Powder Technology, 37 (1984) 705 - 17 6 105

CAPILLARY FORCES - MODELING AND APPLICATION IN PARTICULATE TECHNOLOGY

H-Schubert
Bergakademie Freiberq
GDR 9200 Freiberg, German Democratic Republic-

Abstract
Properties and behaviour of solid particulate systems can be substan-
tially controlled by capillary forces, above all,their flow behaviour,
agglomeration and moisture retention_ In this paper, at first the
capillary binding forces in dependence on the essential variables are
briefly discussed, after this the liquid retention in bulk materials
and strength models for moist particulate systems. Further on, the
modeling of the flow properties of moist bulk materials and the pel-
letization of granular materials are dealt with,
São tratados

Introduction
Properties and behaviour of particulate systems in nature and techno-
logy can be substantially controlled by capillary forces. Within the
scope of the symposium, this paper is exclusively concerned with par-
ticulate solids_ Here, capillary forces can play an important role or
may even be decisive for the flow behaviour of fine bulk materials,
the agglomeration of granular materials, and the moisture retention in
particulate systems_

In order to characterize the capillary forces generated by liquid

bridges in comparison with other interaction forces between two par-
ticles, figure 1 shows a representation given by Rumpf Ill_
Capillary binding force of a liquid bridge
If a liquid of low viscosity forms a bridge between two particles
(figure 2), a force FH acts between them consisting of two components,
the surface tension force FR, and a force Fp due to the difference of
the pressure outside and inside the bridge:
FH = FR + F (1)
P
Nhile the surface tension force FR always brings about an attraction,
the capillary pressure pk

@ Elsevier SequoiafPrinted in The Netherlands

106

a b

0,r 1 10 foopmlooo 10-3 10-P 10-y lpm 10

d- dr -
Model_~~~=O_72-10-3N/un;
4=O"

a,= 0.4nm

Figure I Adhesion forces Iv. d.WuaZs-, eZectrostatic and capiZZcny

forces1 betieen
al smooth sphere and smooth plate,
bl rough sphere and smooth pZate,
contact distance a = a = 0-a nm
(data of Rumpf CIII. O

pk = alq(I/RI + I/R21 (2)

surface tension of the liquid

;1g
1’ R2 principal radii of the curvature of the 1 iqui d surface
can only contribute a positive component to the adhesion force, if it
produces a pressure deficiency within the bridge. For spheres of equal
size, the adhesion force FH is given by:

FH = qg d f (ar, 0, a/d) (3)

CL bridge angle
0 contact angle

The adhesion forces between equal spheres, unequal spheres, and also
for other two-parti cl e geometries have been calculated, both on the
basis of a circular approximation and for an exact liquid-profile des-
cription of the bridge (see e.g. 12-101). Moreover, results of calcu-
1ations are available which take into account the influence of gravity
[8]. However. this influence may be neglected for particle sizes
d < 1 mm [2,10]. It has also been found out, that the shape of bridges
between irregularly shaped particles can often be interpreted as being
rotation-symmetrical-in good approximation C21, Further on, there
are some comparisons between experimentally measured adhesion forces
and calculated values (see e-g_ [5,8,9,11])_
 107

F+Lgz.+re
2 Liquid bridge between two sphe_KcaZ pari5cZes _

Because it is impossible to derive explicit analytical formulas, a

representation of the results in diagrams is advantageous_ They are
meanwhile avai 1 able for a areat number of two-particle geometn es _ The
representation of the rel a%i onships in a dimension1 ess form with an
adequate choice of the parameters is preferable. The most comprehensive
publication of this kind is the book by Helmar Schubert, published re-
cently t lOI_

Liqui d retention in a bulk materi al

A bulk material has a void space, existing as a branched polymorphic
capillary system in dependence on the particle size distribution, the
shape distribution and the structure of packing.

!*Jhen a bulk material is in contact with moist air, water vapour is ap-
preciably adsorbed and forms adsorption layers. If, however, the humI-
di ty approaches saturation (for bulk materials in the range cf about
P/PC = 0.6 - 0.85, p - partial pressure, p - vaoour pressure), then
cap1 llary condensation will occur and mois e ure &ll be oresent mainlv
in the form of liquid bridges at the contact points betkseen the part:-
cles. Such a liquid bridge is stable if its vapour pressure equals the
partial pressure of the water vapour in the surrounding air, i _e. when

& = exp [- .g] (4)

molecular weight of water

M\4water density
E gas constant
T absolute temperature

According to that, with increasing relative humidity liquid bridqes

will first form at points, where equation (4) can be fullfilled,-i.e.
where neighbouring particles or adsorption I ayers are in a direct con-
tact_ At points where a > 0, 1 iquid bridges can only exist at corres-
pondi ngly higher rel ati ve humidities, or these points are even incaoa-
ble of forming liquid bridges on the-basis of capillary condensation_

Considering the moisture of a bulk material independently of its origin,

108

it can be generally said, that a small quantity of liquid saturation S

(saturation S is the relation between void volume occupied by the
liquid and the total void volume) causes the formation of bridges
between the individual particles (figure 3a). Here, the liquid bridges
co-exist with adsorbed water 1 ayers , but their contribution to the
moisture content is usually much greater. This region is called the
pendular state (figure 3a). By increasing the amount of liquid, we
first get the funicular state (figure 3b) , where both 1 iqui d bridges
and pores filled with liquid are present, and then the capi 1 lary state
(figure 3c), where the pores are completely filled. The capillary
pressure p is decisive for the liquid retention. For a given parti-
culate sys k em, it depends on the 1 iqui d saturation S according to a
curve shown schematically in figure 4 (see e.g. [4,14-191)_ There is a
pronounced difference between the curve trends for drainage and imbi-
bition (capillary hysteresis 19,10,201) _

F?cgure 3 States of Ziqzcid bonding in a buZk materiat:

al pendu_.tar state,
bi fwzicuZar state,
cl capiZZary state.

Figure 4 Capi ZZary pressure pk as a function of the Ziquid satma-

tion S.
 109

In order to compare the capi 1 lary pressures in different particulate

systems and thus their ability for liquid retention, the definition
of an average or characteristic value is recommendable. For this,
predominantly the so-called entry capillary pressure p (entry
suction pressure) is used (figure 4) 14,161, that is g!&n for ade-
quately wettable materi al s by :

_l-& o19
Pk,E = a E 5 (5)

dST = 6 Vp/Ap SAUTER-diameter

volume or surface of the particles, respectively_
vPy AP
where a = 6 - 8 for packs of particles with a narrow size range (see
e-g. [4,16,21,22]) and a = 1.9 - 14-5 for wider particle size distri-
buti ons _

Strength models for particle beds and agglomerates

These models have been primarily derived for the tensile strength_ For
this, a number of -partly far-reaching- assumptions have to be made
(see e.g. [4,9,X-301)_
Two basic models can be distinguished:
a. The bondings are transmitted by liquid bridges at the contact
points of the particles.
b. The void space is filled with a wetting liquid of low viscosity_

In the first case and for equal-sized spheres the model derivation
yields for the tensile strength aZ:

1-E FH (6)
aZ=ET

mean adhesion force transmitted at a contact point_

FH
Even if the prerequisites on which the derivation of equation (6) is
based are approximately met, a difficult problem remains, to find an
appropriate expression for the mean adhesion force FH as a function of
the 1 iquid saturation _ Here, we do not consider the case that 1 iquid
bridges hcve not formed yet, but adsorption 1 ayers already exist and
influence the interaction forces in the humidity range p/pg < 0.5 t121.
With,increasing moisture, liquid bridges develop more and more in
dependence on the material properties and the contact geometries above
P/PO = 0.6 - 0.85 and existing bridges are filled up_ Strength models
for low saturations-should reflect these facts. But up to now, no ade-
quate solution is known.

Further difficulties arise when the prerequisites with regard to the

uniform particle size and shape are no more satisfied_ The problem in
question is here the same as in the whole particulate technology_
Quantitative model statements are restricted -in some cases consider-
ably- by the fact, that it has not yet been possible to take sufficient-
ly into account the characteristics of the particle size distribution
and the shape distribution C36,37 1.
110

In order to make a comparison between the tensile strengths calcula-

ted according to equation (6) and test data with moist agglomerates of
a relatively narrow particle size distribution, Helmar Schubert [9]
assumed a constant liquid distribution on the bridges. Further on, he
used the relative distance a/d as adaptation parameter between theore-
tical and experimental data.

If the void space is completely filled with liquid, the interfacial

forces exist only at the surface of the agglomerates and give rise to
binding forces. In the range of high amounts of saturation S, for the
tensile strength oz is valid:

oz = s pk
where the capillary pressure p is a function of the saturation (see
also figure 4) and we have to &-lstinguish between the cases drainage
and imbi bi tion. For drainage the entry suction pressure pk according
to equation (5) provides an approximation for the tensile SErength. In
the funi cul ar state, both bridge bonding and bonding caused by regions
filled with liquid contribute to the strength according to their pro-
portions oiJb and (S pk)’ 12,9,11,311.

In figure 5 tensile strengths of limestone agglomerates calculated and

measured b-y Helmar Schubert are compared [2,9].

1.6 PkGPiffavP&!%,,E
Nkn? l

1.4 0 cr, Tensile

Strength
_

1.2--\
* m-

z 08.-

-0 0.2 0.4 0.6 0.8 1.0

Saturation S

F7zg7.Pe 5 CaZcuZated (soZid cuzzel and measuzzed tensiZe strengths oz

as we22 as measured eapiZ2~ pressures pk of moist aggZo-
merates, consisting of Ernestone pozticZes (mean particZe
size 71 p, E = 0.4151, as a function of the saturation in
the case of imbZbition (data of HeZmar Schubert C2jl.

Modeling of the flow properties of moist bulk materials

In recent years many investigations have been focused on the flow
properties of bul k materials _ Therefore, adequate theoreti cal know1edge
 111

and corresponding experimental methods based on the continuum mecha-

nics are largely available for
the design of bunkers and silos (see
e.g. 132-343). Now, however , one of the most important problems is, to
explain the macro-behaviour of a bulk material as a result of the
interactions between the individual particles. At the present state
of development, the aim can only consist in the derivation of relat-
ively simple equations which reflect the relations between the flow
or strength properties and the main variables. In order to evaluate
the unconfined yield strength bc of a bulk material as a function of
the essential variables in the pendular state, it is presupposed that
the yield locus is given by a straight line (figure 6)_ In this case
we obtain with the help of the flow criterion by Colomb/Mohr C33,391:

Cos pi sin fJi

uC = 2 Tc 1 - sin I$~ = 2 aZ 1 - sin di (8)

For a known internal angle of friction r$- a relationship between the

unconfined yield strength oc and the tenzile strenath az can be ob-
tained when equation (6) is substituted into equation (8) :
sin pi FH
(Tc = zc!+ (9)
l-Sln@i -j-z

FQqre 6 YieZd Zoos.

The further model development is based on the following assumptions

125,26,271:
a. compl ete wetting,
b. to derive the relationship between the bridge angle and the moist-
ure content XV = m -/ms (m - water mass, m - solid mass), the
curvature of he fblee liqhlid surface is nealected,

Under the prerequisites taken (equal sized spheres, 0 = Cl), the adhe-
sion force at an individual particle contact is given by:
With that fo’% lows from equation (9) :

sin +Ji
8.25(1 - E) (510
ac =
~ ’ - sin pi d
(‘11)

Ps - solid density
n 1 - 1 iquid density.

The entry suction pressure p according to equation (5) with a = 8

proves to be suitable for th&‘Eharacterization of the mean capillary
pressure in the liquid bridges 125,26,271. This can be explained by
the fact, that in the pendular state the new formation of bridqes and
the filling-up of existing ones occur parallel. !*lith equation (5) we
obtain from equation (la) :

sin ai
B-25(1 - E)(Z - E)
c”= = .- % 1 2 xw (12)
1 - sin fJi d
EL.&

In the case of a real bulk material, d must be substituted by a char-

acteristic mean value of the particle size distribution. !Jith narrow
size distributions the median value is appropriate, for wider ones the
TER-di ameter dST_

According to equation [ 12) the unconfined yield strenght of a moist

bulk nateria’B depends on the particle size d, porositv E, internal
angle of friction $-, and lastbut not least on the moistire content X
Rith fine materials’this moisture can be a function of the relativ!.
humidit:! ogling to adsorption, the range of capillary condensation at
the particle contacts only being of interest. The adhesion forces of
these condensed liquid bridges can be strength-determining.

By modif:Gng known equations C353, the following relationshio between

the porosity E, the major principal stress d1 and the consolfdation
stress ~~~59 = ~~(~-0.5) can be obtained:
n
1- r_=_=_
%ch
p‘5

density
1
2 I 1
_

“i/m
3
(13)

%ch - bu’Ek n - exponent

The and n can be determined by means of the

results of us, we obtain for the flow function ff,
according to Jenike C321:

(14)
 113

With lower compressibility of the bulk material, n -C< 1 is valid, so

that a rough estimation of the flow behaviour is given by:

0.057 ~3~ (1 - sin 9;) d

I .
ffp (15)
sin @j V(P~/PJ) Xw
Olg

12
kPa
10

0
0 2 4 6 8 10 kh 12
6 c,m --
The test results for the comparison with the model were obtained by
the application of a Jenike shear cell with dolomite, limestone, glass
sand, coal, and various potash salts. The test data and the calculated
values are plotted in figure 7 C26,273. Figure 8 shows measured and
calculated ff -values as a function of the moisture content for a
glass sand (16%500 urn) and a potash salt KC1 98 (crvstatlization
product with 98% KC1 , 40-400 urn) 1381. In considerat>on of the model
assumptions on the one hand and the differing properties of the bulk
materials tested on the other hand, the validity of the model state-
ments can be characterized as quite satisfactory according to the
results available up to now.

Agglomeration of granular materials by capillary forces

In technology the controlled utilization of capillary forces is used
in pelletization and partly for selective flocculation.

For characterizing the main parameters which influence the strength

of green pellets, we can refer to the statements made. Thus, qualita-
tively similar curves are valid for the strength as a function of the
amount of saturation 5 as they are represented in figure 5. According
to it, the capillary state is most advantageous. This is also in
agreement with the results of strength tests (see e.g. [40-421). The
influence of the particle size of the material to be pelletized can
be evaluated from equation (7) when the entry capillary oressure is
introduced for the capillary pressure. Therefore, a minimum fineness
is required to ensure a minimum strength. The fineness required to a
given apnlication is, of course, also influenced by other material
proper-t-i&s C40,43,443, From experience, the soecific surface of iron
ores should be at least 150 to 200 m2/kg (Blaine-test!) [40,42,451.
If the specific surface is too large, after wet grinding the moisture
content cannot be reduced by vacuum filtration to the required amount,

The increase of the green strength with decreasing porosity can also
be deduced from the models mentioned. The porosity depends on the
particle size distribution of the mater-i.11 and on the pelletizing
process i tsel f.

On the basis of the model, there exists .I linear relationship between

the surface tension of the liquid and the green strength. This has
also been confirmed experimentally 1163.

Pli th decreasing wettabi 1 i ty of the sol id surface, the binding forces

are reduced and thus the strength, too. Hence, in oelletizing hydro-
phobic materials, difficulties arise (e.g. flotation concentrates).

The grinding process before pel 1 eti zation has a oronounced effect. Met-
ground materials need a higher moisture content than those produced by
dry-grinding E46,471.

The selective flocculation of hydrophobic particles in aqueous pu!ps

by utilization of non-polar oil bridges has been used in mineral pro-
cessing for a long time. The formation of these bridges requires an
appropriate oi 1 addition and its dispersion by agitation. One of the
previous applications was the Convertol-process 1481. Further on,
there are the processes we1 l-known under the term agglomeration flo-
tation E493. Recently, greater attention has been paid again to selec-
 115

tive flocculation in coal preparation (see e.g. 121,50-523). The appli-

cation is, however, limited for economic reasons.

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