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Surface Forces
Surface Forces
ChemE 554/ove
Type of Force
Ionic bond
Coulombic force
Covalent bond
Electrostatic force
(wave function overlap)
Metallic bond
Hydrogen Bond
Van der Waals
Energy (kcal/mol)
180
240
170
283
26
96
210
(NaCl)
(LiF)
(Diamond)
(SiC)
(Na)
(Fe)
(W)
(HF)
2.4
(CH4)
Distance
2.8
2.0
N/A
4.3
2.9
3.1
significant in the
range of a few to
hundreds of
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Source: Handbook of Micro/Nanotribology, ed. Bharat Bhushan, CRC Press N.Y. p. 269 (1995).
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Covalent Bond: The standard example for a covalent bond is the hydrogen atom. When
the wave-function overlap is considerable, the electrons of the hydrogen atoms will be
indistinguishable. The total energy will be decreased by the "exchange energy", which
causes the attractive force. The characteristic property of covalent bonds is a
concentration of the electron charge density between the two nuclei. The force is
strongly directed and falls off within a few ngstroms.
Ionic Bonds: These are simple Coulombic forces which are a result of the electron
transfer. For example in lithium fluoride the lithium transfers its 2s-electron to the
fluorine 2p-state. Consequently the shells of the atoms are filled up, but the lithium has a
net positive charge and the fluorine a net negative charge. These ions attract each other
by Coulombic interaction which stabilizes the ionic crystal in the rock-salt structure.
Metallic Bonds and Interaction: The strong metallic bonds are only observed when the
atoms are condensed in a crystal. They originates from the free valency electron sea
which holds together the ionic cores. A similar effect is observed when two metallic
surfaces approach each other. The electron clouds have the tendency to spread out, in
order to minimize the surface energy. Thus a strong exponentially decreasing, attractive
interaction is observed.
where L is the surface tension, R the gas constant, T the temperature, V the mol volume
and p/ps the relative vapor pressure (relative humidity for water). The surface tension L
of water is 0.074N/m (T=20C) leading to a critical Van der Waals distance of water of
LV/RT = 5.4 . Consequentially, we obtain for p/ps=0.9 a Kelvin radius of 100 . At
small vapor pressures, the Kelvin radius gets comparable to the dimensions of the
molecules, and thus, the Kelvin equation breaks down.
The meniscus forces between two objects of spherical and planar geometry can be
approximated, for D R, as:
4R L cos
F R >> D =
(1 + D / d )
where R is the radius of the sphere, d the length of PQ , see Fig. 1, D the distance
between the sphere and the plate, and the meniscus contact angle.
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Fig. 1: Capillary meniscus between two two objects of spherical and planar geometry
Pull-off Force
The medium for capillary interaction is the capillary neck. Structured bulk water
strongly affects the surface tension of the water-air interface, i.e., the mechanical
properties of neck side-walls. At the water-solid interface, the water experiences surface
adhesion that competes with the molecular self-association of bulk water. At sufficiently
low humidity, i.e., in a spatially confined liquid film of only a few molecular layers, it
can be expected that the interfacial interaction is powerful enough to distort the bulk
structure.
Salmeron and co-workers employed SFM adhesion measurements on mica surfaces
as a function of the humidity and noticed that there are three distinct force regimes as
illustrated in Fig. 2 (experimental confirmation provided in Fig. 3). In Regime I, the
measured pull-off forces are depressed if compared to the forces in Regime II and III.
The qualitative force behavior from regime I to II has been confirmed by others with
hydrophilic SFM tips on mica.(10,14) In order to reflect on the possibility that the
qualitative transition behavior resembles structural change of water, it has first to be
discussed on how a structural change would affect the observable force.
II
III
Relative Humidity
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Figure 3 shows the results of pull-off force vs. RH measurements conducted with a
hydrophilic tip on a silicon sample. At low RH (40%), the pull-off force is constant. In
the mid-RH range (40%RH70%), the pull-off force increases with increasing RH. A
pull-off force RH hysteresis is noticeable in this regime. At 40% RH a force discontinuity
occurs. The transition seems to be more pronounced for decreasing humidity than for
increasing humidity, which is an instrumental artifact due to improved control of RH for
decreasing humidity. At RH larger than 70%, the pull-off force decreases with increasing
humidity. The transition RH does not change with spring constants.
Fig. 3: Pull-off force vs. RH
measured between a hydrophilic tip
and a flat silicon sample.
measured when increasing RH,
measured when decreasing RH.
40
30
20
10
0
0
20
40
60
80
100
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at significantly different RH values. The thickness of the water film on the substrate
surface depends on RH. Thus, the restructuring transition in water occurs in the vicinity
closest to the silicon substrate, because the water film is thinning with decreasing
humidity. Note that only one hydrophilic surface is necessary to form a water film.
Hence, the water restructuring process and its detection in pull-off force measurements
should not depend on the cantilever probe material as long as the sample is hydrophilic.
For a hydrophobic tip coated with n-octadecyltrichlorosilane (OTS), on the same
silicon substrate as above, one observed however constant pull-off forces (i.e., forces
independent of RH) in the entire range from 10% to 80% RH (Fig. 4). Consequently the
water structuring model based on force-distance curves is inconsistent. A much more
likely interpretation for the force instability at 40% RH is the ability or inability of the
water film to form a liquid joining neck between the adjacent surfaces at high and low
RH, respectively.
Fig. 4: Pull-off force vs RH
measured between a sharp SFM tip
coated with OTS and a flat silicon
sample. The pull-off force is
independent of humidity.
40
30
20
10
0
0
20
40
60
80
100
Hence, based on the above results, the three regimes in pull-off force SFM
measurements for adjacent hydrophilic surfaces (Fig. 3)can be interpreted as follows: In
regime I, no capillary neck is developed, and the pull-off force is dominated by van der
Waals interactions. A capillary neck is formed at about 40% RH, which corresponds to
the force discontinuity observed between regimes I and II. We can understand this
transition-like behavior of the pull-off force by considering the minimum thickness
requirement of water precursor films for spreading(28,29). The height of the precursor
film can not drop below a certain minimum, e, which is
1/ 2
1/ 2
A
; S = SO SL .
(2)
e = a0 ; a0 =
S
6
where a0 is a molecular length,(29), S the spreading coefficient, A the Hamaker constant,
SO the solid-vacuum interfacial energy, and SL the solid-liquid interfacial energy.
We propose that the formation of the capillary neck also requires a minimum height
of the water film. No capillary neck forms between two surfaces until the water film
thickness reaches the minimum thickness. The water film thickness was found to increase
with the increase of RH (i.e., p/ps).(19), i.e., the thickness of the water film on the silicon
surface is too thin to form a capillary neck with the probing tip for RH less than 40%.
When the water film thickness reaches the minimum thickness requirement at 40% RH, a
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capillary neck forms between the tip and the substrate surfaces, leading to a sudden
increase of the pull-off force.
The magnitude of pull-off forces measured on hydrophilic silicon surfaces below
40% RH is 83 nN (Fig. 3 and 4). For RH larger than the critical RH, in the mid-RH
regime II (Fig. 2 and 3), the capillary force dominates the pull-off force if both surfaces
are hydrophilic. Thus, the SFM observable the pull-off force is not a direct measure
of the capillary force only. In regime II the pull-off force can be described as the sum of
the capillary force (Fcap) and van der Waals interaction force (Fvdw), i.e.,
Fpull = Fcap + Fvdw
(3)
In regime I, the pull-off force is restricted to van der Waals interaction between the
cantilever tip and the sample surfaces. Both Fcap and Fvdw are attractive.
In the high RH regime III (Fig. 2 and 3), the pull-off force decreases with increasing
RH for a hydrophilic tip. Mate and Binggeli(5) discussed the decrease as the interplay
between capillary forces and the forces related to the chemical bonding of the liquid in
the gap. This leads to the following expression for the pull-off force:
p
G
a
a
= = kT ln
Fpull = Fcap + Fvdw + Fchem ; Fchem =
(4)
z
v
v
ps
where Fchem(5) is the force related to the chemical bonding with G the Gibbs free energy,
a the area of the liquid film, v the molar volume, the chemical potential.
Measurements with hydrophilic cantilever tips on ionic surfaces, such as calcium
fluoride, CaF2, show a similar qualitative trend in the pull-off force at low RH as found
above on silicon surfaces. At intermediate RH, the pull-off force collapses very rapidly
with increasing RH. This can be explained by ion-diffusion from calcium fluoride surface
into the water film, which has a strong affect on the material properties such as the
surface tension.
Roughness effects can explain why force values for presumable microcontacts (silica
glass sphere) at low loads are significantly smaller than expected from Eq. (1). The
roughness of the sphere is 10 nm rms determined from a 2nd-order flattened AFM image
over 1 m2 area of the sphere surface. At low load, the sphere makes contact with
multiple nanosized asperities. This leads to a significant decrease in the pull-off force in
the van der Waals interaction regime compared to an atomically smooth sphere. The
argument also holds in the capillary regime. The force instability measured with silica
glass spheres is widened by the asperity size dispersion, and the magnitude of the pull-off
force is determined by the number of asperities in contact. Halsey and Levine suggested
that the adhesive force between two rough spheres was dependent on the total amount of
the fluid present.(30)
Capillary force equation for nano-contacts
We derived the capillary force equation for nano-contacts from the sphere-plane
approximation, found in reference(25), with the distinction that we did not require a large
contact area, and thus, do not restrict our capillary force equation to large sphere radii, R
(Fig. 2).
Starting from the surface free energy of the system, W,(25)
W = s + c ; s = (d 2 + 2 R 2 sin 2 ) ; d = R (1 cos ) ,
(5)
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where is the angle of MOP , s the wetted surface area, and c a constant. The capillary
force can be introduced as
dW
d
F =
= R 2 [2 sin (1 + cos )]
.
(6)
dD
dD
where D is the distance between the sphere and the plane. The differential term of the
angle with D can be obtained by an isovolume consideration (dV/dD = 0) of a
simplified meniscus volume (ABMQN), V, which equals the volume of the cylinder
ABMN minus the volume of the spherical cap MNQ. The simplified meniscus volume is
R 3
V = R 2 sin 2 ( D + d )
(1 cos ) 2 (2 + cos )
(7)
3
Equation (7) leads to the following relationship:
d
tan
=
(8)
D
dD
2 R(1 cos )1 +
d
This equation is also applicable to small contacts. The capillary force is derived by
substituting equation (8) into equation (6), i.e.,
(1 + cos ) 2
,
(9)
F = R cos
D
cos 1 +
d
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12 6
A C
C2
C 6
( r ) = 6 + 12 = 4 ; = ; =
.
r
r
4B
A
r
r
The potential is also referred to as the 6-12 potential because of its (1/r)6 and (1/r)12
distance, r, dependence of the attractive interaction and repulsive component,
respectively. The empirical constant represents the characteristic energy of interaction
between the molecules (the maximum energy of attraction between a pair of molecules).
, a characteristic diameter of the molecule (also called the collision diameter), is the
distance between two atoms (or molecules) for (r) = 0. The LJ potential is depicted
below. Examples for the LJ parameters, and , are provided in Table 2.
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Table 2:
Substance
()
/k
H2 (light element)
Ar (noble gas)
2.915
3.418
38.0
124
Polyatomic Substances
Air
N2
3.617
3.681
97.0
91.5
Hydrocarbons
CH4
n-C6-H14
3.822
5.909
137
413
10
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Table 2
Notice: The energy of interaction between flat surfaces is per unit area!
One notices the significantly impacted distance dependences. While, Van der Waals
atom-atom interactions are very short ranged (~1/r6), macroscopic Van der Waals
interactions are long ranged (e.g., sphere-sphere: ~1/D).
C [10-79 Jm6]
50
1500
140
[1028 m-3]
3.3
0.6
3.3
A [10-19 J]
0.5
0.5
1.5
Derjaguin Approximation
The Derjaguin Approximation relates the force law, F(D), between two curved
surfaces to the interaction free energy per unit area, W(D), between two planar surfaces.
This makes this approximation a very useful tool, since it is usually easier to derive the
interaction energy for two planar surfaces rather than for curved surfaces. The Derjaguin
Approximation reads as follows:
F ( D )curved 2R*W ' ' ( D )planar ,
where D is the separation distance, and R*is the combined curvature of the two surfaces,
i.e., 1/R*=1/R1+1/R2.
The Derjaguin Approximation is valid not only for additive inverse power law potentials
(such as Van der Waals interactions) but for any type of force law, whether attractive,
repulsive or oscillatory, as long as the range of the interaction and the separation distance
D is much smaller than the curvature.
To illustrate the power of the Derjaguin Approximation we will provide a derivation
based on the inverse power law potential. We start with the pair potential
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w (r ) =
C
,
rn
(1)
(2)
Fig. 1
Now we let a single molecule of the sphere at distance D interact with the planar surface
in figure 1 which yields the following interaction potential:
w( D ) = 2C
z=D
x =0
dz (z
xdx
+ x2 )
n/2
2C
dz
2C
=
=
;n > 3
n 2
(n 2) D z
( n 2 )( n 3 )D n3
(3)
2 2C 2
( n 2 )(n 3)
z =2 R
z =0
( 2 R z ) zdz
( D + z )n 3
(4)
based on equation (3), a molecule-plane distance of D+z, and unchanged number density
in the sphere and the plane. For very small distances (i.e., D<<R) only small values of z
contribute which simplifies the integral as follows
2 2C 2
2 Rzdz
W( D ) =
,
( n 2 )(n 3) z =0 ( D + z )n3
(5)
and yields the following final solution for the interaction energy between curved surfaces
W( D ) =
4 2C 2 R
( n 2 )(n 3)( n 4 )( n 5 )D n 5
(6)
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Note that the radius, R, in figure 1 represents the combined radius, R*, in the case of two
curved surfaces. In the case of Van der Waals forces, i.e, n=6, the interaction energy
becomes
W ( D )curved =
2 C 2 R
(curved surfaces)
6D
(7)
W ( D ) 2C 2 R
=
=
(curved surfaces)
D
6D 2
(8)
C 2
(planar surfaces),
12 D 2
(9)
(10)
Example:
For two spheres in contact (D=, interaction distance), the interaction energy W()
can be replaced by two times the surface energy, , which yields a contact interaction
force for curved surfaces of
F(D) curved = 4R * .
+
A kT
2
2
2
2
4 1 + 3 2 + 3 8 2 n 2 + n 2 n 2 + n 2
n1 + n3 + n2 + n3
1
3
2
3
)(
)(
){ (
)
) (
)}
13
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where e is the absorption frequency (e.g., for H2O: e = 3 x 1015 Hz). Table 11.2 (below)
provides non-retarded Hamaker constants determined with the Lifshitz theory (eq. 11).
Source: Intermolecular & Surface Forces, J. Israelachvili, Academic Press.
Retardation Effects
The van der Waals forces are effective from a distance of a few Angstroms to several
hundreds of Angstroms. When two atoms are a large distance apart, the time for the
electric field to return can be critical, i.e., comparable to the fluctuating period of the
dipole itself. The dispersion can be considered to be retarded for distances more than
100 , i.e., the dispersion energy begins to decay faster than 1/r6 (~1/r7).
For macroscopic bodies retardation effects are more important than for atom-atom
interactions (see Fig. below).
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=
W = W1 + W2 =
D
12 Do 2 D 2 12Do 2
In contact (i.e., D=Do) W = 0. In the case of isolated surfaces, i.e., D = , W =
A
.
2
12Do
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Thus, in order to separate the two surfaces one has to overcome the energy difference
A
W=W(Do)- W(D=)=, which corresponds to the adhesive energy per unit area
2
12Do
of W''=212. Hence, the interfacial energy can expressed as function of the Hamaker
A
constant and the cutoff distance: 12 =
.
24Do2
Cutoff Distance
The challenge is to determine Do, which unfortunately cannot be set equal to the collision
diameter (i.e., the distance between atomic centers). Let us assume a planar solid
consisting of atoms that are close-packed. Each surface atom (of diameter ) will have
nine nearest neighbors (instead of 12 as in the bulk). When surface atoms come into
contact with a second surface each atom will gain (12-9)w=3w=3C/6 in binding energy.
Thus, the energy per unit area, S=2sin(60 deg) = 23/2, is
1 3w
3C
3C 2
2
; = 3
12 = = 8 =
2
2 S
2
where reflects the bulk atom density for a close packed system. Introducing the
A
3C 2
3A
=
2.5
A
it follows Do = 0.16 nm. Do = 0.16 nm is a remarkable
For = 0.4 nm and 12 =
24Do2
"universal constant" yielding values for surface energies that are in good agreement
with experiments as shown in the Table below.
Source: Intermolecular & Surface Forces, J. Israelachvili, Academic Press.
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(22) R Aveyard, JH Clint, D Nees: Theory for the determination of line tension from capillary
condensation. Journal Of the Chemical Society-Faraday Transactions 93 (1997) 4409-11.
(23) AW Adamson: Physical Chemistry of Surfaces, John Wiley & Sons, Inc., New York, 1990.
(24) EA Vogler: Structure and reactivity of water at biomaterial surfaces. Adv. Coll. Int. Sci. 74 (1998) 69117.
(25) JN Israelachvili: Intermolecular and surface forces, Academic Press, London, 1992.
(26) G Meyer, NM Amer: Appl. Phys. Lett. 56 (1990) 2100.
(27) R Luginbhl, A Szuchmacher, MD Garrison, JB Lhoest, RM Overney, BD Ratner: Comprehensive
Surface Analysis of Hydrophobically Functionalized SFM Tips. Ultramicroscopy 82 (2000) 171-79.
(28) R Bruinsma: Slow spreading of polymer melts. Macromolecules 23 (1990) 276-80.
(29) PG de Gennes: Wetting: statistics and dynamics. Rev. Mod. Phys. 57 (1985) 827-63.
(30) T Halsey, A Levine: How sandcastles fall. Physical Review Letters 80 (1998) 3141-44.
(31) A Marmur: Tip-surface capillary interactions. Langmuir 9 (1993) 1922-26.
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