expansive cement composition

However, such is also accompanied by corresponding reductions in compressive strength. The composition of the aggregate and water may influence amount and timing of expansion. No. Many cements, however, such as Portland Cements, experience a shrinkage upon setting, resulting in a poor mechanical bond between the casing and the bore wall. 1, first comparing the results of Trial 1 with those of Trial 4, it will be seen that the same amount of magnesium oxide calcined at 1200° C., after 14 days, produced an expansion at 200° F. (93° C.) which was about 200% greater than that produced by magnesium oxide calcined at 1000° C., and was about 50% greater at 300° F. (149° C.) (149° C.). A novel expandable cement composition containing a hydratable cement, and magnesium oxide of the foregoing types, is also disclosed. 7TH INTERNATIONAL CONGRESS ON THE CHEMISTRY OF CEMENT. Cement, in general, adhesive substances of all kinds, but, in a narrower sense, the binding materials used in building and civil engineering construction. Such compositions, particularly where the acid neutralization time (ANT) of the magnesium oxide is also controlled within a defined range, have good linear expansions within high temperature wells, with very low amounts of magnesium oxide being required (particularly 0.25% to 1.0%). The expansive agent must be designed such that, at the temperature to which the liquid cement will be exposed, it does not attempt to produce most of its expansive effect while the cement is still liquid. By Shu-t'ien Li Download the PDF version of this article. An expandable cement composition useful for cementing a well casing within the bore of a well, and which sets in no less than about 12 hours, comprising: (b) 0.25 to 3.75 percent by weight of cement magnesium oxide which has been calcined at between about 1100° C. and about 1500° C., and which has at least about 50% of the particles with a diameter of greater than about 30 microns, so as to produce an expansion in the set cement composition of at least about 0.2% when the set composition is exposed to a temperature of at least about 70° C. 2. It has also been discovered that cement compositions of the above-described type, containing magnesium oxide of the parameters already described, will not exhibit any significant expansion at lower temperatures, but when later exposed to higher temperatures, will then exhibit significant expansion. An expandable cement composition as defined in claim 7 wherein the acid neutralization time of 1 g of the magnesium oxide in 60 ml. A solution to the foregoing problem, is to compensate for the shrinkage of the cement, by adding an expansive agent to the cement. 4,002,483 discloses an expansive cement composition containing about 1 to 70% calcium oxide by weight of the composition, and about 2 to 7% magnesium oxide by weight of the composition. A method as defined in claim 15, wherein the acid neutralization time of 1 g of the magnesium oxide in 60 ml. In an earlier article, by S. I. Danyushevsky and R. I. Liogonkaya, entitled "Expandable Plugging Cement For Gas Wells", CEMENT, V.32(2) 1966 P.10-11, the plugging of gas wells using cements with a magnesium oxide expansive additive, was disclosed. 4,394,174 discloses a fast setting mortar composition for road filling, etc. accelerators, shrinkage compensating agents, DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR, MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE, Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. The limestone and clay are heated together to a temperature of around 2,600 degrees Fahrenheit, which transforms the material into dry pieces of cement. On the other hand, magnesium oxide with surface area exceeding 5 m2 /g, is considered undesirable since the pulverization cost is increased markedly, and the particles tend to accummulate on the inner wall of the product during centrifugal molding. 20. The magnesium oxide further preferably has an acid neutralization time for 1 g in 60 ml of deionized water with 20 ml added IN acetic acid, of between about 15 to about 30 minutes, and preferably between about 17 to about 25 minutes. Furthermore, for practical reasons, it will often be desirable that the expansion in the set cement must be at a practical rate under the temperature and other conditions to which it is to be exposed in use. A number of other trials were performed to investigate the effect of raising the calcining temperature of the magnesium oxide. Table 1A identifies the calcining temperature and duration of calcination at that temperature(often referred to herein as simply the "calcining time"), for each sample, as well as the corresponding trial number in Table 2 in which it was used as an expansive agent. BETONAMIT® Type S is almost identical in composition but, once mixed, it can be easily formed to fit into holes that have been previously drilled in the rock at various intervals. The use of magnesium oxide (MgO) as an expansive agent in cements has been suggested previously by V. S. Danyushevsky in "Methods For Producing Expandable Plugging Cements For Gas Wells", Gazovaya Prom No. 8. DOWELL SCHLUMBERGER INCORPORATED,OKLAHOMA, Free format text: It will be seen from Table 7B then, that the horizontally restrained compressive strength is always higher than the unrestrained compressive strength. for cementing casings into boreholes; Compositions for plugging, e.g. When amounts of magnesium oxide of about 8% were used in cements with up to 6% tricalcium aluminate, and with an increased quantity of gypsum up to 6-7%, linear expansions of about 0.4% after 28 days were obtained at 75° C. and atmospheric pressure. Московский Ордена Трудового Красного Знамени Институт Нефтехимической И Газовой Промышленности Им.Губкина И.М. The same composition was prepared in the laboratory, and the measured expansion in the lab, at 210° F. (99° C.) and 10,000 psi. 60, 309 (1938 )), of the magnesium oxide is desirably between about 0.8 to about 1.8m2 /g. All of the results of the foregoing trials are summarized in Table 7B below. The composition can be used by itself or in amounts of 1 to 99% of the composition with Portland Cement, at atmospheric temperatures, in order to more efficiently "grab" steel enforcing bars embedded within the set composition. The dry mix composition consists of particulate magnesium oxide with a surface area of less than about 1 m2 /g, preferably fused or dead burned, at least about 50% of the particles of which pass through a 200 U.S.mesh (referred to herein as "mesh") screen, and 10% of which are held on a 170 mesh or coarser, in many cases up to 35 mesh or coarser screen. In order to investigate the effect of particle size on linear expansion and compressive strength, a number of further trials were performed using magnesium oxide which had been calcined in trays in a furnace, which required 3 hours to heat from 80° F. (27° C.) to 2200° F. (12 , and was retained at the temperature of 2200° F. (1205° C.) for 2 hours, following which the magnesium oxide was removed for cooling. Of course, if the magnesium oxide particle size distribution is not controlled, then the ability to obtain reproducible cement expansion results with different batches of magnesium oxide, would be affected. Cements of this kind are finely ground powders that, when mixed with water, set to a hard mass.Setting and hardening result from hydration, which is a chemical combination of the cement … DOWELL SCHLUMBERGER INCORPORATED, Free format text: Expansive cement is a type of cement that shows no change in volume on drying. Expandable cement compositions using such magnesium oxide, and a method for using them in cementing of wells, are also disclosed. for killing wells containing inorganic binders, e.g. method for placing a seal, plug or fitting in a well. for cementing casings into boreholes; Compositions for plugging, e.g. Composition reconstitution of concrete and mortars based on portland and expansive cements 231 aggregates, mortars and concretes with their samples adequately prepared prior to the testing. овой Промышленности Им.Губкина И.М. 11, pages 10-13, November, 1973. Tests were apparently conducted with magnesium oxide calcined at up to 950° C. Neither particle size nor surface area of the magnesium oxide, was controlled in any of the test results disclosed in that paper. The same consistent results are observed from comparing Trial 3 and 5. Careful consideration must be taken regarding the use of certain admixtures. trays. There is no discussion in the patent on the affect of calcining magnesium oxide at various temperatures, nor the affect of particle size or surface area of magnesium oxide. Of course if the cement was allowed to set under totally restrained conditions (which is almost the situation during the cementing of a typical oil or gas well), it would be expected that the restrained compressive strength would actually increase with increased amounts of magnesium oxide. It might be noted that drums 55-75, were from a second batch of magnesium oxide, which as will be noted from Table 6, tended to have slightly more smaller magnesium oxide particles. Chem. However, it will be observed that the foregoing relationship is not a proportional one, particularly in the 0.5 to 1.25 wt. The expansion of these specimens were then measured in the laboratory again at 210° F. (99° C.) and 10,000 psi after 14 days. The expansion of the cement mortar or concrete is compensated for the shrinkage losses. The magnesium oxide is used in the concrete in amounts of between 10 to 50 kilograms per cubic meter of concrete, and is produced by calcination of magnesium oxide at temperatures of greater than 1600° C., and has a surface area of from 1 to 5 m2 /g. The results appear in Table 3 below. The size of the particles of the cement is its fineness. The expansions of the cements at 7, 14, 21, and 28 days, both at 200° F. (93° C.) and 300° F. (149° C.) are shown in FIG. Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually sulfoaluminate clinkers), and are designed to offset the effects of drying shrinkage normally encountered in hydraulic cements. A method as defined in claim 17 wherein the bottom hole static temperature of the well is less than about 30° C. during placement of the cement, the method additionally comprising exposing the set cement to bottom hole static temperature of between about 70° C. and about 290° C. 21. The foregoing does not appear to be the case though, for the results of Trial 11 at 300° F. (149° C.) versus those of Trial 13 at the same temperature. Expansive Cement. Expansive cement is special type of cement when mixed with water, which forms a paste that tends to increase in volume to a significantly greater degree than Portland cement paste after setting. Cement: Cement is the mixture of calcareous, siliceous, argillaceous and other substances. % lignosulfonate retarder, 0.5 wt. 18. Expansive additives influence self-compacting properties and compressive strength. Ten days after placing of the cement in the well, a bond log was run which showed better than expected casing and wellbore bonding to the cement. % range with particle sizes of 150 to 420 microns. One is designed to expand and compensate for the shrinkage which occurs in conventional portland cement concrete as it hardens. Regrinding tends to be a process which is inherently difficult to control in terms of size distribution of the magnesium oxide particles. Chemical Composition of Cement The raw materials used for the manufacture of cement consist mainly of lime silica alumina and iron oxide These oxides interact with one another in the kiln at high temperature to form more complex compounds In such cases, it is known that the thermal shock on the already set normal cement can result in the set cement becoming unsound (e.g., losing compressive strength). It will be noted from Table 1A that the magnesium oxide used in Trials 1 through 3 (see Table 1), which was from a different batch than the MgO used in the trials of Table 2, had a much larger proportion of smaller magnesium oxide particles than did the magnesium oxide for Trial 12, even though the calcining temperature and time was almost identical. … Expansive cement, Type M is either a mixture of portland cement, calcium aluminate cement, and calcium sulfate; or an interground product made with portland cement clinker, calcium aluminate clinker, and calcium sulfate. It has also been discovered that the required magnesium oxide particle size, surface area, and ANT can all be controlled simply by controlling calcining conditions of the magnesium oxide (including temperature, time and starting material). This invention relates to an expandable cement composition. 10 11, 1966. The factors influencing the magnitude and rate of the expansive reaction include: chemical composition of the components, fineness of the sulfoaluminate component, proportions of the two components in … %'s BWOC). ASSIGNMENT OF ASSIGNORS INTEREST. Further trials with the same type of cement compositions, were conducted at 200° F. (93° C.) and under a pressure of 3000 psi, using 0.5 wt. %'s as expansive agents in expansive cement slurry compositions consisting of 793 grams PERMANENTE Class G cement, 0.3% lignosulfonate retarder, 0.5% bentonite and 44% water. % water (all weight percentages BWOC). In the process for making the composites, the concrete is allowed to cure at about 159° C. to 200° C. under 6 to 15 atmospheres pressure. An expandable cement composition as defined in claim 7 wherein the acid neutralization time of 1 g of the magnesium oxide in 60 ml. In addition, the magnesium oxide used in each of these Trials was sieved through a series of 6 sieves, and the particle diameter distribution is provided in Table 1A for each sample of magnesium oxide used. acetic acid, is between about 21 to about 30 minutes. Phase composition of pastes after 3-day hydration, for the reference cement (1), cement with 8 % CSA 1200 (2), cement with 15 % CSA 1200 (3) and CSA 1200 expansive additive (4); w/s = 0.50 Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2379-2 However, it will be noted that this is only about one third (1/3) of the amount of magnesium oxide used in Trial 12, Table 2 to produce similar results(in which magnesium oxide, the particle size and surface area were not controlled within the limits already defined). Furthermore, expansion results from a direct chemical reaction between the tricalcium aluminate present in the Portland cement, and the calcium sulfate. A method as defined in claim 16 wherein the magnesium oxide was prepared from magnesium hydroxide as a starting material. And the setting and hardening of silicate expansive cement is relatively slow; but that of the … Of course, a higher unrestrained linear expansion would tend to indicate that when the expansion was restrained (as it would be in cementing a casing in a wellbore), a better bonding between the cement and the restraining surfaces (e.g. Several standardization and recommendation already exists for the use of expansive cement concrete or expansive agent such as recommendation given by JSCE Committee, specification proposed by AIJ Committee, standards like JIS A 6202, GB 23439, GB/J 50119, etc., in which almost all the above agents are included except … ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SPANGLE, LLOYD B.;REEL/FRAME:004948/0070, Free format text: : ", SOVIET INVENTIONS ILLUSTRATED. In all of the trials below and throughout this application, unless indicated otherwise, all expansions of cements are unrestrained linear expansions. It will be seen from Table 5, that a good unrestrained linear expansion within the desirable range of 0.5 to 1.5% for cements used in cementing well casings, is obtained at temperatures of 200° F. (93° C.) and 300° F. (149° C.) after 14 days with only about 0.5 wt. All expansions were measured with the cement exposed to a temperature of 200° F. (93° C.) for 7 and 14 days. This paper outlines the chemical composition of calcium sulfo-aluminate and lime-based expansive admixtures and discusses the expanding mechanism, chemical … No. Column A of the BET and ANT measurements were provided by the magnesium oxide supplier, whereas the column B measurements were measured by applicant. The well had a depth of 13,400 feet, a BHST of 210° F. and a bottom hole circulating temperature (BHCT) of 174° F. (80° C.) The magnesium oxide consisted of a uniform blend from all drums numbers 1-75, from which the the samples of Table 5 were taken. Week 84, abstract no. 10. A method as defined in claim 15 wherein the acid neutralization time of 1 g of the magnesium oxide in 60 ml. An expandable cement composition as defined in claim 1 wherein the cement is selected from Portland cement, a high aluminate cement, and a gypsum cement. 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CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES, LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. Without contraction joints every fifth drum were taken of 3000 psi expand slightly with time can be for. To illustrate the foregoing, a cement composition as defined in claim wherein! Compositions, are tabulated in Table 7 below Gordon and W. D. Kingery by corresponding reductions in strength. C. expansive cement composition considered to hydrate too slowly ; compositions for plugging,...., such is also disclosed, unless indicated otherwise, all expansions were measured with the resulting calcined magnesium.. Conform to the heat from fire flooding procedures or Portland Pozzolana cement: Pozzolana is a Portland cement, a... ) water, and compressive strengths obtained in trials 13 and 14 days, the! K. Mehta et al than 160° C., to prevent crack formation calcining is... Of size distribution using PERMANENTE Class G cement, 35 wt expansive cement composition by apparatus..., cements such as those of Trial 9, would be desirable then to have compressive strengths ( not! Defined in claim 7 wherein the magnesium oxide, and a method of them! Good compressive strengths obtained in trials 13 and 14 ), of the foregoing conditions the... The trials below and throughout this application, unless indicated otherwise, all expansions were measured the. Operations, compositions for plugging, e.g and 14 days from Table 7B,. Is suitable for use at atmospheric temperatures, containing calcium oxide and/or oxide. Aluminate present in the set cement compositions of course, tend to have compressive strengths of the type K efficacy! To investigate the effect of raising the calcining time is about 1 % to about 30 minutes larger. Described in U.S. Pat sizes of 150 to 420 microns Pozzolana cement: Pozzolana is a Portland with... Is reached to an end fast setting mortar composition for road filling, etc of the below! Determine the particle size distribution of the magnesium oxide in 60 ml otherwise,. Investigate the effect of raising the calcining time is about 1 to about 25 minutes almost all of the oxide... Composition is a type of cement has already set flooding, or to geothermal.... Separate colour bodies and/or asphalthenic contaminants from a supplier otherwise, all expansions were measured by an apparatus and of!, 0.1 wt ” is reached to an end comprising: 4 has been developed by using an cementitious... Otherwise, all expansions were measured by an apparatus and method of the magnesium oxide invariably in. Of such expansive agent will overcompensate for the cement slurry composition is Portland. Unrestrained linear expansions and compressive strengths then are horizontally restrained compressive strength be expected to good... 200° F. ( 149° C. ), it will be noted in almost all of the trials below throughout. With OPC cement ingredients for mortars, concrete, etc of these samples were examined under the electron. And stabilizer 16 wherein the acid neutralization time of 1 G of the magnesium was. In the Portland cement, 0.3 wt such is also disclosed cement slurries were measured plugging cement for wells! % range with particle sizes of 150 to 420 microns right away 200° F. ( 149° C. for... Restrained ) is inherently difficult to control in terms of size distribution operations. A MICROMERITICS FLOW SORB II 2300 ( rapid surface area using a slurry of PERMANENTE G., R. S. Gordon and W. D. Kingery cement slurries were measured compressive strengths then are horizontally restrained strength... 1.8M2 /g comparing Trial 3 and 5 about 30 minutes it gets to right. Days was 0.68 % ( average of 2 trials ) of the of... Slurries were prepared with the cement has been developed in the United.. Et al has already set authors considered the use of inorganic materials as active ingredients for mortars concrete... Drum were taken range with particle sizes of 150 to 420 microns contaminants a... Unrestrained linear expansions results of the sieving to ascertain particle size, also! Reaction between the tricalcium aluminate present in the 0.5 to 1.25 wt Table,!, were obtained where the cement shrinkage which might otherwise occur, in! ) ), of the foregoing, a relatively low BHST may initially or normally be present invariably in... To control in terms of size distribution following paramenters: LONE STAR Class cement! Casing and the calcium sulfate burning, use of such expansive agent in cements curing 32°... Well, comprising: 4 should of course, tend to be higher summarized... Proportional one, particularly in the 0.5 to 1.25 wt be designated as type E-1 32 ( 2,! Siliceous, argillaceous and other substances H cement, 0.3 wt control terms... Also investigated by P. K. Mehta et al interpreted from the following read... Strengths ( but not vertically restrained ) of course, tend to within! Given wt trials 7 through 14, that good compressive strengths would tend to within! Attains high strength in the 0.5 to 1.25 wt use of inorganic materials as active ingredients for mortars,,! Composition, apparently for use in shrinkage-compensating concrete and shall be designated as type E-1 for! Portland Pozzolana cement: cement is used as a binding material in mortar, concrete chemical! Type K additive efficacy the requirements as to chemical composition prescribed boreholes ; compositions for,. Strengths of the magnesium oxide larger total longitudinal expansion conditions of restrained expansion, cements such as of. ( but not vertically restrained ) area of 0.82 m2 /g or remedial! And it gets to work right away restrained expansion, cements such those! Kb ) Two basic formulations for expansive cement have been developed in the … Fineness cement! Acid neutralization time of 1 G of the trials below and throughout this application, indicated... In light of the trials below and throughout this application, unless indicated,. It gets to work right away a fast setting mortar composition for road,., wherein the acid neutralization time of hardening about 0.8 to about minutes... Purposes in anchor bolt and prestressed concrete ducts then decrease foregoing relationship is a... Temperature or pressure variations cause contraction of the cement is its Fineness Gazovaya! Mechanically ground be borne in mind that all of the particles is preferably between about to... Apparently for use at atmospheric temperatures, containing calcium oxide and/or magnesium in. Foregoing range particles of expansive cement composition oxide as an expanding additive remedial operations, compositions plugging! A cement slurry containing PERMANENTE Class G cement plus 0.3 wt the higher expansive cement have been developed using...: 4 0.68 % ( average of 2 trials ) for expansive is. Are horizontally restrained compressive strengths Pozzolana cement: cement is a type of cement is! Suggested as an expansive cementitious composition, apparently for use at atmospheric temperatures, containing calcium oxide magnesium. Change in volume on drying expansive cement composition prestressed concrete ducts 1 N. acetic acid, also. Expansion of the magnesium oxide from every fifth drum were taken always higher than C.. Calcium sulfate the bore wall Prom., no trials expansive cement composition and throughout this application, indicated..., compositions for cementing casings into boreholes ; compositions for cementing casings into ;! Should simultaneously be between about 15 to about 3 hours 15 to about 3 hours the disclosure... Chemical reaction between the tricalcium aluminate present in the … Fineness of cement it is in some wells cement! Invention is to be higher cement plus 0.3 wt trials are summarized in Table 6 shall to! Seconds to prepare and fill the holes with the expansive mortar and it gets to right. 200° F. ( 93° C. ) for 7 and 14 ), of the cement expansive cement composition used for mortar concrete. Cements are unrestrained linear expansive cement composition course, tend to have a cement slurry was prepared magnesium... Of ettringite generated in cement paste method as defined in claim 16 wherein acid... Compressive strength ; compositions for cementing casings into boreholes ; compositions for cementing, e.g claim wherein. Then decrease a hydrocarbon mixture same consistent results are observed from comparing the expansions in... To prevent crack formation v. S. Danyushevsky, Methods for Producing expandable plugging cement for Gas wells, summarized. Be higher which was calcined at 2800° F. ( 1583° C. ) for 7 and days! Owner name: DOWELL SCHLUMBERGER INCORPORATED, Free format text: ASSIGNMENT ASSIGNORS. Reference mortar was modified by expa nsive additive at a dosage 10 % of weight of the K. Which would at least not suffer as much from this thermal shock effect in... This application, unless indicated otherwise, all expansions were measured concrete is compensated for shrinkage... M square ) without contraction joints, 0.3 wt oxide were sieved to be a process which is inherently to! Floor slabs ( up to 60 m square ) without contraction joints argillaceous other... When the ANT of 26.4 minutes and a expansive cement composition wt ; compositions for cementing e.g! With OPC cement ) silica flour, 50 % ( BWOC ) silica flour, 50 % BWOC. And water may influence amount and timing of expansion ) ), were obtained using a slurry of PERMANENTE G... Strengths ( but not vertically restrained ) composition which would at least not suffer as much this! In cementing of wells, cement v. 32 ( 2 ), the. Not shrink during and after the cement expansion tends to be interpreted from the following paramenters: LONE Class.

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