PERMEABILITY OF SATURATED SANDS, SOILS AND CLAYS B Y P. C. CARMAN Department of Chemistry, Rondebosch, University of Cape Town IT has long been known that, in any porous medium, the rate of flow of a fluid through the mediuna is proportional to the pressure gradient in the direction offlow(Muskat, 1937). Thus, if Q c.c./sec. are obtained from a column of length L cm., and cross-sectional area A cm.2, when the pressure difference across the column is AP g./cm.2, then u = Q = K~ (D'Arcy's law), (1) where u is the apparent linear rate offlowin cm./sec, and K is a coefficient. It is also generally recognized (Muskat, 1937) that u is inversely proportional to the viscosity of the fluid, -q poises, whence Then Klt which will be called the permeability, depends only on the nature of the bed, and is independent of the fluid, of the pressure gradient, and of the dimensions of the bed. In short, in a bed of rigid particles, the permeability depends only upon the size, shape, and mode of packing of the particles forming the bed. Many attempts have been made to calculate Kx theoretically from these variables. The most widely known and accepted is that of Slichter (1897-8), whose equation for a bed of uniform spherical particles of diameter d cm. can be put in the form, ^ = 10-2f, (3) where Kz is a function of the porosity e, and varies from 84-3 when e = 0-26 to 12-8 when e = 046, these being approximately the extreme limits of e for spheres in regular modes of stacking. The variation in K2 stresses the importance of changes in porosity, and is, indeed, in rough agreement with experimental values. In recent years, the theoretical basis of Slichter's equation has been attacked (Graton & Fraser, 1935; Darapsky, 1912), and, further, it has always suffered from the incon- P. C. CARMAN 263 venience that no guidance is given for an "effective diameter" to be substituted for d when particles are neither uniform nor spherical. In the newer type of treatment (Kozeny, 1927; Carman, 1937, 1938; Kriiger, 1918), size and shape of particle are included by the specific surface, /Socm.2/cm.3 For uniform spheres, 80=6/d, and, conversely, for irregularity of size and shape, one can define, if desired, an effective diameter dm = 6/S0. In Kozeny's equation (Kozeny, 1927; Carman, 1937), or, since ^ = 980 cm./sec.2, and k is found experimentally to be 5-0, 1 9 6 w e3 IA x where the effect of porosity is given by the porosity function, e3/(l — e)2. The derivation of this equation is as follows. In a circular pipe, Poiseuille's law is given by ad* AP /K . 5) u < - s i jz- Now, if, instead of the diameter de, one uses the hydraulic radius m, where _ volume of pipe ~ area of wetted surface' ^' it is seen that m = jde2L + TrdeL = -£, (7) so that w (8) 2 ^ ' In this form the equation becomes roughly applicable to pipes which are not circular in section. Thus, for rectangular and elliptical pipes, if one were to replace k0 for the factor 2-0, 1% would vary as follows: Shape of cross-section Circle Ellipse: (a) major axis = 2 x minor axis (6) major axis = 10 x minor axis Rectangles: (a) width=height, i.e. square (6) width = 2 x height (c) width = 10 x height (d) width is infinite k0 20 2-13 2-45 1-78 1-94 2-65 3-00 More complex shapes fall within the same limits of k0, the majority grouping in the region &0=2-0-2-5. Now, the pore space in a granular 2.64 Permeability of Saturated Sands, Soils and Clays bed may be regarded as a single channel of rather involved shape, but of constant cross-sectional area, namely, eA, where e is the porosity and A is the total area of the cross-section. If the cross-sections of the porespace were divided arbitrarily into simpler shapes, there would be a preponderance of elongated shapes, comparable with rectangles and ellipses, rather than circular, square and triangular shapes. Thus, if equation (8) were to be applicable, one would expect k^ to be nearer 2-5 than to 2-0. It is particularly to be noted that the assumption of a constant fractional free area within a given bed implies a random packing of the particles. In regular modes of packing, as Graton & Fraser (1935) have remarked, there is a large and regular variation of fractional free area from crosssection to cross-section; and the average fractional free area in one direction is different from that in another, so that permeability would vary with the orientation offlowto the structure of the bed. A completely random arrangement, from its very nature, must have the same permeability in all directions, and this is also in accord with experimental observations. The essential part of the Kozeny theory lies in applying equation (8) to granular beds. Once one has assumed that this is feasible, further refinements are readily introduced. First, correction has to be made for the actual length, Le, of the path taken by the fluid as it passes through a bed of thickness L. Second, the actual velocity of the fluid in the porespace will not be u, i.e. the apparent velocity over the total area, A, since the free cross-sectional area is only eA, and, further, it must actually travel a distance Le when appearing to travel a distance L. Thus, the actual velocity will be - -y-. Summarizing these points, one obtains e LJ e L 2-5 774 K ' or and, if one substitutes AP u=Kx —=•, •qL then E =€J where Jfc = 2-5 &\ i JT> . (12) Evaluation of m is readily made, since it is merely the ratio of the P. C. CARMAN 265 pore-space per unit volume of the bed, e, to the surface per unit volume of the bed, S, i-e. m=J (13) Since particle volume per unit volume of the bed is (1 — e), 8 = (l-c)S0, (15) Experiments by the writer (Carman, 1937) have indicated that, on the average, a fluid flows at 45° to the axis of the bed, i.e., to the direction in which flow is measured. This would make LJL — \/2, so that the theoretical value of k is 5-0, in agreement with the value obtained by experiment. EXPERIMENTAL EVIDENCE FOR KOZENY'S EQUATION A great deal of evidence for equation (4) has been collected and discussed elsewhere (Carman, 1937), and the writer has also investigated the equation systematically for variations of viscosity, of particle size, of particle shape, and for mixtures of particles of various sizes and shapes (Carman, 1938). These tests cover a range of porosity from 0-26 to 0-9, which corresponds to a 2000-fold range of the porosity function, e3/( 1 — € ) 2 > the most characteristic feature of Kozeny's equation. A notable point in these investigations has been the constancy of k under all conditions. Theoretically, variations of the order of 20 % might well have occurred, since both JCQ and LJL might be expected to vary with the shape of the pore-space. The actual variation in k is within 5 %, so that, for a given specific surface and porosity, the permeabihty is fixed within this limit of accuracy. The writer has made use of this fact for the converse prooessof determining specific surface from permeability measurements. In the experiments just cited, the least particle size was dm — 89 fi. In a second part, to be published shortly, verification of Kozeny's equation has been extended to particles with an effective diameter, dm = 2-7^. It is sufficient here merely to present a few data to illustrate the method of approach and the agreement obtained. In order to obtain an absolute test of Kozeny's equation in the range dm = 10 fi —100 fi, a powder of spherical glass particles, prepared by the 266 Permeability of Saturated Sands, Soils and Clays method of Sklarew (1934), was divided into three fractions of three different sizes, and each examined microscopically. The size analyses, each based on a count of 1000 particles, are shown in Table I. The total area of 1000 particles is ir'ENd2, and the total volume, £77 TiNd3, so that the specific surface, So, is given by So = y^™ , and the average particle size, dm, by <?m = - V A 7 , . These data were then used to obtain the calcu- lated values of K1 in Table II, where they are compared with "observed" permeabilities. It will be noted that agreement was equally good using both absolute ethyl alcohol and acetone, showing the validity of equation (4). Table I. Size analyses of spherical glass particles Number of particles, N Size range in /1 Average size ,— Fraction in range d VI 2-5 3-5 7-5 5-10 15 10-20 25 20-30 35 30-40 50 40-60 75 60-90 100 90-110 125 110-140 Totals Specific surface, <S0 cm. 2 /cm. 3 Average particle size, dm 38 109 331 404 97 19 2 — 1000 2070 29/x j. Fraction II 103 96 125 426 235 15 — 1000 950 63/i Fraction in 90 261 307 266 76 1000 653 92 M Table II. Permeability of spherical glass particles Material Fraction I Fraction II Fraction III Liquid Acetone Acetone Alcohol Alcohol Acetone Alcohol Acetone Alcohol Viscosity 17 0-00415 0-00415 0-0154 0-0154 0-00415 0-0154 0-00415 0-0154 Porosity 6 0-338 0-360 0-360 0-370 0-390 0-384 0-375 0-392 * i (observed) 4-24 x 10-" 4-98 x 10-« 4-95 x 10-" 5-62 x lO- 8 3 1 9 xlO- 6 3 0 9 x 10-* 6-25 x 10- 6 7-41 x lO- 5 (calculated) 4 0 3 x lO-o 5-18 x l O - 6 5-18 x 10~« 5-82 x 10-« 3-46 x 10- 5 3-23 x 10- 5 6-19 x 10- 5 7-5 xlO~ 5 In the case of small, irregular particles, it is not possible to measure So accurately by examination under the microscope, but, if equation (4 a) is accurate, it should be possible to calculate So for two powders, by measuring Kx for each, and then to calculate Kx for any mixture from the values so obtained. 267 P. C. CARMAN 2 Two quartz powders, tested in this way, gave So=22,500 cm. /cm.3 (or dm = 2-7fj.), and <S0 = 6340 cm.2/cm.3 (or d m =94/i), respectively. When mixed in equal proportions, the calculated specific surface should be £ (22,500+ 6340) = 14,400 cm.2/cm.3 Two tests on the permeability of the mixture gave # , x 10' (observed) 2-32 306 t 0-436 0-456 Kt x 10' (calculated) 2-47 303 In another series of experiments, mixtures of a highly purified grade of kieselguhr, with a porosity e=0-849, were made with samples of the second quartz powder, the porosity of which was 0-47. The values of So, obtained from the permeabilities, were, respectively, 17,200 cm.2/cm.3, (rfm = 3-5/x), and 6340 cm.2/cm.3, so that a mixture containing a fraction, x, by volume of the kieselguhr, should have a specific surface given by So = 6340 x (1 -x) + 17,200z = (6340 +10,770a;) cm.2/cm.3 Table III. Permeabilities of mixtures of kieselguhr and quartz powder (volume fraction of kieselguhr) 000 0-020 0-044 0-123 0-262 0-400 0-495 0-740 0-900 1-00 e porosity 0-470 0-485 0-530 0-607 0-670 0-721 0-751 0-806 0-831 0-849 e»/(l-e)2 0-37 0-43 0-675 1-45 2-76 4-82 6-74 13-9 201 26-6 Kt x 10* (observed) 0181 0-203 0-299 0-462 0-631 0-762 0-895 1-31 1-49 1-76 J j X 11 (calculat 0196 0-282 0-484 0-645 0-83 0-97 1-33 1-53 In Table III, there are given observed values of Klt and the values calculated from these values of So. The two constituents were chosen to provide a wide range of porosity, and the range of the porosity function, es/(l — e)2, is shown in Table III. The agreement between the calculated and the observed values of Kx shows undoubtedly that this function expresses the true relation between porosity and permeability. MODIFICATION OP KOZENY'S EQUATION FOR CLAYS Although, in most cases, experiment is overwhelmingly in favour of Kozeny's theory, this does not appear to be the case for clays. This is well shown by an important series of experiments by Zunker (1932), who investigated the permeabilities of a certain heavy clay soil over a wide 268 Permeability of Saturated Sands, Soils and Clays range of porosities. The data are given in the first two columns of Table IV, and, in the second last column, there is the ratio of Kx to the porosity function, €3/(l —e)2. According to Kozeny's' theory, this should be a constant, but, instead, it is apparent that Kt decreases very much more rapidly than the porosity function. Similar observations have been obtained more recently by Macey (1938), so that the behaviour, in a greater or less degree, seems to be common to all clays. Table IV. Zunker's data on permeabilities of a clay soil , x 10 10 e 9-72 8-94 9-66 7-42 2-89 2-10 1-65 1-23 0-591 0-587 0-582 0-562 0-503 0-479 0-460 0-443 € = e - [0-262 (1-e)] 0-484 0-479 0-472 0-448 0-373 0-342 0-319 0-298 K1 x 1010 x ( l -c)7e* 7-87 7-47 8-52 7-98 5-62 5-20 4-94 4-38 KT x 1O 1 0 x(l-e)Vei3 14-3 13-9 16-1 15-8 13-8 14-3 14-8 14-4 Owing to its great importance with respect to the permeability of soils, this behaviour of clays merits a detailed discussion. The evidence for Kozeny's theory is so strong that it appears reasonable to regard it as the "normal" law of permeability and therefore to seek some cause for the "abnormal" behaviour of clays. A first suggestion, which has been favoured by Terzaghi (1925) and by Macey, is that liquid viscosities in very narrow, capillary passages are higher than normal, and that viscosity increases as the diameter of the capillary decreases. This would give a qualitative explanation of the phenomenon, but does not lend itself to quantitative expression unless the relation between viscosity and capillary size is known. Such changes of viscosity, however, seem to be invalidated by the interesting experimental work of Bastow & Bowden (1935), for these workers have proved that viscosities of simple liquids show no sign of alteration in rectangular channels down to 1/J, in width. A more profitable suggestion was made by Zunker himself and later incorporated by Kozeny (1932) into an extension of his own theory. This was to assume that a film of water is held stationary at the surface of the clay particles, with the result that the effective pore space, in which water is free to flow, is reduced. An indication of the amount of water so held is given by what Zunker calls the "hygroscopicity " of the clay, i.e. the weight of water retained by 100 g. of clay (dry weight) when dried in a desiccator at 20° C. For the clay soil under consideration, the hygroscopicity was 7-53. Since the true density of the fully dried clay was 2'68 g./cm.s, this may be converted more conveniently for our present P. C. CARMAN 3 269 3 purposes to 0-202 cm. of water per 1 cm. of solid volume. The hygroscopicity represents water bound so firmly by the clay that it has a negligible vapour pressure at 20° C, and may therefore be regarded as giving a rough measure, probably on the low side, of the water bound so firmly that it remains stationary when percolation takes place. If the two quantities are equated, the free pore space, when the total pore space is e, must be e1 = [e-0-202 (1—e)], since, in each 1 cm.3 of the bed, there will be (1— e) cm.3 of solid volume, and hence 0-202 (1—e) cm.3 of "hygroscopic water". In modifying his theory, Kozeny (1932) substituted the free pore space «! for the total pore space e in equation (14), obtaining Thus, when one substitutes S = (l — e) So, the modified equation becomes and the ratio of Kz to the new porosity function e13/(l—e)2 should be constant. Actually, to obtain constancy, as shown in Table IV, it was necessary to assume that the volume of the stationary film was 1-3 times that of the hygroscopic water, so that the expression for €x became [e - 0-262 (1 —e)]. As pointed out above, this is quite reasonable, and leaves unaffected the main fact that the two quantities are comparable. The average value of Kx x (1 — e)2/ei3 in the last column of Table IV is 14-7 x 10-10, and, according to equation (17), this is equal to gjkS02 or 196//S02, whence &0 = 3-65 x 105 cm.2/cm.3 and the effective particle size is dm = 0-164/*. It is thus possible to calculate the thickness of the stationary layer, for every cm.3 of solid volume has a surface, 3-65 x 105 cm.2, and 0-262 cm.3 of water in the stationary layer. The average thickness of the layer, 8, is thereby 7-2 x 10-' cm., i.e. 72 A., or about thirty molecular diameters. At first sight this appears rather excessive, but, in the past, layers of 1000 and 3000 A. have been postulated to explain the plasticity of clays (Houwink, 1937). Although such excessive thicknesses are no longer considered probable, Mattson (1931) has shown that, when water is added to a dry clay soil, there is a definite heat of adsorption until the amount of water corresponds to a film of the order of 40 A. in thickness. Further additions involve no further heat change. This is at least of the same order as 8. Exactly in what form the water is retained is still not quite certain, since it is difficult to conceive of an adsorbed film exceeding 10 A. The 270 Permeability of Saturated Sands, Soils and Clays more recent advances in the structure of clay minerals may possibly clear up this matter. Clay minerals are characterized by a layer structure in which there is a very strong resistance to rupture across the layers, but very weak forces holding the layers together. It is this which accounts for the typical shape of clay particles, namely, laminae in which the length and breadth greatly exceed the thickness. The most typical mineral in soil clays is beidellite (Marshall, 1936), which, as has been proved by Hofmann et al. (1934), is capable of a very large and indefinite degree of hydration between the layers, accompanied by a uni-directional expansion at right angles to the layers. The following visualization of Kozeny's modified theory seems therefore a reasonable one. One may imagine 1 cm.3 of the clay soil completely water free. The porosity is e, and the particle surface, therefore, S=(l—e)S0. Since the particles are very thin laminae, this surface will be represented by the two flat sides of each laminae, for the contribution of the edges will be negligible. Water is next admitted to fill the pore space. Part of this is adsorbed strongly, while another part, several times greater, will hydrate the clay and cause the laminae to increase considerably in thickness. This swelling, together with the adsorbed layer, corresponds to a reduction in the effective pore space. Further, since an increase in thickness will not affect the flat surfaces of the laminae, the value of S will remain practically unchanged, i.e. it will still be equal to So (1 -e), where So is the specific surface of the unhydrated clay. In other words, in transforming from equation (14) to equation (16), Kozeny is justified in assuming that the effective pore space is reduced from e to elt while the value of S suffers no modification. This viewpoint cannot be considered unless it can first be shown that the amount of swelling in each layer falls within reasonable limits. If the average laminar thickness is t cm., the specific surface So is equal to 2/t, and, conversely, t is equal to 2/S0, i.e. 0-55 x 10"5 cm., or 550 A. Assuming a spacing of 12 A. between layers for the unhydrated clay, this gives the average number of layers in a lamina as 45-5. Now suppose the whole of the water represented by the "stationary film thickness", S, is used for hydration and swelling. Then, since this film is present on both sides of each lamina, the amount of swelling in each layer is 28/45-5, i.e. 3-2 A., a value well within the limits suggested by the work of Hofmann et al. Thus, a sample of montmorillonite, which swelled in water till the spacing between layers was 19-6 A., gave a spacing of only 9-6 A. on drying at 350° C. It is interesting to note that Mattson calculated his value of 40 A. for the "adsorption film" by assuming /S0 = l-2xl0 6 cm. 2 /cm. 3 . If one P. C. CARMAN 271 carries out a similar calculation to the above, assuming the water is not adsorbed but used for hydration, the swelling in each layer amounts to 5-8 A. DATA OF TERZAGHI ON PERMEABILITY OF CLAYS Apart from the data of Zunker, the only published data appear to be some measurements made by Terzaghi (1925), which are printed as a graph of rather small dimensions. The data given in Table V were read from an enlargement of this. These figures were read from experimental points, and not from the curves drawn through them, except in the case of the highest permeability and porosity for each clay. This last reading was justified, since, according to the text, the curves were drawn to pass through experimental points which lay outside the published graph, and which therefore represented higher porosities and permeabilities than any reproduced in Table V. The values of K± were calculated from Terzaghi's permeability coefficients on the assumption that the viscosity of the water corresponded to a temperature of 10° C. A point worth noting is that Terzaghi proved the validity of equation (1) (D'Arcy's law) for clays, since he obtained consistent permeabilities on varying both the thickness of the clay beds and the pressure gradient across them. Table V. Terzaghi's data on permeability of clays Clay A B C K, x 1010 2-4 101 0-35 0-21 013 005 2-4 0-62 0-35 0-24 2-4 1-35 0-51 0-40 007 Kj x 1010 e2 x (I-*) 2 /* 3 0-56 0-36 2-65 0-287 0-51 1-83 0-214 105 0-46 0-188 0-76 0-442 0-56 0-425 0163 0-27 0-405 0134 1-90 0-369 0-593 0-98 0-262 0-524 0-70 0-225 0-50 0-55 0-203 0-486 0-287 0-42 10-9 0-238 9-4 0-38 5-8 0-186 0-338 5-4 0170 0-325 1-6 0119 0-284 €t for clay A = e-0-455(l-e) e t for clay B = e-0-55(l-e) «i for clay C = e-0-23(l-c) € AjXll x (1 -e) 10-0 10-2 10-4 9-8 9-9 7-4 7-8 7-9 7-7 7-7 34 38 35 37 21 As shown in Table V, Terzaghi's data conform very well to Kozeny's modified theory, except, in the case of clays A and C, for permeabilities so small that their accuracy was doubtful, both in the original measurement and in the writer's attempt to read the plotted points from Terzaghi's graph. Journ. Agrio. Sci. xxix 18 272 Permeability of Saturated Sands, Soils and Clays The values of So for these three clays, calculated from the quantities in the last column of Table V, are, respectively, 44 x 105 cm.2/cm.s for clay A, 5-0 x 105 cm.2/cm.3 for clay B, and 2-35 x 105 cm.2/cm.3 for clay C. The corresponding values of 8 are, therefore, 103, 110 and 99 A. If one carries out a calculation for the "average amount of swelling per layer", similar to that given for Zunker's clay soil, the values reached are 5-5 A. for clay A, 6-6 A. for clay B, and 2-8 A. for clay C. It is to be noted that clays A and B fall into a different class from clay C, and that the latter is in the same class as Zunker's clay soil. This is in accord with their nature, for, whereas clays A and B •were pure plastic clays, clay C was little more than a "sandy mud", containing 59-1 % of sand, and Zunker's substance was a soil containing 51-8 % of particles over 2/x in diameter. The calculation of "average swelling per layer" is based on the assumption that the material is a pure clay, and it is undoubtedly true that, were it possible to make allowance for silica particles, and to calculate on the clay alone, the average swelling per layer would be of the same order as for the plastic clays. A distinctive feature of Kozeny's theory is that the permeability becomes zero while the porosity has still quite a considerable value, namely, e = 0-207 for Zunker's clay soil, and e = 0-313, e = 0-355 and e = 0-187, respectively, for clays A, B and C. This is not brought out very well by Zunker's results, but Terzaghi's data show clearly how rapidly the permeability falls toward zero as the limiting porosity is approached. SUMMARY It is shown that the permeability of a water-saturated sand or fine powder can be calculated with considerable accuracy, if the porosity and the specific surface are known. In particular, the Kozeny theory here discussed leads to a very useful relationship between permeability and porosity. It is shown that clays do not conform to the theory in its simple form, but that it may be modified to give a satisfactory representation of the data available. The physical grounds for this modified theory are discussed in some detail, and it is shown that, while it is open to criticism, it is at least in harmony with our present knowledge of clays. An important deduction which follows from the modified theory is that clays may have zero permeability at quite considerable porosities, e.g. at e = 0-207 for a clay soil, and e = 0-355 for a plastic clay. P. C. CARMAN 273 REFERENCES BASTOW, S. H. & BOWDEN, F. P. (1935). Proc. roy. Soc. A, 151, 220. CABMAN, P. C. (1937). Trans. Instn chem. Engrs, 15, 150. (1938). J. Soc. chem. Ind., Lond., 57, 225 T. DARAPSKY, A. (1912). Z. Math. Phys. 60, 170. GRATON, L. C. & FRASER, H. J. (1935). J. Oeol. 43, 785. HOFMANN, U., ENDELL, K. & WILM, D. (1934). Z. angew. Chem. 47, 539. HOWINK, R. (1937). Elasticity, Plasticity and Structure of Matter, pp. 333 et seq. Cambridge. KOZENY, J. (1927). S.B. Akad. Wiss. Wien, 136a, 271. (1932). Kulturtechniker. 35, 478. KRTJGER, E. (1918). Int. Mitt. Bodenk. 8, 105. MACEY, A. (1938). Private communication. MARSHAT.T,, C. E. (1936). Sci. Progr. 30, 422. MATTSON, S. (1931). Soil Sci. 33, 301. MUSKAT, M. (1937). Flow of Homogeneous Fluids through Porous Media, pp. 55 et seq. New York. SKLAREW, S. (1934). Industr. Engng Chem. (Anal, ed.), 6, 152. SOCHTER, C. (1897-8). Rep. U.S. geol. Surv. 2, 305. TERZAGHI, C. (1925). Engng News Bee. 95, 832. ZTJNKER, F. (1932). Z. PflErnahr. Dung. A, 25, 1. (Received 8 August 1938) 18-2
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