C6-C200 liquid paraffin-These hydrophobic nonaqueous materials are preferablymixed with oil soluble surfactants so as to enhance their hydro-phobicityO A wide variety of surfactarlts can be used in the process of the instant invention. These surfactants include anio-nic, cationic, nonionic and ampholytic surfactants. These sur-fac~a~ts are described in the ~ook Surface ACtiVe Agents_and ~ Q~ by Schwartz9 Perry and Becih, Interscience Publishers, Inc.~ New York; New York.
The only requirement which must be met by the surfactant is that it be able to stabilize the water droplets and clay particles in the oil phase sufficiently to protect the mixture from premature gelling under low shear mixing conditions.
Anionic surfactants include carboxylic acids,'i.e.,fatty acidst resin acids~ tall oil acids and acids from paraffin oxi-da~ion products. Also included among the anionic surfactants are alkyl sulfonates~ alkylaryl sulfonates, mohogany and petroleum sulfonates, phosphates and lignin.
Cationic surfactants include quaternary ammonium com-pounds, e.g., salts of long chain primary, secondary and tertiary amines as well as quaternary amine salts with 7 to 40 carbon atoms~ Styrene copolymers containing pendant quaternary ammonium groups including drivatives of ~rimethylamine or dimethylethano-lamine are also useful cationic surfactants.

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Unprotonated amines fall into the class of non-ionic sur-~actants. A preferred group of amines have the general formula:
Rl I

wherein Rl Rl and R2 may be independently selected from the yroup consisting of hydrogen, Cl to C20 a;Lkyl, C6 to C20 aryl and C7 to C20 alkylaryl radicals.
Various polyamine derivatives are useful within the scope of the instant invention. The preferred polyamine deri-vatives are those having the general formula:r _ 3 \ ,5 ,7 Rg N - C - C - N _ R4 R6 R8 x n R3~ R4~ R59 R~ R7 9 R8, Rg and y are chosen from the gxoup consisting of hydrogen, Cl to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radicals and substituted derivatives thereof and x is an integer of from 1 to 100, The substituted deriva-;:~ tives are preferably selected from the group consisting of ; oxygen, nitrogen, sulfur, phosphorus and halogen containing deri- 20: vative. The most preferred material is:
2 (cH2cH2NH~3c~2cH2NH2 In general, the preferred surfactants are the product~

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,; ' ~ ' ' obtained by the reaction oE the polyamine described above with various polyalkyl succinic anhydrides, such as polyisobutylene succinic anhydride, polypropenyl succinic anhydride and polyiso-butenyl succinic anhydride.
A preEerred polyamine derivative, formed by reacting together an alkyl succinic radical, and the polyamine has the gen-eral formula:

H C ~ C C~ R5 ~7 Rgl 3 3 H C - C~ 6 R8 ~x (A) wherein n varies from 10 -to 60, preferably 10 to 30, most prefer-ably 15-17, x varies from 1 to 100, preferably 3 to 10, R5, R6, R7, R~ and Rg are hydrogen Cl to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radical and substituted derivatives thereo~, preferably hydrogen and y is selected from the group consisting of hydrogen and oxygen containing hydrocarbyl radicals having up to 10 carbons, e.g., acetyl. Typically, the surfactants have a molecular weight ; on the order of about 1000.
Nonionic systems include the polyethenoxy surfactants, i.e., polyethoxy ethers of alkyl phenols, polyethoxy ethers of alcohols, etc. The polyethenoxy ethers are especially useful in the invention as their solubility may be varied according to the 20~ weight of ethylene oxide added to the alkyl phenol starting mater-ial. Another nonionic surfactant which is particularly useful is sorbitan monooleate which is known in the trade by the name of _ ~ ~

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Span~80* and manufactured by the Atlas Chemical Company. Ampho-lytic surfactants contain both an acidic and a basic function in their structure and therefore wil:L be cationic or anionic accord-ing to the pH of the solution in which they are dissolved.

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4~5 The ~inal component of the shear sensitive fluids of the instant invent~on is water~ preferably fresh water, but as pre-viously stated, any water may be employed so long as it does not contain any material or pollutant in high enough concentration to interfere with the gelling of the water swellable material~
The composite made up of the above recited ingredients can assume a number of physical conditions all of which are in~
cluded within the scope of the instant invention and all of which will function as shear thickenihg fluids.
In one embodiment, ~he clay component will be encapsu-lated in the pre~iously defined oil phase (hydrocarbonaceous component and surfactant) and this encapsulated clay will in turn be suspended in the water wherein the water will exist as the continuous phase~
In an alternative embodiment, the clay as discrete parti-cles will be encapsulated in the oil phase while discrete droplets o~ water will also be encapsulated in the oil phase (the discrete clay particles and water droplets existing as separate entities, separated by the oil phase) which oil phase in this embodiment is 2 n the continuous phase.
In either embodiment, the clay and the water are kept separate until such time as their mixing is deliberately desired, and this is accomplished by subjecting the composite to a shear force, as by passage through the nozzle of a drill bit, of suf-ficient intensity to rupture the oil-phase envelope. Sufficient shear can also be generated by pumping the composite through the pipe at such a rate that a sufficient pressure drop is created to rupture the oil envelope.
In a preferred embodiment, the clay is a bentonite clay, the hydrocarbon oil is SlOON~ a C30 paraffinic liquid oil, and the surfactant is chosen from the group of materials having formula corresponding to Compound ~, previously definedO

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Most pre~erably, polyamines o~ the formula Al or A2 below are employed: ~ .
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from Exxon Chemical Co.
In addition, the composition may have included in it, : either in~the oil phase or in the water, preferably the oil phase, a fiberous material such as fiberglass, asbestos~ wood fiber, cellulose~ shreaded paper, cotton seed hulls, sugar cane bagasse, : : 13 peanut shells, shreaded oId tires, etc., which is substantially : impervious to the action of the water and to the oil phase. These added materials serve the purpose o~ imparting increased mechanic-~7~ : al strength and rigidity to the gel paste which sets up, upon rupture of the oil envelope, when the clay and water phases inter-act.
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The ~hear thickening fluid may also have added to it materials such as barite, hematite, galena, ilmenite, etc.l which are commonly used for increasiny the density and drilling fluids~
These weighking agents are not water-swellable and will not participate in the shear-thickening effect of the instant inven-tion but would be added if higher density formulations were particularly desired. If used, the weighting agents will absorb some of the surfactant, especially if the agent is finely powdered.
With the one proviso that the clay and the water are never mixed before their introduction into the hydrocarbonaceous phase, the composites of the instant invention, whether water continuous or oil continuous, are prepared by mixing the compon-ents in any order. In general, the oil surfactant and clay are mixed together employing any convenient mixing apparatus. The clay can be added to premixed oil and surfactant, or clay can be added to the surfac~ant and then the oil added or vice-versa.
Alternatively, the oil can be added to the clay and then the sur-factant added, or the oil-surfactant combination can be added to the clay. Any technique is acceptable so long as the clay becomes encapsulated by the oil-surfactant phaseO
The composite of the instant invention has its components present in the following ranges (expressed in parts by weight):
Clay lOO
Wa~er 150 to 400 Oil 50 to lSO
Surfactant 5 to 50 The effectiveness of the liquid-membrane well control fluid is illustrated clearly in the following examples, summarized in Table I.
When 10~ bentonite was mixed with 90% water, a thick gel was formed with a viscosity of 2200 cp. When bentonite was en-capsulated by liquid membrane No. 1 (3% polyamine A 97% SlOON) .

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and then mixed with water at a 1/9 ratio, the mixture had only a viscosity of 350 cp~ When a second formulation was used for en-capsulation of the bentonite clay particles (LM No. 2~ 5% poly-amine A 95~ SlOON), the viscosities of the mixture of the encap-sulated bentonite and water (1/9 to 1/24 ratio encapsulated clay to water) were in the range of 4 to 5 cp, indicating that the encapsulation was indeed very effective and that the mixture was almost as fluid as water (viscosity of 1 cp) and therefore would be easily pumpable down the well. The last experiment shows that when the above rnixture is subjected to a strong shear in a Waring blender similar to that as would be encountered upon being pumped through drilling bit noæzles~ the membranes were ruptured, expos-ing the bentonite particles to the surrounding water, a thick gel was found which had a viscosity of 2085 cp. In an actual opera-tion, this would mean that the gel would be formed after the mix-ture was pumped through the drilling bit nozzles, which would presumably plug the well and prevent the flow of the unwanted fluids in or near the well bore or generate a paste at the precise location desired to seal off lost circulation ~ones or channels 2~ in cement behind casings or holes in casings or improperly sealed liner hangers, etc., in other words, generate a paste capable of effecting the desired control in the well~

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The following example presents an embodiment of a shear thickening well control fluid and its use. Although this embodi-ment is the subject oE a separate paten-t application, S.N.
360,293 filed even date herewith i.n the names of E. Drake, et. al., it provides a preferred embodi.ment of the present invention. The composite comprises SlOON* paraffinic oil available from Exxon Company U~A, surfactant A2 availa~le as Paranox 106 availabl.e from Exxon Chemical Co. USA, KWK* granular bentonite, with a grain size of 20-70 mesh, available from American Colloid Company and a water solution of P-250* polyacrylamide availablé from American Cyan-amide Company. The composite was prepared according to the follow-ing procedure: a known weight of surfactant was dissolved in a ]cnown weight of oil; a known weight of granular bentonite was mixed with the oil/surfactant solution, resulting is a slurry of clay in oil/surfactant; polyacrylamide was d.issolved in water to give a solution of the desired strength; the a~ueous solution of polyacrylamide was added to the clay slurry with mixing resulting in the suspension of discrete droplets of polymer solution in the oil/surfactant. The resulting system is described as an oil con-tinous phase system.
; In a specific example, 10.5 grams Paranox 106 surfactant 59.5 grams SlOON, 120 grams granular bentonite, 2.0 grams poly-acrylamide (Cyanamer P-350*) and 200 grams potable water were formulated to yield an oil continuous system. This system was ~ stable to low shear for about 10 minutes. Vpon being subjected to : high shear (upon discharge through a nozzle), the material set up into a gel having a strength of about 15,000 lb/100 ft .
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Two formulations were compared, one a powdered bentonite system and the other a granular bentonite system, the granular system being similar to the system described in copending applica-tion S.N. 360,293 to Drake, Morrison and Dawson filed September 16, 1980, except for the absence o~ water-soluble/water-swellable polymer. These systems had the following compositions:

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1. 1250 y water 30 0 5 g 32 . 6% Paranox 106 in S100~1 30.5 g powdered bentonite 2. 125. g water 37.5 g 21.7~ Paranox 106 in SlOON
75. g KWK granular bentonite System 1 had a gel time of about 4,2 minutes w.ith a gel strength of 5,400 lb/100 ft2. System 2 had a gel time of 0 minutes with a gel strength of 15,000 lb/100 ft2. In system 2, the water was absorbed immediately by the granular clay and the fluid gelled immediately.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composite comprising a water-swellable material capable of rapidly forming a high strength gel when mixed with water, an oil-surfactant phase and water wherein the water-swellable material, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft2, and the water are kept separated, until mixing is desired, by the intervening oil-surfactant phase.

2. The composite of claim 1 wherein the water swellable material is selected from the group consisting of montmorillonite clay and attapulgite clay.

3. The composite of claim 1 wherein the oil comprises mineral oil, C6 to C1000 paraffinic oil, motor oil, substituted paraffinic oil wherein the substituents are selected from the group consisting of halogens, amines, sulfates, nitrates, carboxy-lates and hydroxyls.

4. The composite of claim 2 wherein the oil is a C6 to C200 liquid paraffin oil.

5. The composite of claim 1 wherein the clay is 100 parts by weight (pbw) of the composite, the water is 150 to 400 pbw of the composite, the oil is 50 to 150 pbw of the composite and the surfactant is 5 to 50 pbw of the composite.

6. The composite of claim 5 wherein the surfactant is the product obtained by the reaction of the polyamine wherein R3, R4, R5, R6, R7, R8, R9 and y are chosen from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radicals and substituted derivatives thereof and x is an integer of from 1 to 100 with polyalkenyl succinic anhyd-rides, reaction proceding at the R3, R4 substituted nitrogen.

7. The composite of claim 6 wherein the polyalkenyl succinic anhydride is selected from the group consisting of poly-isobutylene succinic anhydride, polypropenyl succinic anhydride and polybutenyl succinic anhydride.

8. The composite of claim 6 wherein the surfactant is represented by the general formula:

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(A) wherein n varies from 10 to 60, x varies from 1 to 100, R5, R6, R7, R8 and R9 are hydrogen C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radical and substituted derivative thereof, and y is selected from the group consisting of hydrogen and oxygen contain-ing hydrocarbyl radicals having up to 10 carbons.

9. The composite of claim 8 wherein n varies from 10 to 30.

10. The composite of claim 8 wherein n varies from 15 to 17.

11. The composite of claim 8 wherein x varies from 3 to 10.

12. The composite of claim 8 wherein the surfactant is represented by the formula:

and

13. A shear thickening composite stable to pumping com-prising a water swellable material capable of rapidly forming a high strength paste when mixed with water, an oil-surfactant phase and water wherein the water swellable material, present in suffic-ient quantity so as to form a paste having a strength of at least 2000 lb/100 ft, and the water are kept separated, until mixing is desired, by the intervening oil-surfactant phase which phase remains intact until ruptured by the application of a sufficiently high shear.

14. The composite of claim 13 wherein the water swellable material is montmorillonite clay or attapulgite clay.

15. The composite of claim 13 wherein the oil comprises mineral oil, C6 to C1000 paraffinic oils, motor oil, substituted paraffinic oil wherein the substituents are selected from the group consisting of halogens, amines, sulfates, nitrates, carboxy-lates and hydroxyls.

16. The composite of claim 14 wherein the oil is a C6 to C200 liquid paraffin oil.

17. The composite of claim 13 wherein the clay is 100 parts by weight (pbw) of the composite, the water is 150 to 400 pbw of the composite, the oil is 50 to 150 pbw of the composite and the surfactant is 5 to 50 pbw of the composite.

18. The composite of claim 17 wherein the surfactant is the product obtained by the reaction of the polymer wherein R3, R4, R5, R6, R7, R8, R9 and y are chosen from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radicals and substituted derivatives thereof and x is an integer of from 1 to 100 with polyalkenyl succinic an-hydrides.

19. The composite of claim 18 wherein the polyalkenyl succinic anhydrides are selected from the group consisting of polyisobutylene succinic anhydride, polypropenyl succinic anhyd-ride and polybutenyl succinic anhydride.

20. The composite of claim 14 wherein the surfactant is represented by the general formula:

(A) wherein n varies from 10 to 60, x varies from 1 to 100, R5, R6, R7, R8 and R9 are hydrogen C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radical and substituted derivative thereof, and y is se-lected from the group consisting of hydrogen and oxygen containing hydrocarbyl radicals having up to 10 carbons.

21. The composite of claim 20 wherein n varies from 10 to 30.

22. The composite of claim 20 wherein n varies from 15 to 17.

23. The composite of claim 20 wherein x varies from 3 to 10.

24. The composite of claim 18 wherein the surfactant is represented by the formula:

and

25. The composite of claim 17 wherein the clay is suspended in the oil-surfactant phase and this clay slurry is sus-pended in the water, the water being a continuous phase.

26. The composite of claim 17 wherein the clay is suspend-ed in the oil surfactant phase as discrete particles and the water is also suspended in the oil-surfactant as discrete droplets, the oil-surfacntant phase being a continuous phase.

27. The composite of claim 20 wherein the clay is suspend-ed in the oil-surfactant phase yielding a slurry and this clay slurry is suspended in the water, the water being a continuous phase.

28. The composite of claim 20 wherein the clay is suspend-ed in the oil-surfactant phase as discrete particles and the water is also suspended in the oil-surfactant phase as discrete par-ticles, the oil-surfactant phase being a continuous phase.

29. A method for treating a well penetrating a subter-ranean formation to block off unwanted flow paths comprising in-troducing into said well a shear thickening composite stable to pumping comprising a water swellable material capable of rapidly forming a high strength paste when mixed with water, an oil-sur-factant phase and water wherein the water swellable material, present in sufficient quantity so as to form a paste having a strength of at least 2000 lb/100 ft2, and the water are kept sep-arate, until mixing is desired by the intervening oil-surfactant phase, and subjecting said shear thickening composite to high shear mixing thereby rupturing the intervening oil-surfactant phase, mixing the water swellable material and the water causing it to thicken rapidly into a high strength semi-rigid paste which blocks off unwanted flow paths.

30. The method of claim 29 wherein the high shear mixing consists of passing the shear thickening fluid through the ori-fices of a drill bit or nozzle in the well.

31. The method of claim 29 wherein the water-swellable material is bentonite or attapulgite clay.

32. The method of claim 29 wherein the shear thickening composite is 100 parts by weight (pbw) clay, 150 to 400 pbw water, 50 to 150 pbw oil and 5 to 50 pbw surfactant.

33. The method of claim 32 wherein the clay is montmoril-lonite clay or attapulgite clay, the oil is mineral oil, C6 to C1000 paraffinic oil, 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 the polyamine.

wherein R3, R4, R5, R6, R7, R8, R9 and y are chosen from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radicals and substituted derivates thereof, and x is an integer of from 1 to 100 with polyalkenyl succinic anhydrides, reaction proceding at the R3, R4 substituted nitrogen.

34. The method of claim 33 wherein the surfactant is represented by the general formula:

(A) wherein n varies from 10 to 60, x varies from 1 to 100, R5, R6, R7, R8 and R9 are hydrogen C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radical and substituted derivative thereof, and y is se-lected from the group consisting of hydrogen and oxygen containing hydrocarbyl radicals having up to 10 carbons.

35. The method of claim 34 wherein n varies from 10 to 30.

36. The method of claim 34 wherein n varies from 15 to 17.

37. The method of claim 34 wherein x varies from 3 to 10.