Abstract:
An anaerobic sealant composition is employed to seal a pipe joint between pin and box members intended for use in petroleum drilling operations. The composition is applied to one or both of the members. The members are then joined and the composition cured into a solid form which bonds to the members and fills the space between them. The constituents of the composition can be selectively varied to control its lubricity which also affects the make up torque. Additionally, the concentration of the sealant composition can be selectively varied to control the break out torque of the joint to which it is applied, and preferably make the break out torque substantially greater than the make up torque. Excellent seals can be obtained using lower grade pipe, and the pin and box members can be made up with the application of lower torque to the assembly without reducing the sealing capabilty of the connection. The preferred composition also serves as a rust and corrosion inhibitor for the joint.

Description:
This is a continuation of co-pending application Ser. No. 893,710, filed on Aug. 6, 1986, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     I. Field of the Invention 
     The present invention relates to an anaerobic sealant composition employed to seal pipe joints between pin and box members intended for downhole tubular goods used in petroleum drilling operations. The invention encompasses not only the sealant composition itself but the method of its application to the pipe joint structure, and the resulting connection. 
     For purposes of the invention, the term &#34;petroleum&#34; will be taken to include, but not necessarily be limited to, operations related to the exploration, drilling, and extraction from the earth of oil, gas, water, and geothermal materials as well as the disposal of nuclear and/or toxic wastes. Additionally the term &#34;pipe&#34; will be used for convenience to refer to all downhole tubular goods, whether it be tubing, drill pipe, casing, production pipe, or the like. 
     The term &#34;drilling&#34;, likewise, will be taken to include exploration for and extraction of materials from the earth as well as formation of a deep hole through which the materials are extracted. It will be understood, however, that pipe having the same characteristics of that used in petroleum operations can also be used in the opposite sense, that is, to return materials into the earth. Such a procedure is involved in the return of petroleum products to underground storage or the transfer of nuclear wastes to underground containment fields. Thus the term &#34;drilling&#34;, for purposes of the invention, will also include preparation for such storage of petroleum or other products or disposal of nuclear or other wastes beneath the surface of the earth. The invention herein is concerned with the connection between two lengths of pipe. The ends to be joined of the two lengths of pipe are commonly referred to as a &#34;pin&#34; and as a &#34;box&#34;. In this context, a &#34;pin&#34; may be an externally or internally threaded end of pipe and a &#34;box&#34; may likewise be an externally or internally threaded end of pipe and a coupling connected thereto with suitable threads for receiving a pin. However, these terms should be read sufficiently broadly to cover connecting mechanisms other than threads. Also, the term &#34;make up&#34; and variations thereof are taken to mean assembly of two pin and box members, and the term &#34;break out&#34; and variations thereof, are taken to mean disassembly of the pin and box members. 
     II. Description of the Prior Art 
     The problems associated with petroleum drilling operations are many and extreme. The conditions experienced include extremes in temperature, not only between polar regions and equatorial regions, but also of the products being extracted and the high temperature of the formations at depth. Pressures can be intense in the depths of the earth as well as exposure to the harsh corrosiveness of such toxic materials as sulfur dioxide and hydrogen sulfide. 
     Particularly grueling are the stresses imposed on downhole tubular goods in the instance of a string of pipe which may be many thousands of feet in length. 
     Couplings or tubular connections for lengths of pipe are of paramount importance in the drilling operation and serve two primary functions. In the first instance, they hold the weight of the pipe which can amount to two million pounds or more and they serve to seal the pipe both against incursions from its exterior as well as loss of the products being extracted. The customary type of pipe connections used in drilling operations are threaded joints and the industry standards which have been established by the American Petroleum Institute (API) are known as &#34;API 8-round&#34; and as &#34;API buttress&#34; threads. 
     Leaking pipe connections have represented a significant problem to the petroleum industry, and the problem continues although recent research and development efforts by connection manufacturers and operators have made significant improvements in the technology. Premium connection designs employing various combinations of interference-fit threads metal-to-metal seals, new generation of non-metallic seal materials, higher alloyed steels, and computer/numerical control machining technology have been developed and are very effective. Typical of such premium connection designs are those disclosed in Blose U.S. Pat. No. 4,244,607 issued Jan. 13, 1981 and U.S. Pat. No. Re. 30,647 reissued June 16, 1981. These patents are incorporated in and made a part of this application, by reference, as being typical of the technology relating to premium connections. 
     Some of these designs include &#34;Teflon&#34; brand o-rings, or the like, as sealing aids. In this instance, sufficient material must be removed from the pipe end in the region of the joint to accommodate the o-ring. 
     Such removal necessarily weakens the joint and increases the stresses imposed on the joint. Furthermore, the o-ring material does not have sufficient plasticity to satisfactorily seal the interstices of the joint. 
     Nonetheless, failures continue to occur due in part to greater sensitivity of many of these designs to handling, running, and environmental factors. Single failures of production strings have cost millions of dollars and they continue to occur as industry continues to push back the technology frontier. One of the most pervasive causes of these connection failures is leakage. Aside from design problems, many new connections are easily damaged by a variety of common rig and handling procedures. 
     As a further effort to prevent leaking connections, sealing materials have been developed and are widely used by the industry. Numerous such sealing materials are available such as Shell high pressure thread compound produced by Shell Oil Corporation, EXXON 706 thread compound produced by EXXON Corporation, and &#34;Liquid-O-Ring&#34; brand thread compound manufactured by Oil Center Research, Inc. of Lafayette, La. These materials meet API standards and are referred to as &#34;API modified&#34;. Typically, the components of these sealing materials include an oil based lubricant, and sealant components which may include, for example, powdered graphite, lead powder, zinc dust, and copper flake. There is no chemical reaction between the sealant components and the lubricant. The composition is merely a mixture and there is no curing step involved in its preparation or use. These sealing materials remain in a liquid form, seeking any voids which are present between the mating threads within the joint. 
     While such sealing materials have worked reasonably well, they are, in composition, primarily a lubricant and only secondarily a sealant. The sealant components of the mixture seek out the voids within the threaded joint, but if a hole is large enough, the sealant material will extrude out and the sealant will no longer be effective for its intended purpose. It also often occurs in the harsh environment in which drilling operations take place that the liquid component of the sealant material bakes off in the extreme heat to which it is exposed, leaving voids and the metallic sealant components behind. These components typically have particle sizes lying in a range of 50 to 500 microns. This is not only undesirable during normal drilling operations, but becomes even more of a problem during disassembly of the pipe. Customarily, the same pipe can be used in a number of reinstallations in the same well or installations in successive wells. This, of course, is desirable because of the heavy expense of the piping. However, in the instance in which the lubricant bakes off, the metallic particles left behind are of a gritty consistency and, upon disassembly, sometimes causes gelling to occur on the threads of the pipe. This causes the pipe to be more difficult to disassemble and severely limits the reuseability of the pipe. 
     SUMMARY OF THE INVENTION 
     It was with knowledge of the prior art and the problems existing which gave rise to the present invention. The present invention, then, is directed towards a curable sealant composition which is employed to seal a pipe joint between pin and box members intended for use in petroleum drilling operations. In its preferred form, the composition is a single component anaerobic material which is applied to one or both of the members. The members are then joined and the composition cures into a solid form which bonds to the members and fills the space between them. The constituents of the composition can be selectively varied to control its lubricity which also affects the make up torque. Additionally, the concentration of the constituents of the sealant composition can be selectively varied to control the break out torque of the joint to which it is applied, and preferably make the break out torque substantially greater than the make up torque. Excellent seals can be obtained using lower grade pipe, and the pin and box members can be made up with the application of lower torque to the assembly without reducing the sealing capability of the connection. The preferred composition also serves as a rust and corrosion inhibitor for the joint. 
     Subsequent discussion refers primarily to this preferred composition. The curable sealant composition of the invention (hereinafter &#34;sealant&#34;), in its preferred form, is a high viscosity anaerobic resin which may be combined with powders of PTFE (polytetrafluoroethylene) and/or polyethylene having particles approximately 10 microns in diameter for lubrication. Having a consistency between a thick liquid (e.g. maple syrup) and a soft paste (e.g. toothpaste), the sealant polymerizes between close fitted metal surfaces to provide sealing and resistance to loosening with a low break out strength. The sealant remains liquid indefinitely while exposed to the air. Upon application to and make up of connections, however, complex reactions occur in the sealant which cause it to polymerize in the absence of air to form a hard, high molecular weight, material with adhesive and sealant properties. These reactions are further catalyzed by the presence of iron, copper, nickel and other metals. 
     The sealant has been specifically designed for use in sealing downhole petroleum drilling pipe joints. While such pipe joints have traditionally been of a threaded nature, the application of the sealant need not be limited to threaded joints but can be applied with similar results to a variety to other types of joints as well. It may used on slightly oiled, cadmium and zinc plated, black oxide, and phosphate and oil coated parts and still obtain satisfactory results. For a maximum benefit, parts should be wipe cleaned, but need not be solvent cleaned to remove an oil coating. This is for the reason that petroleum based oils by nature have an iron content sufficiently high to cause the resin or monomer in the anaerobic sealant to polymerize. 
     Some of the benefits of the sealant include the fact that it can be applied to the mating surfaces of the pin and box members either by machine or by hand. In the instance of threaded joints, the sealant seals between the threads to prevent spiral leak paths. Indeed, the sealant seals all voids including microgrooves and other regions such as the metal to metal seal areas as found in premium connections. The sealant contains no lead (which is toxic to human beings), is non-stringy (and therefore easy to apply), and employs no flammable solvents (which would be particularly hazardous on a petroleum drilling rig). 
     Primary benefits of the invention, in addition to its excellent sealing ability, reside in its lubricity which improves the ability to make up and break out pipe joints, in its chemical stability and in the ability to adjust its cohesive and adhesvie strength so as to achieve a desired predetermined value of break out torque. As a result of some of these benefits, the sealant will extend the life of production strings and will permit the upgrading of cheaper pipe for higher pressure applications. 
     A particularly important feature of the invention resides in the ability to provide a different break out torque for different members of a pipe joint. Specifically, it is common practice to use lengths of pipe in the field which have a pin at one end and a box at the opposite end. In this instance, the box portion of the joint is usually assembled in a factory, then the pipe is shipped to the drilling site. As noted above, the constituents of the sealant composition can be controlled to thereby control the break out torque of the joint. According to this further embodiment of the invention, the concentration of the resin or  monomer can be consistently different when applied to the mutually engageable surfaces of the box than when applied to the pin such that, upon subsequent breakout, the same end of each ensuing length of pipe will be a pin and its opposed end will be a box. In this way, handling of the pipe is facilitated to a substantial extent. Prior art sealants customarily are not applied until make up as the pipe is descending into the well. However, with this embodiment of the invention, the sealant having one concentration of the resin or monomer would preferably be applied at the factory at the time of assembly of the box portion of the joint. Then, the sealant having a different concentration of the resin or monomer would be applied during make up in the field. 
     Other and further features, objects, advantages, and benefits of the invention will become apparent from the following description. However, it is to be understood that both the foregoing general description and the followed detailed description are exemplary and explanatory but are not restrictive of the invention. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The basic composition of the sealant with which the invention is concerned is of a generally known formulation which has been be used in a variety of other applications. Examples which have disclosed the use of monomer compositions having anaerobic properties are U.S. Pat. No. 3,625,875 to Frauenglass et al and U.S. Pat. No. 3,969,552 to Malofsky et al. These patents are incorporated in, and made a part of, this disclosure by reference. 
     The monomers contemplated for use in the invention disclosed herein are polymerizable acrylate esters. As used herein, &#34;acrylate esters&#34; includes alpha-substituted acrylate esters, such as the methacrylate, ethacrylate, and chloroacrylate esters. Monomers of this type, when mixed with a peroxy initiator as described below, form desirable adhesives and sealants of the anaerobic type. 
     Anaerobic adhesives and sealants are those which remain stable in the presence of air (oxygen), but which when removed from the presence of air will polymerize to form hard, durable resins. This type of adhesive and sealant is particularly adaptable to the bonding of metals and other nonporous or nonair permeable materials since they effectively exclude atmospheric oxygen from contact with the adhesive or sealant, and therefore the adhesive or sealant polymerizes to bond the surfaces together. Of particular utility as adhesive or sealant monomers are polymerizable di- and other polyacrylate esters since, because of their ability to form cross-linked polymers, they have more highly desirable adhesive or sealant properties. However, monoacrylate esters can be used, particularly if the monacrylate portion of the ester contains a hydroxyl or amino group, or other reactive substituent which serves as a site for potential cross-linking. Examples of monomers of this type are hydroxyethyl methacrylate, cyanoethyl acrylate, t-butylaminoethyl methacrylate, glycidyl methacrylate, cyclohexyl acrylate and furfuryl acrylate. Anaerobic properties are imparted to the acrylate ester monomers by combining with them a peroxy polymerization initiator as discussed more fully below. 
     One of the most preferable groups of polyacrylate esters which can be used in the adhesives or sealants disclosed herein are polyacrylate esters which have the following general formula: ##STR1## wherein R 1  represents a radical selected from the group consisting of hydrogen, lower alkyl of from one to about four carbon atoms, hydroxy alkyl of from one to about four carbon atoms, and ##STR2## R 2  is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of from one to about four carbon atoms; R 3  is a radical selected from the group consisting of hydrogen, hydroxyl, and ##STR3## m is an integer equal to at least 1, e.g., from 1 to about 15 or higher, and preferably from 1 to about 8 inclusive; n is an integer equal to at least 1, e.g., 1 to about 20 or more; and p is one of the following: 0, 1. 
     The polymerizable polyacrylate esters utilized in accordance with the invention and corresponding to the above general formula are exemplified by but not restricted to the following materials: di-, tri- and tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di(chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate and trimethylol propane triacrylate. The foregoing monomers need not be in the pure state, but may comprise commercial grades in which inhibitors or stablizers, such as polyhydric phenols, quinones, etc. are included. As used herein the term &#34;polymerizable polyacrylate ester monomer&#34; includes not only the foregoing monomers in the pure and impure state, but also those other compositions which contain those monomers in amounts sufficient to impart to the compositions the polymerization characteristics of polyacrylate esters. It is also within the scope of the present invention to obtain modified characteristics for the cured composition by the utilization of one or more monomers within the above formula with other unsaturated monomers, such as unsaturated hydrocarbons or unsaturated esters. 
     The preferred peroxy initiators for use in combination with the polymerizable acrylate or polyacrylate esters described above are the hydroperoxy polymerization initiators, and most preferably the organic hydroperoxides which have the formula R 4  OOH, wherein R 4  generally is a hydrocarbon radical containing up to about 18 carbon atoms, preferably an alkyl, aryl or aralkyl radical containing from one to about 12 carbon atoms. Typical examples of such hydroperoxides are cumene hydroperoxide, tertiary butyl hydroperoxide, methyl ethyl ketone hydroperoxide and hydroperoxides formed by the oxygenation of various hydrocarbons, such as methylbutene, cetane and cyclohexene. Other organic substances, such as ketones and esters, including the polyacrylate esters represented by the above general formula, can be oxygenated to form hydroperoxy initiators. However, other peroxy initiators, such as hydrogen peroxide or materials such as certain organic peroxides or peresters which hydrolyze or decompose to form hydroperoxides frequently can be used. In addition, U.S. Pat. No. 3,658,624 describes peroxides having a half-life of less than 5 hours at 100° C. as suitable in somewhat related anaerobic systems. 
     The peroxy initiators which are used commonly comprise less than about 20 percent by weight of the combination of monomer and initiator since above that level they begin to affect adversely the strength of the adhesive and sealant bonds which are formed. Preferably the peroxy initiator comprises from about 0.1 percent to about 10 percent by weight of the combination. 
     Other materials can be added to the mixture of polymerizable acrylate ester monomer and peroxy initiator, such as quinone or polyhydric phenol stabilizers, tertiary amine or imide accelerators, and other functional materials such as thickeners, coloring agents, etc. These additives are used to obtain commercially desired characteristics, i.e., suitable viscosity and shelf stability for extended periods (e.g., a minimum of one month). The presence of these additives is particularly important when peroxy initiators other than organic hydroperoxides are used. For a complete discussion of the anaerobic systems and anaerobically curing compositions, reference is made to the following U.S. Pat. Nos. 2,895,950 to Vernon K. Krieble, issued July 21, 1959; 3,041,322 to Vernon K. Krieble, issued June 26, 1962; 3,043,820 to Robert H. Krieble, issued July 10, 1962; 3,046,262 to Vernon K. Krieble, issued July 24, 1962; 3,203,941 to Vernon K. Krieble, issued Aug. 31, 1965; 3,218,305 to Vernon K. Krieble, issued Nov. 16, 1965; and 3,300,547 to J. W. Gorman et al, issued Jan. 24, 1967. 
     However, the aforesaid monomer compositions have been modified (e.g. by adjusting the strength, lubricity, etc.) for the purposes with which the present application is concerned, specifically, as a sealant for pipe joints, and more particularly, between pin and box members intended for use in petroleum drilling operations. Indeed, monomers having anaerobic properties have been totally unknown in the role disclosed herein and provide highly desirable results of a nature previously unknown. 
     As noted above, the sealant is applied to mating metallic surfaces in a liquid state. It may be applied in any suitable manner as, for example, by brushing, by means of a mechanical applicator, by a ribbon applicator, or by sponge. So long as the parts so coated remain exposed to the air, the sealant remains in its liquid state. However, when the parts are joined such that the internal interengaging surfaces are no longer exposed to the air, then the sealant cures to the solid state. When this occurs, it forms a physical bond to the outer surface of a metal on which it is coated. The presence of the metal to which the sealant is applied can also inititate and thereby accelerate the curing process. The sealant even fills the microgrooves which are formed in the metal resulting in elimination of leak paths for gases and liquids. The sealant provides an absolute, positive seal which works equally well with API 8-round, API buttress, and with premium connections. While the industry has had good experience with premium connections, the present invention provides a sound back up seal which is far more practical and reliable than &#34;Teflon&#34; brand o-rings, for example, that have come to be widely used. Effectively, the sealant of the invention provides a plastic seal throughout the area, without the need to machine expensive grooves (which weaken the pipe) as is required for the &#34;Teflon&#34; seal. 
     Physical properties of the preferred sealant of the invention include the following: 
     
         ______________________________________PHYSICAL PROPERTIES UNCURED SEALANT______________________________________Flash Point         &gt;100° C. (212° F.)Appearance          pink viscous liquidDensity             1.25Viscosity           150-500 Pa&#39;s(Brookfield Viscometer type HBT               (150,000-500,000 cP)#6 Spindle, 2.5 rpm @ 23 ± 2° C.)______________________________________Composition    21/2 RPM   20 RPM   Thixotropic Ratio______________________________________11296    75 cP      30 cP    2.5SL21     80 cP      26 cP    3.1SL22     67 cP      20 cP    3.4______________________________________ Note: Thixotropic ratio refers to the gap filling ability of the sealant and to its ability not to drip when applied. The above numbers reflect this ability of the sealant; specifically, the greater the thixotropic ratio i than 1.0, the less it will drip. Other desirable properties of the sealan in its uncured state include: its ability to be easily dispensed, as from a squeeze tube; its stability, that is, its long shelf life in a package prior to being used; its low toxicity, that is, lack of lead or other heavy metals among its constituents; its nonflammability, that is, its flash point above 212° F. Its lubricity is a measure of how much tension is applied to a joint with a given amount of torque. 
    
     Lubricity 
     Tension (recorded in 100&#39;s of pounds) at the following torques: 
     
         ______________________________________    inch poundsComposition      100    200         300  400______________________________________11296      12     25          38   51SL21       15     33          49   68SL22       18     39          60   80______________________________________PHYSICAL PROPERTIES CURED AND CURING SEALANT    (Unseated) Break               Prevail (180°)______________________________________Cure Speed: Inch pounds break/prevail measured on3/8 × 16 iron nuts and bolts after 24hours @ 70° F. 11296      1 in. lb.   1 in. lb.SL21        6 in. lb.   2 in. lb.SL22        8 in. lb.   3 in. lb.Ultimate Strength: As above but after 4 hours @ 200° F.11296      50 in. lb.   0 in. lb.SL21       60 in. lb.   2 in. lb.SL22       60 in. lb.   5 in. lb.______________________________________ Note: Unseated break means that the nut is free spinning on the bolt. Other desirable properties of the sealant in its cured and curing state include its cured lubricity; its resistance to heat: it has been tested to 330° F. in heat cycling tests; its resistance to chemical attack (it is essentially chemically inert); and its hot strength  since it is a thermoset plastic composition, the sealant has a high hot strength. 
    
     It was previously noted that the sealant may contain PTFE and/or polyethylene additives in the form of a powder for lubricity. Each of these additives may be provided in the range of 0-20% by weight. PTFE increases lubricity slowly while polyethylene increases lubricity at a rapid rate per unit amount added. 
     In its liquid form, the sealant lubricates as well as or better than existing API thread compounds. Furthermore, because the sealant contains no solvent, there can be no &#34;bake out&#34; or loss of volume under temperature or with time as with known thread compounds. Because there is substantially no loss of volume when it is cured, it prevents leak paths from developing. Furthermore, in its cured solid state, when the pipes are disassembled, the sealant is pulverized into a powder form with lubricating qualities and continues to be as effective a lubricant as it was previously in its liquid or uncured state. This is because molecules of the sealant penetrate and remain in micro-burrs which exist on threads and other surfaces in the connection and reduce the galling effect caused by them. 
     The resulting threads are substantially clean and require little preparation for re-use. Thus, the sealant of the invention serves as a lubricant during both the make up and break out operations at the same time that it is an effective seal. 
     Another primary benefit is that the sealant permits sealing at lower make up torques than currently used with non-curing sealants since the curing sealant will plug larger gaps throughout the joint. With known sealants, high torque is necessary in order to prevent leakage, even with premium connections. It will be appreciated that with lower torque, there is less deformation of the pipe and hence a higher life expectancy to be anticipated from the thread. This would enable the use of API 8-round thread and API buttress thread in virtually all instances, thereby eliminating the need for the higher priced premium connections. This is important when one considers that a current price range for API 8-round connections is between ten dollars and twenty dollars per coupling whereas that for premium connections is between two hundred and five hundred dollars per coupling. In some specialized instances, the premium connections can cost even more than five hundred dollars per coupling. 
     Another benefit of a lower torque requirement is that less stress is imparted to the pipe connections assuring that the pipe will be more resistant to the corrosive effects of such highly toxic substances as hydrogen sulfide and sulfur dioxide which are common in petroleum well environments. Such toxic substances are known to corrode stressed regions in connections more rapidly than unstressed or lesser stressed regions. 
     Another significant benefit of the invention resides in the ability to control the strength of the sealant, by adjusting the percentage of its constituents. When translated into oil field terminology, this means that the break out torque can be controlled. Specifically, the greater the percentage of resin or monomer, the greater the break out torque when the sealant is applied to a pipe joint, and vice versa. Strength may also be increased by increasing the amount of mineral fillers, although not to the extent of resin variation. Typical mineral fillers are titanium dioxide used as a whitening agent and mica used as a strengthening filler. 
     Still another benefit of the invention is the ability to assure a substantially higher break out torque than make up torque in those connections where a low makeup torque is desirable. This is achieved by controlling the concentration of the ingredients in the sealant composition. In the preferred embodiment, the ingredient being controlled is the polymerizable acrylate ester monomer. This will assure that an end will not break out inadvertently due to a low make up torque. 
     The foregoing benefit of controlling break out torque by adjusting the concentration of the resin or monomer in the sealant composition leads to still another benefit of the invention. Specifically, it is desirable from a materials handling standpoint to know which end of a reusable pipe being withdrawn from a well will be a pin and which end will be a box so that the pipe can be uniformly stacked pending further use. This object can be achieved by applying sealant having one concentration of monomer to the box when it is assembled (most likely at the factory), then applying sealant having a different concentration of monomer to the pin at the drill site. The concentration of the monomer would be known in each instance such that the torque for break out of each portion of the joint would likewise be known. By maintaining the concentration of the monomer uniform in each instance, as the pipe is withdrawn from the well for subsequent use, the same end of each subsequent length of pipe will be a pin and its opposite end will be a box. Heretofore, there was no way of knowing whether an end of pipe would be a box or a pin upon break out. This created difficulty with subsequent operations which would be alleviated by the invention. 
     In addition to adjusting the percentage of the resin or monomer in the sealant composition to adjust break out torque, by making further adjustments to the formulation, it can be made certain that the prevailing strength is less than the break out strength. Prevailing strength is defined as the torque used to unscrew a pin from a box after the pin has been rotated through an arbitrary arc, for example, 180°. If prevailing strength is not maintained to a value less than the break out strength, the torque may increase with continued unscrewing of the pin from the box with the result that the disassembly of the pin and the box will become extremely difficult. 
     In current practice, relatively high torques are used for make up and something less than the make up torque is required for break out. This latter situation is not desirable, but is a characteristic of a joint to which known sealants have been applied. The higher torques are required to ensure sealing in the connections. The following is an extract from Test Summary 4 below of this disclosure. It clearly shows how the connection was made up to lower torques when the sealant was applied without compromising its sealing capabilities. 
     
         ______________________________________Make-up    Torques - Ft-Lbs                   Pressure Test - psi______________________________________API        2,500        Leak at 1,500      35,000       Leak at 8,000Sealant    2,500        Held at 8,000______________________________________ 
    
     Typically, using known sealant materials, break out torque is less than make up torque. However, by reason of the invention, break out torque can be made greater than make up torque by controlling the properties, specifically, the percentage of resin or monomer in the cured polymer. For example, in the above test, the connection broke out at a torque somewhat less than make up torque when made up with API compound. When the sealant was used, and the connection made up to 2,500 Ft-Lbs, the break-out torque was 14,000 Ft-Lbs. 
     Still another significant benefit of the invention is the chemical stability of the sealant. Specifically, its composition is such that it is inert to the chemicals normally encountered in petroleum drilling operations. Furthermore, the sealant composition is non-toxic when properly used and will not pollute the environment as will the known sealants, which contain heavy metals such as lead, nickel and the like. Substantial experimentation has indicated no adverse effects with exposure to chemicals encountered in oil field use, including hydrogen sulfide and sulfur dioxide. 
     Another significant feature of the invention is the self cleaning ability of the sealant. Specifically, upon break out, the solid polymeric material pulverizes and leaves a fine coating on the threads. This fine coating does not interfere with subsequent make up, but has been found to effectively prevent oxidation to an extent better than most known corrosion resistant protective coatings. 
    
    
     Extensive testing has been performed regarding the sealant, and the following reflect some of the more significant tests which have been performed to date using both the anaerobic sealant composition of the invention and previously known compositions in a variety of applications. 
     Test Summary 1 
     In this group of tests, the connections used were standard &#34;VAM&#34; single metal-to-metal seal connections with buttress threads. &#34;VAM&#34; is a trademark of Vallourec, a corporation with headquarters in Paris, France, and one of the leading manufacturers of premium connections. Leaks were created on the test sides of the connections by grooves filed into the seals. The connections when made up with API (American Petroleum Institute) modified premium thread compounds, and then they were tested as follows: 
     (a) 27/8 inch tubing, Pressure: 10,000 
     psi nitrogen. Heat cycling: ambient to 320° F. Tension: 200,000 lbs. 
     (b) 31/2 inch casing. Pressure: 10,000 psi hydrostatic 
     (c) 75/8 inch casing. Pressure: 9,000 psi nitrogen. Heat cycling: ambient to 300° F. 
     In all instances, the connections sealed when the anaerobic sealing composition was applied to the crippled side of the connection. The break out torques averaged approximately 150% of make up torques. There was no evidence of galling. 
     Test Summary 2 
     Pipe Size: 75/8 inch 
     Connection types: &#34;VAM&#34; premium connections with metal-to-metal seals and buttress threads. 
     Two pup joints and two end plugs were assembled with three couplings respectively interposed between the pup joints and the end plugs. One of the end plugs would not hold pressure above 4000 psi, preventing the testing of the complete assembly. This connection was further crippled by notches filed into the seal to cause it to leak. The anaerobic sealant composition of the invention was then applied to the thread area, and the connection was made up again and the entire assembly was subjected to heat and pressure cycling for several days. The connection held pressure through the threads for the entire test period, while leaks occurred in several of the healthy connections in the assembly. The maximum pressure was 9000 psi of nitrogen, and the temperature was cycled from ambient to approximately 300° F. 
     Test Summary 3 
     This test used 21/2 inch 8-round thread tubing and was designed to compare the anaerobic sealant composition of the invention with an API modified high pressure thread compound manufactured by Shell Oil Corporation: 
     The sample comprised two threaded pins and a single coupling. One pin contained a machined groove to simulate a field defect. The groove was cut to the root of the thread for the entire length of the thread. The groove was cut 0.060 inches wide at the nose of the pin and tapered to 0.020 inches wide at the end of the thread. 
     The sample was made up to 2,300 ft-lbs. of torque using a light application of API Modified pipe dope manufactured by Shell Oil Corporation. The sample was pressure tested with nitrogen gas and a leak was noted immediately on the grooved end. It was disassembled and additional API Modified was applied to the grooved end to simulate field conditions. The sample was remade to 1,900 ft-lbs. of torque using the same amount of turns used during the initial make up. Internal gas pressure was then applied and at 3,500 psig pipe dope was noted extruding at the machined groove. A leak developed and the internal pressure bled down to zero psig. 
     The sample was disassembled, cleaned, and inspected. The sealant of the invention was applied to the grooved end, while API Modified was applied to the other pin end. The sample was made up to 1,700 ft-lbs. and allowed to cure at ambient temperature (approximately 95° F.) for five hours. Internal gas pressure of 7,500 psig was applied and held for two hours. No leakage was observed. 
     Subsequently, the sample was subjected to 235° F. temperature for one hour. Internal gas pressure of 5,500 psig was applied for one hour while maintaining the elevated temperature and no leakage was observed. The sample was allowed to cool to ambient temperature while maintaining the 5,500 psig internal gas pressure. No leakage was observed. 
     The sample was then disassembled, cleaned and inspected. Torque of 5,772 ft-lbs. was required to break out the pin with the machined groove and 5,382 ft-lbs. of torque was required to break out the API Modified pin end. The grooved pin broke out smoothly and without problems. No galling was observed on either pin end. 
     Test Summary 4 
     Thread Design: 75/8 inch wedge 
     Test (a): This was designed to test a &#34;Teflon&#34; ring as a back-up seal in a known leaker. At 2,500 ft-lbs. of make up torque it leaked at 1,500 psi. At 35,000 ft-lbs. it leaked at 8,000 psi. The inventive composition was applied and the connection was made up to 2,500 ft-lbs. It held 8,000 psi. The break out torque was 14,000 ft-lbs. 
     Test (b): This connection was made up to 35,000 ft-lbs. with API Modified dope and was subjected to a combined tension and internal pressure load of 588,000 lbs. It leaked at 10,000 psi. The inventive composition was applied and under the same conditions, the connection held 13,000 psi. 
     Test (c): This connection was made up with API dope to 40,000 ft-lbs. It leaked at 5,000 psi. In an effort to test performance of the inventive composition under adverse conditions, the box end of the connection was completely filled with 16 lb drilling mud, and the joint was stabbed into the mud. It sealed to 13,000 psi with no adverse effects from the presence of the drilling mud. 
     
         __________________________________________________________________________Test Summary 5Threads/Mat&#39;l   Test/Notes    Results__________________________________________________________________________(a) Using preferred compositionof invention:pipe: 31/2 inch diameter           Made up connection to                         No leaks12.7#/ft-SM2550 approx. 4,000 ft-lbsThreads from a previous           (whereas usual min-test, but still in good           imum torque for con-condition. Pins were           nection is 5,220 ft-lbs).dry-honed with Moly Kote.           Made up connectionCouplings phosphated.           allowed to cure for 2The torque shoulder and           hours. Hydrostatic30° seal area were           test @ 10k psi for 2crippled to thereby           hrs. Connection brokencreate a leak path.           apart:           #11 @ 5,800 ft-lbs.           #12 @ 6,200 ft-lbs.Same as above   Another made up con-                         No Test           nection to check break           out torque after short           cure time: 1 hour. Con-           nection broken apart:           #11 @ 4,500 ft-lbs.           #12 @ 4,500 ft-lbs.Using API modified compound:Same as above   Same as above (long                         #11 leaked           cure time) except:                         @ 3,000 psi           Connection broken                         #12 leaked           apart:        @ 5,000 psi           #11 @ 3,600 ft-lbs.           #12 @ 3,750 ft lbs.(b) Using preferred compositionof invention:same as (a)     Made up connection to                         No leaks           approx. 4,000 ft-lbs.           Allowed to cure for 5           hours. Hydrostatic test           to 10k psi overnight.           Connection broken apart:           #1A @ 6,000 ft-lbs.           #5B @ 6,300 ft-lbs.same as (a)     Another made up connec-                         No test           tion to check break out           torque after short cure           time: 30 min. Connection           broken apart:           #1A @ 4,750 ft-lbs.           #5B @ 4,750 ft-lbs.Using API modified compound:same as above   Same as above (long                         After 15 min.           cure time) except:                         #1A leaked           No information re.                         @ 5,100 psi;           connection broken                         then, #5B           apart.        leaked when                         repressured to                         7,000 psi(c) Using preferred compositionof invention:same as (a)     Made up connection to                         No leaksexcept only     approx. 4,000 ft-lbs.pin #1B was     Allowed to cure forcrippled        20 hours. Gas (N.sub.2)           test @ 7,500 psi for           1 hour.           Then, pressure                         No leaks           removed and connection           heated to 300° F.;           Gas (N.sub.2) test @           10,000 psi for 1/2           hour.           Connections broken apart:           #1B @ 5,700 ft-lbs.           #3B @ 6,300 ft-lbs.Using API modified compound:same as above   Made up connection to                         No leaks           approx. 4,000 ft-lbs.                         @ 5,000 psi           Allowed to cure for                         #1B leaked           20 hours. Hydrostatic                         @ 10,000 psi           test to 10,000 psi(d) Using Composition ofinvention:Pipe: 27/8      Made up connection to                         No Leakinch diameter; 7.7 lbs/ft.;           approx. 3,000 ft-lbs.N80 Treated same as (a)           (optimum torque) gasabove; only one side           (nitrogen) test atcrippled        3,600 psi overnight           Gas pressure increased                         Slight leak;           to 6,500 psi. External                         small steady           tensile load added for                         stream of           total tensile load of                         bubbles coming           approx. 200K lbs. No                         in through           temperature increase                         water in which           yet           assembly immersed.           Assembly heated to 300° F.                         Leak appeared to           (w/hot glycol); pressure                         stop; no more           increased to 8,600 psi;                         bubbles visible           hot cycle maintained           approx. 2 hours.           Assembly cooled by flush-                         Leak reappeared;           ing with cold water to                         small steady stream           approx. 120° F.; pressure                         of bubbles visible           dropped to approx. 6,500                         through water.           psi.           Another hot cycle                         No leak visible           Another hot cycle                         Leak visible again(e) Using Composition ofInvention:Pipe: 27/8 inch diameter           Made up connection to                         No Leaks7.7 lbs/ft; N80 approx. 4,000 ft-lbs.VAM premium connec-           External tensile load:tion; Treated same as           approx. 170,000 lbs;above: only one side           gas pressure (nitrogen)crippled        to 9,500 psi           Temperature raised to                         No Leak visible           approx. 300° F. (hot           glycol); short time           cycles at hot and cold           Assembly cooled with                         Leak appeared;           cold water flush                         small steady                         stream of bubbles           Temp increased for                         No Leak visible           second hot cycle           Assembly cooled for                         Leak visible again;           second cold cycle                         small steady stream           Temp increased for                         No leak visible           third hot cycle           Assembly cooled for                         Leak visible again;           third cold cycle                         small steady stream           Two more hot and cold                         Small pattern of           cycles        leaking__________________________________________________________________________ 
    
     Test Summary 6 
     For these tests, the connections used were VAM-PTS 27/8 inch N80 premium connections. No galling was evident in the connection or on the pin throughout the test. In order to understand the terminology, col. (1) represents the time of day; col. (2) is tensile load created by the internal applied gas pressure (nitrogen); col. (3) is load applied by pulling frame; col. (4) is combined load of cols. (2) and (3); col. (5) reflects heat cycling; and, with respect to col. (6), leaks were recorded in estimated bubbles per minute escaping from a leaking connection and fed into a jar of water through a small diameter tube. 
     
         ______________________________________First Thermocycle:            Test Composition #20 (2)      (3)       (4)     (5)(1)   int. press          tensile load                    comb. load                            temp. (6)time  (LBS)    (LBS)     (LBS)   (°F.)                                  remarks______________________________________10:05 37353    162900    200253   76   no leak10:18 37737    164100    201837  301   no leak10:41 37900    162900    200800  101   no leak11:02 37980    163900    201880  299   no leak11:19 38069    163990    202059  101   120 B.P.M.11:27 38061    163800    201861  306   no leak11:57 38100    163200    201300  108   leak &amp;                                  end of test______________________________________ 
    
     Results: 
     No leak on first 2 complete cycles 
     Small leak on 3rd cold cycle 
     Leak sealed on 3rd hot cycle 
     
         ______________________________________SECOND THERMOCYCLE            TEST COMPOSITION #22 (2)      (3)       (4)     (5)(1)   Int. press          tensile load                    comb. load                            temp. (6)Time  (LBS)    (LBS)     (LBS)   (°F.)                                  remarks______________________________________16:53 13787    150139    163926  80     017:13 43342    155126    198468  312    017:35 45278    159272    204550  288    017:41 45270    159597    204867  281    017:47 38402    152183    190585  96    16017:53 35329    165291    200620  92    16017:58 40500    165157    205657  324    518:02 43491    165443    208934  307    518:11 36955    165539    202494  93    16018:14 35661    166036    201697  96    16018:16 40683    165997    206680  323    018:20 43402    156521    199923  310    018:26 37874    156845    194719  95    18018:28 36512     76235    112747  96    18018:31 35865     3400      39265  97    18018:33 35197     70159    105356  98    18018:35 34478    169513    203991  99    180______________________________________ 
    
     Results: 
     No leak on initial cycle 
     Leak on cold cycles 
     Leak reduced or stopped during hot cycle 
     
         ______________________________________THIRD THERMOCYCLE            TEST COMPOSITION #21 (2)      (3)       (4)(1)   int. press          tensload  comb. load                            (5)   (6)time  (LBS)    (LBS)     (LBS)   temp. remarks______________________________________10:16  1323    134625    135948  297   No Leaks10:18 13604    134281    147885  295   through-out10:23 18873    134376    153249  291   test10:26 18840    134109    152949  29010:30 19162    134223    153385  33010:31 19169    134051    153220  30410:37 17180    134223    151403  10310:40 19021    134242    153263  10510:45 20337    134281    154618  30610:48 21187    133994    155181  31210:54 19680    133765    153445   9911:03 18079    133860    151939  10211:24 17557    134739    152296  10011:27 18830    134090    152920  26611:31 20186    134147    154333  28611:38 18927    133879    152806   9211:42 18124    133994    152118   9711:49 22465    133879    156344  29411:53 23230    133841    157071  29711:59 21464    133918    155382   9912:04 20335    133956    154291  10412:05 20080    180690    200770  10312:14 19350    180289    199639   9912:18 21302    179850    201152  27612:20 21985    180060    202045  28712:26 20622    180213    200835   9812:30 19678    180060    199738  10012:31 19680    141904    161584   9912:32 19586    128663    148249   9912:32 19600     78470     98070   9812:34 19487     78566     98053   9812:36 19367     78699     98066   9712:36 19398     48435     67833   9712:37 19452     2770      22222   97______________________________________ RESULTS: Seal held throughout test.FOURTH TEST     API COMPOUND______________________________________API compound was applied to the test connectionsand it leaked profusely at low pressure. 
    
     Test Summary 7 
     A test downhole was run on actual well on July 6, 1986. This comprised a string of 75/8 inch wedge connection, 1,200 ft in length in the form of a linear at the bottom of a 12,800 ft. well. The pipe made up very smoothly with no problems. The pipe stuck in the hole during the lowering of the string, which necessitated the pulling of the string. This resulted in the unusual opportunity to break the pipe out after more than a week of exposure to downhole conditions. The connection broke out very smoothly, with a minimum of cleaning required as compared to normal conditions using API pipe dopes. The average make up torque was 20,000 ft. lbs, and the average break out torque was 30,000 ft./lbs. There was no evidence of galling. The test can be summarized as having been completely successful. 
     The well is located about 10 miles southwest of Lafayette, La. 
     Drilling rig--Glasscock 73 
     Operation--Davis Oil 
     Connection manufacturer--Tubular Corporation of America, Houston, Tex. 
     While the preferred embodiments of the invention have been disclosed in detail, it should be understood by those skilled in the art that various modifications may be made to those embodiments disclosed without departing from the scope thereof as described in the specification and defined in the appended claims.