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RATE 0

MEIVTATI

Nonflscculated Suspensions of Uniform Spheres


As an initial step i n developing a more complete understanding of sedimentation in concentrated suspensions of fine powders, a study is presented of sedimentation in a simple system, under conditions of laminar flow. The effect of concentration o n the rate of fall of uniform well-dispersed spheres is investigated both theoretically and experimentally. Tests with suspensions of tapioca particles in oil provide empirical solutions of functions of concentration left undetermined by the theoretical analysis. Tests with fairly uniform microscopic glass spheres support the conclusions drawn from t h e tests with the larger tapioca particles.

HAROLD H. STEINOUR, Portland Cement Association, Chicago, 111.

H I S article is the first of a series on sedimentation phenomena. The work was planned primarily to develop a better understanding of the settling of fresh portland cement pastes, an occurrence commonly called bleeding. An extensive investigation of this property was made by Powers (16, 17). The present studies were undertaken to resolve some of the questions raised by his analysis. A cement paste is a concentrated, flocculated, aqueous suspension of solid particles, of a wide range of sizes, slowly reactive to water. To develop the theory of its sedimentation beyond the stage to which i t had been advanced, experiments were made with simpler systems. Only the sedimentation of welldispersed uniform spheres is covered in this article, in which the effect of concentration on the rate of settlement is investigated under conditions of laminar flow.
CONDITIONS IN SUSPENSIONS O F UNIFORM SPHERES

At Reynolds numbers, 2rV,p,/q, u p to 0.6 (11) a solid sphere in an infinite expanse of fluid falls a t a uniform velocity given by the Stokes law (16):

I n order to make a general analysis, identical arrangements of the spheres in different suspensions will be assumed. At a given concentration of spheres by volume the problem then becomes one of comparing laminar flows in composite flow spaces having the same shapes. When the sizes of the flow spaces are also the same, as they are when the sphere sizes are the same, the average velocities depend only on the velocity gradients at corresponding points, because equal gradients a t such points in flow spaces of the same sizes and shapes obviously mean identical flows. Accordingly, a suitably defined velocity gradient and a characteristic length or dimension of the flow space are sufficient to fix the average relative velocity of spheres and fluid when only a particular concentration is concerned. Indeed, the velocity must be proportional to the product of the first powers of the gradient and the length, for only this combination of the variables has the dimensions of velocity. Hence, it may be concluded that a t a given concentration the average velocity is proportional to the average velocity gradient or rate of shear a t the sphere surface, and to the average spacing between spheres, At constant concentration this spacing is proportional to sphere radius T . When the volume concentration is changed, the flow space necessarily changes in shape. The spacing between spheres will

Within the given range of Reynolds numbers, the flow around a sphere is laminar, or streamline, and inertial effects are negligible. I n a suspension in which there are many spheres instead of one, the rate of sedimentation is less than the velocity given by the Stokes law. However, if the conditions are such that isolated spheres will fall in accordance with Stokes law, and if the spheres are of uniform size and density and are well distributed throughout the fluid, the rate can be represented by the Stokes velocity multiplied by a term which is a function of concentration only. This is shown by the following study which also partially evaluates the new term; the restrictions that have been stated here regarding the nature of the suspension are assumed throughout the development. The spheres would necessarily all settle at a common constant rate if they were in a stable uniform arrangement and if wall and bottom effects were negligible. I n an actual mixture the distribution of spheres cannot be strictly uniform, but under the best conditions a fixed arrangement and constant velocity are . rather closely maintained. Hence, the fluid space can be assumed to maintain a constant shape within which a steady laminar flow pattern is established. Relative to the spheres the flow velocities increase from zero a t the sphere surfaces to maxima in the intervening regions.

Figure 1.

Fine-Pearl Tapioca Particles before TreatmenL (about 3 X )

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619

also change unless a compensating change is made in the size of the spheres. These changes in the flow space affect the velocity, but since the velocity at any one concentration is always proportional to the rate of shear defined as above, and to the sphere radius, a change in concentration simply alters the constant of this proportionality. Accordingly, the average relative velocity is given by

(4)
where kz = dimensionless pro ortionality constant which expresses ratio o? R / 4 d to q(dv/dn)., at infinite dilution hape factor which is a function of E only, and becomes equal to 1 at infinite dilution Since +g(e) is purely a shape factor, Equation 4 shows that changes in size of flow space caused by changes in E can affect the surface rate of shear, (dvldn),,, directly, only through a possible effect on viscous resistance R. When R is fully evaluated, the only effect of size that will remain undetermined will be that embodied in +I() of Equation 2. Eliminating (duldn) (lv between Equations 2 and 4,

where &(e) = size and shape factor which is a function only of t h e proportion of fluid, e, and reduces to 1 a t infinite dilution.

The ratio & ( E ) / + ~ ( E ) may be replaced by a single function, + ( E ) , which, like its components, becomes equal to unity at infinite dilution. Also, the combination of constants 4kz/kl may be replaced by a single term which can be evaluated from the Stokes law, to which Equation 5 must reduce at infinite dilution. Since the Stokes law in terms of the viscous resistance is

6?r7rV8

(6)

4k2/kl must equal 6, and Equation 5 becomes

'

EFFECT OF CONCENTRATION ON BUOYANCY

10

12

Time, Hundreds of Seconds

Figure 2.

Examples of Sedimentation Curves Obtained for Tapioca in Oil

Fluid friction R equals the motive force, which is the weight of the sphere minus its buoyancy. The buoyancy depends on the gradient of hydrostatic pressure and is therefore affected by the presence of the other spheres. That is, since the spheres all move without acceleration, their entire weight is supported by the fluid, and this means that the hydrostatic pressure developed by a layer of the mixture is determined by the density of the mixture rather than by the density of the liquid alone. Hence, buoyancy is also determined by the density of the mixture. This effect on the buoyancy is recognized in hydrometer practice (II), and the principle has also been applied in some adaptations of the

Since the concentration of solid by volume is ( I - e), + , ( e ) represents a, function of concentration; another effect of concentration i s implicit in (dv/dn).., as will be shown.
0.20

VISCOUS RESISTANCE

E l x = a L I

The rate of shear a t the surface of a sphere, (dv/dn),,, may be evaluated in terms of viscous resistance. This resistance results from viscous forces both normal and tangential to the surface of the sphere. The resultant of the tangential forces is obtained from the fundamental law by which the coefficient of viscosity is commonly defined. As applied to the sphere this is:
-2 R = hq(2) (3) 4rr2 av where 4702 = surface area of sphere, sq. cm. h = dimensionless factor, constant for any given concentration, which corrects for the fact that tangential forces do not all act in line of motion

0.16

*k
Gi

g
0.08

0.12

Because of the constancy of the flow pattern, the resultant of the tangential components of the viscous force maintains a fixed ratio to the resultant of the normal components, a t any given concentration. Thus, a t infinite dilution the resultant tangential force is always twice the normal (16). However, as the concentration is changed, both this ratio and h may change because of the change in shape of the flow space. Hence, a complete expression for the total viscous resistance, or fluid friction, developed by the motion of the sphere is

0 . 0 4

0 . 0 0 0 . 0
0.2
0.4 0.6

0.8

1 .o

E :

Figure 3 . [Q(1--)]'/a

US. E

for Sedimentation of Tapioca in Oil

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol, 36, No. 7


4

3d

p ,

- m)gQ

71.7%

- Pz)gV

This equality reduces to

which, upon substitution from Equation 12, becomes e = ( p , - p z ) / p , - p,). Comparison with Equation 9 shows that pz: = pm, and confirms the previous formulation of the buoyancy as 4/3irrsgp,. Substituting in Equation 12 the value of V given by Equation 11:

I n terms of the Stokes velocity, V,,

Vae2+(e)

(151

APPLICATION OF HYDRAULIC RADIUS

Figure 4.

Log Q/t2 z's. E for Sedimentation of Tapioca in Oil

The function + ( E ) represents effects of both size and shape of flow space. No complete theoretical solution of this function is known but theoretical analyses aimed toward the solution o f this problem were given by Cunningham ( 7 ) and 8moluchowski (20). Recent abstracts of papers not readily obtainable on account of the war show that Burgers (b) has also contributed to this subject. A theoretical study of the effect of the spacing upon axial flow between arrays of parallel cylinders was made by Emersleben (8). A complete theoretical sobtion for spheres is not attempted here, but the effect of size and part of the effect of shapeareevaluated by use of the hydraulic radius; only a residual undeterniined shape factor is left, which remains nearly constant for concentrated suspensions.

Stokes law to suspensions (11, 18) though not always with confidence ( 1 1 ) . That the usage is correct is further shown by the development of Equation 13. Because of the augmented buoyancy the equality between viscous resistance and motive force for a sphere in a suspension is

0.16

0 . 12

4 R = 3MP.3
but,
PI

- 'Pmh
i- E P f l
=

(8)

- Pm

Pa

[(l -

E)

P8

be

Pf)e

(9)

hence

:
y1

0.08

v)

0.04

R=?

7rr3(pS

- m)ge

(10)
0.00
0 . 3 0 . 4 0 . 5
0 . 6
0.7

Substituting this value of R in Equation 7 and solving for V ,

0 . 8

0 . 9

1 . 0

Figure 5.
COMPARISON OF MEASURED VELOCITY AND RELATIVE VELQCITY OF SPHERES Ah-D FLUID

Shape Factor, ' 2 10--1.8E!I--e)

us.

V was defined as the average relative velocity between spheres and fluid whereas the measured velocity is that of the particles relative to a fked horizontal plane, a velocity which will here be represented by Q. The relation between Q and V may be derived by equating the volumes of solid and fluid that move in opposite directions past a unit of horizontal cross section in unit time. That is, (1 - e) Q = E(V - Q), or

The hydraulic radius of a uniform length of conduit may be defined as the flow volume per unit of wetted surface. It h m the dimension of length, is especially suitable, and has long been used, as a general radius term, for conduits of noncircular crosssection. As applied to a suspension, hydraulic radius =
For uniform spheres u = 3 / r and
(1

- e)u
re

(161

eV

(12)

Another expression for the relation between Q and V can be derived by equating the loss in potential energy attending the fall of a sphere and the work done against viscous resistance. That is,

hydraulic radius

3(1
~

- e)

(171

Previously, an T was placed in Equation 2 to represent the relative spacing between spheres at constant concentration. X f

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the hydraulic radius is now used to represent the spacing a t any concentration, the remaining variable factor of Equation 17 must be made explicit in Equation 15 by removal from b(e). That is,

through porous media. For uniform spheres for which u = 3/r, Equation 21 can be expressed in terms of V., as (22) The first experiments of the present investigation were made primarily to determine whether the w,term would be needed for well dispersed (nonffocculated) suspensions of relatively large particles, but they also provided opportunity for a study of .+(E) and e(). These tests were made on suspensions of nearly uniform spherical tapioca particles settling under conditions characterized by low Reynolds numbers.
SEDIMENTATION O F TAPIOCA IN OIL

wher;? @(e) represents those effects of shape that are not evaluated by using the hydraulic radius. When +(e) is treated in this way, Equations 14 and 15 become, respectively,

Since the choice of the hydraulic radius as the spacing factor is an arbitrary procedure, Equation 15 will still be considered, along with Equation 20, in some of the further developments.
SHAPE FACTOR AND w i TERM

As the dilution is increased, Q must approach V , as a limit. Since @/(1 - E) approaches infinity, e() must approach zero; but a t high concentrations O(e) may remain practically constant, and published work indicates that it probably does. Kozeny (12, IS) and Fair and Hatch (9) independently derived equivalent forms of equation for the velocity of viscous flow through granular beds. Fair and Hatch assumed the validity of the hydraulic radius without any additional shape factor. Kozeny did not write in terms of the hydraulic radius but his treatment was equivalent. These authors found reasonable experimental agreement with the equation. Carman (3-6) applied it in tests on many different kinds and shapes of particles and found excellent experimental agreement over a range of porosities from 0.26 t o 0.90. The same form of equation was also found applicable t o flow through wads of textile fibers (83). Powers (I?), starting with the Poiseuille law, developed an equation for the rate of sedimentation or bleeding of concentrated flocculated suspensions of cement and other powders, by using the hydraulic radius and by determining the pressure gradient from the hydrostatic pressure caused by the fall of the particles. This was equivalent to adapting the Kozeny or the Fair and Hatch equation to a sedimentation process. Fair and Hatch had made a similar analysis in adapting their equation t o the flow through an expanded filter bed, in which the sand grains become suspended in upward-flowing wash water. As applied to uniform spheres, those adaptations were equivalent t o Equation 20 except that constants were used instead of e(), and Powers introduced an additional, experimentally derived term, as will be shown. Equation 20 might, therefore, have been developed here by a slight modification of the analysis based on the Poiseuille law. The approach used was adopted instead, in order to analyze conditions a t the individual particles. Although Powers theoretical analysis gave ~ 3 / ( l E ) as the function of E in the rate equation, in order to represent his data he had to subtract a constant, which he called wi, from each E that appeared as an independent factor. This modification was similar to one that Kozeny (I,%) and Carman (4) had also found necessary in a few cases, in permeability tests on clays. Powers final equation in terms, of the symbols used in this article was

Fine-pearl tapioca was dried and soaked in SAE No. 50 lubricating oil under vacuum. Sedimentation tests were made in the same oil a t a series of concentrations. The oil-soaked tapioca grains had a density of4.38 grams per CG. in the surface-dry condition obtained by rolling them on absorbent paper. They were practically uniform spheres about 0.174 em. in diameter. For more than 80% of the grains, variations in diameter did not exceed 10%. Figure 1 shows a representative sample before treatment. The oil had a density of 0.89 gram per cc. and a viscosity of 7.13 poises at 25 C., the controlled laboratory temperature.

Figure 6.

Photomicrograph of Glass Spheres ( X 500)

Isolated black spots in the partialea indioate gas bubbles.

in which the magnitude of toi was dependent upon the powder under test but averaged about 0.28 for portland cements. The numerical constant is the same as Carman (6, 6) found for flow

Most of the tests were made in a 1000-ml. graduated cylinder of the glass-stoppered type, about 62 mm. in diameter. The cylinder, filled to the shoulder with a test mixture, was evacuated and closed. I t was supported manually; first one end and then the other was slowly elevated, and at the same time the cylinder was rotated about the longitudinal axis. This was continued until the mixture appeared uniform; the cylinder was opened to the air after it was finally righted. This method of mixing proved very effective. The better tests showed a practically linear relation between time and amount of settlement throughout the sedimentation, exce t for a slight tapering off a t the finish. Figure 2 illustrates some o r the curves obtained. An approximate determination of the Stokes velocity was made by dro ping single particles centrally into a 62-mm. diameter cylinder &led with the test oil. The average velocity of 152 particles waa 0.1120 cm. per second. By applying the Francis formula (IO) for wall effect, the velocity a t infinite dilution was calculated to be 0.1194cm. per second. The corresponding Reynolds number is 0.0026. The correction of the velocity consisted in mu1 tiplying the experimental value by the factor (1 T / T ) - ~ . ~ where , r and T are the radii of sphere and tube, respectively. No correction for wall effect was made in any of the other sedimentation tests. It was considered that the effect should become rapidly less as the concentration was increased.

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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
and from Equation 18,

Vol. 36, No. 7

The results of sedimentation tests are given in Table I. As the final column showg, all sediments were practically constant in porosity. Information on e() and wi is provided by Figure 3, where [Q(1 - -d)]V: is plotted against e. It is evident that the points up to E = 0.785 are adequately represented by a straight line through the origin. The equation of the line is

e()

1 --d __
E

1O-L82(1-c)

(26)

= 0.123V8

ea

(23)

if the corrected experimental value of 0.1194 cm. per second is assigned to V,. Several conclusions may be drawn from this equation. By comparison with Equation 20 i t indicates that, over a considerable range of high concentrations, the shape factor e() remains practically constant at approximately 0.123. By comparison with Equation 22 it shows that the wi factor which Powers found to be necessary in evaluating the settling rates of flocculated suspensions of particles of microscopic size is not needed for systems of the present type. Finally, it shows that the proportionality constant, 0.123, is somewhat different from the constant 0.10, derived from Powers' equation. Although the data are not so precise but that they could be represented fairly well by a line having a slope based on the factor 0.10, the line would pass to the left of the origin. This is shown by the dashed line of Figure 3 which has been drawn to this slope. If shifted horizontally until it passed through the data, it would indicate a negative value of wi,whereas the values found by Powers were all positive.

Figure 5 is a plot of this Ahape factor against e . The approximate conformity of the factor to 0.123 at the lower values of c illustrates the close agreement between Equations 23 and 24 in that region. Figure 5 indicates, however, that the shape factor remains approximately constant up to E = 0.70 only. The experimental data in Figure 3 show constancy up to e = 0.78 but that limit is indicated by only one experimental point. Other experimental data, to be presented in a later article, support the inference from Figure 5. It appears that for nonflocculated suspensions of spheres the shape factor does not stay constant up to such high values of -d as for beds of particles, for which a limiting value of 0.90 was quoted earlier.
SEDIMENTATIOh OF hlICROSCOPIC GLASS SPHERES IN WATER

TABLE I. SEDIMENTATION TESTS ON TAPIOCA IN OIL


Concn. No. 13" 9 12" 7 21 16a 6 20
5

Pro ortion o f &id, c 0.502 0.508 0.533 0.539 0.559 0.572 0.584 0.592 0.614 0.641 0.665 0.691

X 10' 428 427 427 346: 315,336, 307,336 494,490 474,483 531,538,522 642,657,666 733,746,720 797, 762, 753, 813 749 851, $64, 903,
X48

&, Cm./Sec.,

Velocity,

Av. Velocity, Q X lo5 427 328


492 479 530 655 733 775 867 1088 1194 1588 2095 2260 3315 5955 6120 6870 7160

Settlement per Unit of Initial Ht.


0 IO99

Porosity Sediment 0.454 0.458 0.458 0.463 0.460 0.465 0.463 0.465 0.467 0.464 0.465 0.456 0.464 0.471 0.456 0.487 0.467 0.468
o f

.....

.....

0.150 0.186 0.225 0.245 0.279 0.331 0.374 0.420 0.424 0.490 0.508 0.599 0.792 0.805 0.848 0.861 0.904

.....

.....

.....

.....

3 19 18

1092, 1079, 1094 1242, 1203, 1180,1152 1562, 1600, 1595,1597 2100,2090 2220,2300 3330,3300 5860,6050 6120 6790.6950 6980,7340

......

....

.
a

......

....

cylinder was used.

Test in 92-mm. diameter cylinder; in all other tests a 62-nim. diameter

EMPIRICAL EXPRESSIONS FOR FUNCTIONS OF

I n Figure 3 some of the points a t high values of e fall far below the solid line corresponding to Equation 23. Indeed, since Q cannot become infinite, [&(1 - e ) ] % must become zero at E = 1. An empirical equation which represents all the data, even the limiting velocity at e = 1, is
Q

V8e210-1.82(1-e)

(24)

This equation is based on Figure 4 and was used to place the dotted line in Figure 3. Comparison with Equation 15 shows that it provides the following simple empirical expression for
d e )

:
.+(e)

10-1.82(1-~),

or e - 4 . 1 8 ( 1 - 6 )

(25)

The tests with tapioca appear t o establish the effect of concentration on the sedimentation of uniform spheres which are so large that interfacial phenomena, such as manifest themselves in colloidal systems, are negligible. Ordinary portland cements have average particle diameters of about 10 to 12 microns, as computed from specific surfaces determined by the A.S.T.M. turbidimeter method (1). Only a small fraction of the total weight consists of particles as small as 0.5 micron in diameter. For example, Lea and Nurse ( 1 4 ) reported the following percentages, by weight, of particles smaller than 0.6 micron in diameter in various portland cements: 1.4, 0.5, 0.4, 0.7, 1.0, 0.8, 0.6, 0.4, 1.3. Although such powders thus lie almost wholly outside the conventional colloidal range, they are fine enough to flocculate, to show significant adsorption, and to produce electrokinetic phenomena (62). The important effect of flocculation on sedimentation will be discussed in later articles. The possibility that other surface effects might be capable of modifying the rate of settlement was investigated by making sedimentation tests with fairly uniform glass spheres about 13.5 microns in diameter, designated as glass spheres No. A. The test conditions were not, in general, so satisfactory as in the work with tapioca, because the glass spheres were much less uniform than the tapioca and the quantity was so limited that the tests had to be made on a small scale. However, in the middle range of concentrations the data are believed to be reliable. By sedimentation in water, the spheres were separated from a preparation made by essentially the method of Sklarew (19),a s modified by Sollner ($1). Figure 6 illustrates the quality of the sized preparation. Some of the spheres carried enclosed gas. This caused the average density to be 2.32 instead of 2.5 grams per cc., the density of the solid glass. Because of this gas not all equal-settling particles were strictly the same size. However, a sedimentation analysis in water was made by a special turbidimeter technique ( I ) , using hexametaphosphate as dispersant. Diameters were calculated as though the particles all had the average density. The results are shown in Table 11. They indicate that for about three fourths of the sample the Trariation from the average particle diameter did not exceed 20%. The variation was much greater than for the tapioca particles, but it was believed that segregation would, in general, be prevented by particle hinderance in the suspensions. The specific surface of the sample was obtained by the air permeability method of Lea and Nurse (14) which does not require that the particles all have a common density. The value obtained was 4420 sq. em. per cc., corresponding to an average particle diameter of 13.57 microns. These results are in reasonable agreement with the data of Table 11, which indicate 4520 sq. cm. per cc. and 13.27 microns. By using the diameter of

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TABLE 11. SIZE ANALYSISOF MICROSCOPIC GLASSSPHEIRES A


Diameter, Microns % by Range Variation Weight >21.3 6.7 21.3-19.2 2.1 1.3 19.2-18.1 1.1 1.9 18.1-17.1 1.0 1.2 17.1-16.0 1.1 2.4 16.0-14.9 1.1 4.8 14.9-13.9 1.0 11.6
I . .

Diameter, Miorons Range Variation 13.9-12.8 1.1 12.8-11.7 1.1 11.7-10.7 1.0 10.7- 9.6 1.1 9.0- 8.5 1.0 8.5- 0

$ e &

...

19.7 25.8 18.5 5.2 0.6 0.3

Figure 8, like Figure 4, is a plot of log &/e2 against E , and is therefore a test of Equation 24. The straight line has 8 slope of 1.82, as required by the equation. It appears to be a fair r e p resentation of the data. The points% 6 = 0.85 fall distinctly low, but the trend indicated by the line is sustained by the point at e = 1.0 which is based on the calculated Stokes velocity. The low points at e = 0.85 are less reliable than the others because the suspensions developed diffuse upper boundaries, as dready mentioned.
16

13.57 microns and the limiting Stokes velocity calculated from it and from the average density, the Reynolds number for infinite dilution was calculated t o be 0.0025 a t 27.5' C. Sedimentation tests were made in a straight-walled glass Vial, 20 mm. in internal diameter. T o ensure complete dispersion, a 0.1% ' aqueous solution of sodium hexametaphosphate was used as the fluid medium. The preparations were mixed by slow manual manipulation of the vial somewhat like that adopted with the cylinder of tapioca and oil. Readings of the height of each suspension were taken a t regular time intervals by a micrometer microscope. Enough readings of final heights of sediments were taken to establish that the porosities were essentially constant, as was t o be expected of nonflocculated material. The value of E in these sediments was about 0.38. I n the tests a t the highestfluid contents (at e = 0.85 and 0.80) the upper boundary of $he suspension did not remain sharp during the settlement. At the other concentrations the boundary condition was satisfactory and there appeared t o be no segregation. The temperatures of the suspensions were about 27.5" C. Plots of subsidence of the upper boundary against time were fair approximations t o straight lines a t all fluid contents from E = 0.80 t o 0.65, inclusive. I n Figure 7 the curve for E = 0.70 is typical of the better resUIts. The other curve, for E = 0.55, illustrates an initial irregularity obtained in all tests a t E = 0.60, 0.55, and 0.50. At these fluid contents a steady rate was established only after 10 t o 15 minutes, and then it was distinctly low as compared with expectations based on othkr data. To avoid attaching undue significance t o results obtained from curves exhibiting such irregular phenomena, the rates for these three lowest dilutions, although included in the tabulation of data, were not plotted. The rate data are all presented in Table 1 1 1 .

14

12

9 10
v)

8
E E

+
8
v)

8
7

s
2

2 4
3

10

15 Time, Minutes

20

25

Figure 7. Examples of Sedimentation Curves (Incomplete) Obtained with Aqueous Suspensions of Microscopic Glass Spheres

TABLE 111. SEDIMENTATION TESTS ON MICROSCOPIC GLASS


Fluid Velocity Fluid Velocity Volume e Q, Cm./Sec., X 1 0 6 Volume e Q, Cm./Sec., X 106 0.50 3924, 377" 0.70 2170,2180 0.55 6070,6325 0.75 3100,3080 0.60 994a,1 0 0 0 ' 0.80 4170,4060,4120 0.65 1440, 1445, 1540 0.85 5400,5000,5530 a Test gave abnormal curve of height os. time (Figure 7).

SPHERES -4 IE\' 0.1 yo S O L ~ T I O OF N SODIUM HEXAMETAPHOSPHATE

COMPARISON OF DATA FOR GLASS SPHERES AND TAPIOCA

The average Stokes velocity for the glass spheres was found to be 0.0156 cm. per second when calculated from the average sphere radius determined by the air permeability test, the average sphere density, and the properties of water a t the test temperature of 27.5' C. This value of V , when used in Equation 23 gives results as follows: e Q X 106
0.65 0.70 0.75 1510 2200 3250

It appears from this study that the equations found applicable to the sedimentation of the uniform spherical tapioca particles are also applicable to these smaller glass spheres, which are about the average size of portland cement grains. Evidently no new surface effects large enough t o modify the rate of sedimentation were developed by the reduction in size of sphere. I n drawing these conclusions, the tests at the highest concentrations which developed the peculiarity shown by the curve for e = : 0.55 in Figure 7 were disregarded. They do not appear to be representative of the phenomena to which the theory is t o be applied-namely, the sedimentation of cement pastes. Such pastes, even highly concentrated ones, start settling a t a uniform rate.
SUMMARY

Theoretical considerations show that in nonflocculated suspensions of spheres of uniform size, settling under conditions such that the Stokes law would apply a t infinite dilution, the rate of sedimentation is given by the following equations:

These calculated values of Q are in good agreement with the experimental values shown in Table 111, except that 3250 is a little high, as it apparently should be since Equation 23 has been indicated to hold strictly only up to e = 0.70.

Experiments with sus ension of approximately uniform tapioca particles provide tEe following empirical solutions of the functions of e:

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INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 36, No. 7

where e() is approximately constant a t 0.123 for values of E less than 0.7. Experiments with suspensions of microscopic glass spheres averaging only 0.00136 em. in diameter support the conclusions drawn from the tests with the larger tapioca particles (except for some work a t high concentrations of glass in which uniform rates did not establish themselves until after the sedimentations were well advanced).

Pickett reviewed the applications that are made of fluid mechanics in the theoretical analysis, and L. S. Brown made the photomicrographs. To all of them the w r i h takes this opportunity t o express his thanks and to aoknowledge his indebtednes.
NOMEhC L.4TURE

-1.8

-1.9

-2.0

-2.1

-2.2

-2.3

reciprocal see. (the surface average of derivative of velocity at surface with respeot to the normal to the surface) g = acceleration of gravity, cm./sec.2 h = dimensionleks factor, constant for any given concentration kl,kl = dimensionless constants Q = rate of settlement of top surface of suspension, cm./ sec. r = radius of a sphere, cm. r = radius of a sedimentation tube, em. R = viscous resistance developed by motion of sphere, gram cm./sec.a, (dynes) RT = resultant of the viscous forces acting tangential to the surface of a sphere, gram cm./sec.e, (dynes) p/ = density of a fluid, grams/cc. pn = density of a mixture, grams/cc. pa = density of a solid, grams/cc. p z = density used in computing buoyancy, grams/cc. V = average relative velocity between spheres and fluid, cm./sec. V , = Ti for an isolated sphere, as given by the Stokes law, cm./sec. 20% = dimensionless constant used by Powers (17). e = that part of total volume of suspension that is occupied by liquid, analogous to porosity in beds of particles (at infinite dilution E = 1) +(e), +I() = functions of e only, determined by size and shape of flow space e(), + * ( E ) = functions of e only, detymined solely by shape of flow space q = coefficient of viscosity of a fluid, grams/cm. sec., (poises) u = specific surface of a solid, sq. cm./oc.
5v

(g)

= average rate of shear in fluid at eurface of sphere,

LITERATURE CITED

Figure 8. Logla Q/e us. e for Sedimentation of Microscopic Glass Spheres in 0 . l ~ ~ S o d i u m Hexametaphosphate Solution

At high concentrations, where e() is approximately constant at 0.123, Equation 20 conforms t o a modification of the Kozeny ( l a , I S ) and Fair and Hatch (9) equations, obtained by evaluating the pressure gradient in terms of the hydrostatic pressure produced by the fall of the particles; this was done by the latter authors in treating the problem of flow through expanded filter beds, and by Powers (17) in deriving a n equation for the sedimentation of flocculated pastes of portland cement and othei powders. It is noteworthy, however, that on the basis of Carmans work on flow through porous beds ( 5 , 6 )e ( ~ in ) Equation 20 would be 0.10 instead of 0.123. A significant difference is shown in the effect of concentration on the sedimentation of nonflocculated uniform spheres and on that of the flocculaLed pastes investigated by Powers. To represent his experimental data, Powers found it necessary to subtract a constant, w,, from each E factor; he thus obtained (e - 20,)3/ (1 - e) for the function of E instead of $/(l - E ) . The present work with a much simpler system was undertaken as a first step i n developing the significance of the wz term.
ACKNOWLEDGMENT

Cement, Designation C115-42. Burgers, J. M., Chem. Abstracts., 37, 3652-3 (1943). Carman, P. C., A.S.T.M., Symposium on New Met.hods for Particle Size Determination in Subsieve Range, 1941, 24-35; J. SOC.Chem. I n d . , 58, 1-7T (1939); Tyans. Inst. Chem. Engrs. (London), 16, 168-88 (1938). (4) Carman, P. C., J . A g r . S c i . , 29, 262-73 (1939). ( 5 ) Carman, P. C., J . SOC. Chem. I n d . , 57,225-34T (1938). (6) Carman, P. C., T r a n s . I n s t . Chem. E n g r s . (London), 15, 150-61
(2) (3) (1937).

(1) -4m. SOC. for Testing Materials, Method for Fineness of Portland

(7) Cunningham, E., Proc. Roy. SOC. (London), A83, 357-65 (1910). (8) Emersleben, O., P h y s i k . Z., 26, 601-10 (1925). (9) Fair, G. M., and Hatch, L. P., J. Am. Water W o r k s Assoc., 25,
1551-65 (1933).

(10) (11)
(12) (13) (14) (15)

Francis, A. W., P h y s i c s , 4, 403-6 (1933). Gaudin, A. M., Principles of Mineral Dressing, 1st ed., Chap. 8, New York, McGraw-Hill Book Co., 1939. Kozeny, Josef, Kulturtechniker, 35, 478-86 (1932). Kozeny, Josef, Sitzber. A k a d . Wiss. Wien, 136, IIa, 27t-306
(1927).

Lea, F. M., and Nurse, R. W., J . SOC.Chem. I n d . , 58, 277-83T


(1939).

Page, Leigh, Introduction t o Theoretical Physics, 2nd printing, pp. 239-46, New York, D. Van Nostrand Co., 1928. (16) Powers, T. C., Proc. Am. Concrete Inst., 35,465-88 (1939). (17) Powers, T. C., Research Lab., Portland Cement Assoc., Bull. 2
(1939).

(18) Robinson, C. S., IND. ENQ. CHEM., 18, 869-71 (1926). ENQ. CHEM., , ~ S A L . ED.,6, 152-3 (1934). (19) Sklarew, Samuel, IND.
(20) (21) (22) (23)

These studies on sedimentation Rere undertaken a t the suggestion and with the cooperation of T. C. Powers, who showed helpful interest throughout. The writer was assisted in various phases of the experimental program by Lynn A. Brauer, Richard G. Brusch, Herbert W. Schultz, and Ed\$in M. \Viler. Gerald

Smoluchowski, M. S.,5th Intern. Congr. Mathematicians,


192-201 (1912).

2,

Soher. K., IND. ENG. CEIEM., ANAL.ED.,11,48-9 (1939). Steinour, H. H., unpub. work for Riverside Cement Co. Sullivan, R. R., and Hertel, K. L., in Advances in Colloid Science, 101. I, pp. 37-80, New York, Interscience Publishers, 1942.