Shale Alteration by Water Adsorption ‘Martin E, Chenevert, SPE-AIME, Esso Production Research Co. Introduction Properties of somo argllaceous rocks are known t0 be altered by adsorption of water. Montmorillontic rocks, for example, tend to expand and crumble winen contacted by low-salinity water Quantitative data are available on the behavior and properties of mont- morilonitic sandstones and pure clays, but not for rocks that can be broadly categorized as shales. (A shale can be deseribed as being fine grained, arsil- laceous, highly compacted, and partially dehydrated.) ‘The purpose ofthis work was to observe the behavior and measure the properties of a broad range of shale types—montmorilionitc, illic and chloritic—when exposed to water. Investigators working with clays and montmoril- Ionitic rocks have found that expansion is caused by ‘water or ion adsorption onto the electrically charged surfaces of clays.? Some investigators postulate that fon a molecular scale an “ordering” of the water molecules takes place on the clay, resulting in the water's being “rigid” or “captured”.** The degree of capture (or the extent of total hydration) is best repre- sented by an adsorption isotherm, When the clay is dry it consists of layers that are close together. Ad- sorption produces & net flow of water that causes the layers to separate, thus inducing internal expansive stresses." Hydration reduces the clay's strength'® and density," and alters its electrical resistance.’ Since shales are essentially quartztic-feldspathic rocks that contain clay, it was felt that the mechanism just described would be responsible for most of the property alterations that take place when adsorption occurs. Shales Studied Samples of 50 shales from formations ranging in depth from 300 to 16,000 ft were collected and studied. All shales were restored to their original state of hydra- tion, and samples of 12 shales were preserved at the wellsite and subsequently tested with minimal expostie to weathering. Control samples deliberately exposed to the atmosphere adsorbed water and eventually fragmented. All samples tested adsorbed fresh water (tap water was used) and evidenced physical alteration, It would be inconvenient to present data on all 50 shales. In- stead, results of tests on six shales from as many dif- ferent locations and depths are presented as being typical. Table 1 shows compositions from X-ray analyses of these shales (designated A through F) and gives their locations and depths. Table 1 also shows the weight percent water of each shale when it is in equilibrium with an atmosphere having a. relative humidity of 50 percent. Generally, for shales con- taining an appreciable amount of clay, the weight percent water observed under these conditions. ex- ceeded 3 percent. Shale Adsorptive Potential ‘An adsorption isotherm was obtained by placing a shale in a deacrated, controlled-humidity environment | An adsorptional isotherm technique makes it possible to define quantitatively the hydrational tendencies of any formation, thereby eliminating the cumbersome rock | classification schemes presently used in industry. SEPTEMBER, 1970 141and incrementally changing the humidity at a con- stant temperature. A sample was first ground to 8-10 ‘mesh size and dried overnight at 200°F, Allocations of the sample were then placed in sorption desiceators in which the relative humidity was controlled at values between 10 and 98 percent. The weight of each sample was measured daily, and when equilibrium was reached the weight percent water adsorbed was cal- culated, A desorption isotherm was generated by decreasing the relative humidity in the desiccators incrementally after first hydrating the sample at 98 percent relative humidity. Fig. 1 shows an adsorption desorption isotherm for Shale A. Table 2 shows data forall six shales, including data from two experiments performed on Shale F at high temperatures. Shale F adsorbed slightly higher weight percentages of water at the higher temperatures, but the reasons for this are not known. From the data of Fig. 1 and Table 2, itis clear that for the adsorptive potential of a shale to be specified, equilibrium conditions must be stated. Shale A, for example, has a total adsorptive potential of 3.7 weight percent water starting in equilibrium with a 10 per- cent relative humidity and ending at a 98 percent relative humidity. Starting at 50 percent relative humidity and ending at 98 percent, the adsorptive potential of Shale A is only 2.7 weight percent water over this increment. Note that the incremental adsorp tive potential of this and many other shales tested was highest in the 90 to 98 percent relative humidity range. Density Changes The effect of adsorption (hydration) on the physical appearance of samples of Shale B is shown in Fig. 2. ‘As adsorption progressed the shale expanded, which increased its bulk volume and total weight. If the ‘grain specific gravity (GSG) and weight percent water (WW) are known, bulk specific gravity (BSG) can be calculated as follows: GsG BSG Seay « 1+ G36 ~ (hy ‘0 measure the effect of adsorption on density |esoxenon ‘00 364870369019 RELATIVE HUMIDITY AT 75°F WEIGHT % WATER (ADSORBED OR DESORBED) Fig. 1—Adsorption desorption curves for Shale A. 1132 shale a ‘TABLE 1—SHALE PROPERTIES Weight Parent Ray Analysis Waterst (Garcent an= 05 a Outs 6 a 1 Clete 3 Dolomite 15 45 Gultot Menso Depth Lacation _“(f). SWTeres 18,000 Mite 14 Chloe && 23500 \ Montnotonte 35. Keone 100 S a Quarte32 58 fines Paci Coast 4500 Lovsina 16,000 East Teas 7800 Feldspar 9.0 Catate 04 Montmororite 87.4 Quart 383 35 Fedspar.2 Mites Che 75 fines NaointeS& e—Quar 611 24 Fetdspar 62 ite 26 Chlete 8.4 fines a Quanr03 — Quart 59.5 08 contrat 300 Fetdspar 132 ue ite te } te Chore 104 * TABLE 2—SORPTIVE PROPERTIES OF SHALES Weight Percent ater inEquiur ‘ih @ Relative Hui of: m3 ae 30 a8 32 42 o BS 10 = Desorbed oo Résorbed 75 a ésorbed 75 43 68 Aésorbed 122 5B Adsorbed 210, a Fig. 2—Etfect of adsorption on samples of Shale B. JOURNAL OF PETROLEUM TECHNOLOGY(BSG), tests were made on preserved samples of Shale B. As received, the water content of Shale B was 11 weight percent and its bulk density was 2.27. This shale was placed in fresh water, and within. | hour adsorption decreased its density to 1.62. ‘A series of density measurements made on samples of Shale D, using a standard pycnometer, produced similar results, Twenty-gram allotments of shale chips were first conditioned indifferent, controlled-humidity environments and then divided into two samples each, from which weight percent water and density values were obtained. Fig. 3 shows the close relationship between density and the weight percent water ad- sorbed, again indicating that density reduction is closely associated with adsorption. Field measurements are made of shale densities ‘an effort to predict the occurrence of abnormal- pressure formations. It has been postulated that some thick shale sections deposited and compacted in deep marine environments may have a higher porosity (ower density) than other shales." Exploratory drill= ing is conducted in ancient marine areas, and occa- sionally, after the bit has penetrated thick shale sections, it encounters formations with abnormally high pressures. Changes in density as well as in acoustic and electrical properties of the overlying shales have been measured, so it appears that meas- urement of water content and density as an abnormal- pressure detection technique is well founded. But the Grilling fluids used are generally water-based, and the shale samples used for density measurements are ciceulated to surface by the fluids; during this time, the shale cuttings have ample time to adsorb water and thus lose density In light of the foregoing, it appears that the use of shale density to predict abnormal pressures, although technically feasible, is subject to question from a practical point of view. For shale density to be a useful predictive tool, hydration by contact with drill- ing fluids would have to be controlled, compensated for, or eliminated. Hydrational Strain ‘To measure the strain produced by water adsorption in both unconfined and confined shale samples, strain ‘gauges were attached directly to shale surfaces, and the samples were then immersed in or exposed to ‘water. Linear and radial expansion tests were made, and the degree of anisotropy was measured with one cubical sample. Expansion of Unconfined Shales ‘The effects of hydration on the rate of expansion of five unconfined shales immersed in water at room temperature and pressure are shown in Fig. 4. Ex- pansion was measured perpendicular to the bedding planes. If we compare these results with the data of ‘Table 1, we find that the higher a shale's adsorption potential the more rapidly it expanded. Shale C ex- panded 0.6 percent in about 6 minutes. Shales A and F, with the lowest adsorptive potential, requited 10 hours or moze to approach 0.6 percent expansion. Shale D was omitted from this series of tests since the only samples available were small chips to which strain gauges could not be attached. Te was found in other tests with unconfined samples that expansion is related to weight percent water adsorbed Percent Expansion = (K) (Weight Percent Water Adsorbed) » @ For Shale A, K was found to be 1.32. This value was established by allowing samples of Shale A to adsorb water until a predetermined dimension was reached. ‘The weight of water adsorbed was then determined, ‘This test was not performed on the other shales, but itis felt that to use weight percent water adsorbed to predict expansion, K must be determined for each shale of interest, Expansion of Confined Shales — Linear Adsorption Jn another series of tests, percent expansion was measured as a function of time and linear advance of water through the shale. Samples of Shale A were cut into cylinders 3 in, long. Four strain gauges were attached to the surface of each sample along its axis. Each sample was then coated with wax, except for ‘one end, which was left open for exposure to Water. i . 8 a {4 e “lms Lo & | g I 24 — | , | Esa 5 | & ‘sa geo a} | | BD BUK “GRAIN SPECIFIC GRAVITY 2° ~ o 12 3 4S 6 i y WEIGHT % WATER Fig. 3—Effect of adsorption on density of ‘samples of Shale D. SEPTEMBER. 1970, TIME HouRS Fig. 4—Expansion as a function of duration of adsorption. a3