From Classical to

Molecular TRIBOLOGY

Contact Forces
- Van der Waals
- Capillary Forces

Contact Mechanics
- Fully Elastic Contact Model (Hertz Theory)
- Elastic-Adhesive Contact Model (JKR)

Tribology Basics
- Amontons Laws, Reynolds Lubrication, Adhesive Model

Molecular Motion, Energetics and Time Temperature Superposition

 Eyring Model, Intrinsic Friction Analysis

Molecular Tribology

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Interaction Potentials
Table 1: Short Range Interaction Forces
Nature of Bond

Type of Force

Energy (kcal/mol)

Coulombic force

180
240

Electrostatic force
(wave function overlap)

170 (Diamond)
283
(SiC)

Metallic bond

free valency electron sea

interaction
(sometimes also partially
covalent (e.g., Fe and W)

26
96
210

(Na)
(Fe)
(W)

Hydrogen Bond

a strong type of directional

dipole-dipole interaction

(HF)

Van der Waals

(i) dipole-dipole force

(ii) dipole-induced dipole
force
(iii) dispersion forces
(charge fluctuation)

Ionic bond
Covalent bond

Ren Overney / UW

(NaCl)
(LiF)

1.(CH4)

Molecular Tribology

Distance
2.8
2.0
N/A
4.3
2.9
3.1

significant in the
range of a few to
hundreds of

NME 498A / A 2010

Interactions and Surface Forces

Van der Waals Interaction (Point Particles)
dipole-dipole or induced-dipole interaction
r

Dipole Dipole Interactions Potential: 1/r6 Potential

wVDW ( r ) =
w(r)

Interactions (sketch)

Cvdw
r6

Keesom Interaction
(rotating dipole interaction)

w(r ) =

u12 u 22

3(4 o ) k B Tr 6
2

Debye Interaction
Short range VdW

1/r6

(induced dipole interaction)

w( r ) =

u 2 o

(4 o )2 r 6

London Interaction

Long range Electrostatic 1/r

(QED fluctuation)

attractive (they can also be repulsive)

w(r ) =
Ren Overney / UW

Molecular Tribology

3 o2 h
4 (4 o )2 r 6

NME 498A / A 2010

Interactions and Surface Forces

Dipole Moment and Polarizability
+/- q charge

+ Cl H-

l = 0.127 nm
Permanent Dipole Moment:

u=ql
uHCl = 1.08 D(ebye)
1 D = 3.3310-30 C m

Chemical

Dipole Moment (D)

Non-polar: CO2

0.00

Polar: H2O

1.85

HCl
Ren Overney / UW

Non-Polar Molecule:
Carbon Dioxide (CO2)

Polar Molecule:
Hydrogen Chloride (HCl)
-E

-
+
CO
+
2 Induced Dipole Moment:

uind = E
electronic polarizability
[C2m2/J]

CO2 = 3.110-40 C2m2/J

1.08
Molecular Tribology

NME 498A / A 2010

Interactions and Surface Forces

Semi-empirical Potential: Lennard Jones (LJ)
6-12 Potential

( r ) =

Cvdw
r6

Crep
r12

()

12 6
= 4
r
r

r()
0

Characteristic Parameters
collision paramter
energy of interaction

Ren Overney / UW

wVDW ( r ) =

Molecular Tribology

Cvdw
r6

Interactions between 2D and 3D Objects

Point Interaction

Integral Interaction
Long range VdW 1/D

Two Atoms

C
r6

Atom-Surface

C
6D 3

Sphere-Sphere

A R1 R2
6 D ( R1 + R2 )

Hamaker Constant
A = 2 12C
. molecular number density

AR
6D

Plane-Sphere

Two Cylinders

Two Crossed Cylinders

R1 R2
AL

12 2 D 3 2 ( R1 + R2 )

12

A R1 R 2

6D

Plane-Plane

per unit area

Two Parallel Chain
Molecules

Ren Overney / UW

AR
6D

Interaction Potential (W)

attractive (they can also be repulsive)

Body Interaction

w(r)

Short range VdW 1/r6

W (D ) =

Van der Waals Interaction

Geometry of Interaction

Point Interaction

NME 498A / A 2010

Molecular Tribology

A
12D 2

3CL
8 2 r 5

W (D ) =

AR
6D

NME 498A / A 2010

W (D ) =

Van der Waals Interaction Parameter expressed by

Field Properties Lifshitz Equation

Solid Material

(dielectric constant)

n (refractive index)

12

3.45

Silicon (Si)
Silicon Oxide (SiOx)

3.78

1.45

Mica

1.6

PTFE

2.1

1.359

Fluid Environment

(dielectric
constant)

n (refractive index)

2.03

1.426

Cyclohexane
Lifshitz Eq.
A

AR
6D

3 1 3 2 3 3h e

+
kT
4 1 + 3 2 + 3 8 2

(n

2
1

+ n3

) (n

(n

2
1

)(
){ (n

n3 n2 n3
2

+ n3

)
) (n

2
1

+ n3 +
2

+ n3

)}

absorption frequency e (e.g., for H2O: e = 3 x 1015 Hz)

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Surface Energy
Surface energies based on Lifshitz theory and experimental values.(Source:
intermolecular & Surface Forces, J. Israelachvili, Academic Press)
Surface Energy, (mJ/m )
2

Material

A
(10

Liquid helium

Lifshiz Theory

-20

0.057

A/24 Do
)

Experimental*
o

{Do=0.165nm}

(20 C)

0.28

0.12 - 0.35(at 4-1.6K)

Water

3.7

18

73

Acetone
Benzene
CCl4

4.1
5.0
5.5

20.0
24.4
26.8

23.7
28.8
29.7

H2 o2
Formamide

5.4
6.1

26
30

76
58

Methanol
Ethanol
Glycerol
Glycol

3.6
4.2
6.7
5.6

18
20.5
33
28

23
22.8
63
48

3.75
5.2
4.5
5.0
5.2

18.3
25.3
21.9
24.4
25.3

16.1
27.5
21.6
25.4
25.5

3.8
6.6
7.8

18.5
32.1
38.0

18.3
33
39

n- Pentane
n -Hexadecane
n -Octane
n -Dodecane
Cyclohexane
PTFE
Polystyrene
Polyvinyl chloride

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Adhesion and Surface Energy

The energy of adhesion (or just adhesion), W", i.e., the energy per unit
area necessary to separate two bodies (1 and 2)

W '' = 2 12 ; 12 = 1 + 2 2 1 2
12 interfacial energy
1/2 surface energy of surface 1 and 2

W = W (Do ) W (D = )
=

12

Ren Overney / UW

1
2

12 =

A
12Do

A
24Do2

Molecular Tribology

Do ~ 0.165 nm

NME 498A / A 2010

Capillary Forces
Capillary forces are meniscus forces due to third media condensation.

rK =

LV
p
RT log
ps

R >> d
Fmax
= 4R cos
Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Capillary Forces

VdW only
RH < 35%

Ftotal = Fstv =

RA
1.5 1018 R A[N]
2
24 Do

Capillary will dominate

RH > 40 %

Ren Overney / UW

Ftotal

A
= R
+ 4 water cos
2

24 Do

Molecular Tribology

NME 498A / A 2010

Contact Mechanics

Contact Mechanical Models1:

 Hertz: fully elastic model,
 JKR:
fully elastic model considering adhesion in the contact zone,
 Bradley: purely Van der Waals model with rigid spheres,
 DMT:
fully elastic, adhesive andVan der Waals model.

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Contact Mechanics

Fully Elastic Hertz Model

Combined Radius of Curvature
1
1
1

R = +

R1 R2

Youngs Modulus

1 12 1 22

E* =
+
E
E2
1

3LR
a= *
4E

Hertz contact radius:

Hertz area of contact:

3 LR
A = a 2 = *
4E

Mutual approach:

L Load
2

3
a 2 2 ao 2 with ao = a
1
L=0
R 3 a

1
6 L E* 2 3
3L
3

pmax =
=
p
m
3 R 2
2a 2 2
Molecular Tribology
NME 498A / A 2010

( )

Hertz pressure:
Ren Overney / UW

Contact Mechanics

Elastic-Adhesive JKR Model

JKR contact radius:

L = Ladh

JKR

a3 =

3R
2
L + 3R + 6RL + (3R )

4 E*

3
= R*
2

surface tension

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

A system in which only the sample material is compliant

LJ Adhesive Branch (out of contact)

Elastic Contact
JKR Branch
Approach: At "A" two surfaces during approach deform suddenly
towards each other and form an adhesive interfacial junction at "B".
Retraction: At "C" the adhesive junction is suddenly lost and the force
jumps from the upper branch to the lower LJ branch.
The area described by (ABCD) corresponds to the energy dissipated
during the approach-retraction cycle.
We assumed an infinitely stiff holding system.

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

A system in which the sample and the probe (cantilever) is compliant

LJ Adhesive Branch (out of contact)

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology
The science of Tribology (Greek tribos: rubbing) concentrates on Contact
Mechanics of Moving Interfaces that generally involve energy dissipation

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology

Prehistoric to Ancient Times

~ 7000 B.C. Northern Norway Skier in rock carving

1880 B.C. Egypt Transport of Eqyptian

colossus on the tomb of Tehuti-Hetep. ElBersheh.

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology

Dry and Wearless Friction

The classical Laws of unlubricated Friction
1.

The force of friction is directly

proportional to the applied load.
(Amontons 1st Law)

2.

The force of friction is independent of

the apparent area of contact.
(Amontons 2nd Law)

3.

Kinetic friction is independent of the

sliding velocity. (Coulomb's Law)

Leonardo da Vinci

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology

Dry and Wearless Friction

Fstat (x)= kc x

Fstat

v=0

Fpull
v = const

Fkin

Fkin

Fpull

xo

Fkin Kinetic Friction

Fpull
0

Fstat Static Friction

- Fpull

x1

Def.: Friction Coefficient

Fkin
L

L Load (normal force)

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

10

Tribology Dry Friction

Friction Theoretical Models

Desanguliers (1734) proposed Adhesion
Idea
Eulers (18th century) Asperity Interlocking
Model
Hardys (1922) Theory of Boundary
Lubrication
Bowden and Tabors (~1950) Plastic
Adhesive Model
Mode Coupling Entropic Model (Overney,
Silss, Knorr ~2004)
Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology Dry Friction

Friction Theoretical Models

Eulers (18th century) Asperity Interlocking Model

Hardys (1922) Theory of Boundary Lubrication

Nanometer
Boundary Regime
(ultra thin film regime)
Even Liquids behave
solid-like

= F/A= G (stress strain relationship)

Ren Overney / UW

Molecular Tribology

v
NME 498A / A 2010

11

Tribology Dry Friction

Friction Theoretical Models

Bowden and Tabors (~1950) Plastic Adhesive Model
(i) Real Contact Area  defies Amontons second law,
i.e., friction is dependent on contact area
real contact area
Spherical Real Contact

Apparent contact

Contact radius a determined from Contact Mechanics

(ii) Contact Zones (Asperities) are plastically deformed

kin =

F
= crit r = crit crit
L pm ,crit Ar pm ,crit 2.8Y

Ren Overney / UW

Y material specific
plastic yield stress

Molecular Tribology

NME 498A / A 2010

Tribology

Lubrication Reynolds HL
Newtons law of viscosity

yx =

dv x
dy

(stress strain rate relationship)

viscosity
yx= = Fx/A

y
0

Fx Drag Force

vx
Fx, vo

vo

x
0

no-slip condition

Reynolds Lubrication Assumption for Hydrodynamic Lubrication (HL):

1. The height of the fluid film y is very small compared to the dimensions of the
contact area, the pressure is constant across the fluid film,
2. the flow is laminar, i.e., no turbulence occur,
3. the inertia of the fluid is small compared to the viscous shear (examples of
inertia forces are fluid gravity and acceleration of the fluid),
4. no external forces act on the film.
Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

12

Tribology

Lubrication Reynolds HL
Reynolds Equation of Lubrication

(h )
h 3 p h 3 p

+ 6h ( U1 + U 2 ) + 12V
= 6( U1 U 2 )
+

x x z z
x
x
Simplified for parallel plates
at close distance D:
D

v
D

Friction or Drag Force

D
D

Hydrodynamic Regime

V is directly correlated to D
Gumbel Number NG = P-1
Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology

Molecular Atomistic Phenomena

Observed for Ultrathin Liquids

Stick-slip Phenomena

Israelachvili J.
Model concept: Solid-liquid phase transition

Debye Relaxation

Fluid behavior

solid

D
= o exp
t ;
A

v
D

liquid
Startup
Phase

Observed for Molecularly Smooth Surfaces

Steady Shear
Phase
stop

M x + M x +
Ren Overney / UW

Molecular Tribology

E( x ,t )
= ( t )
x

NME 498A / A 2010

13

Tribology Dry Friction

Molecular Stick-Slip
Experimental Verification

Prandtl - Tomlinson Model

(1920)

(1994 Overney)

SFM/AFM
on bilayer
Lipid Film
Fave=24 nN
Fave=32 nN

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology

Rate Dependence of Friction

Eyring Model: Kinetic Jump Model
Friction depends logarithmically
on velocity
Contrary to Newtons Law (linear)
(for liquids)
Contrary to Coulombs Law (constant)
(for solids)
P

Ren Overney / UW

Polystyrene

= o ' T
= o ' '+ ln v

= Q

= o + p

+ P

Molecular Tribology

NME 498A / A 2010

14

Tribology Intrinsic Friction Analysis (IFA)

Superposition of Friction Rate Isotherms

resulting MASTER CURVE

arb. chosen reference line

(temperature)

ln(aT) shift
Time-Temperature Equivalence

aT =
log G

T 1 T 1

T 2 T 2

GT1

Ea

GT2

log aT2

log t

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology Intrinsic Friction Analysis (IFA)

Friction: Relaxation vs. Probing Rate

377 K
380 K
384 K
388 K
392 K
395 K
398 K
403 K

130

F + F(T) [nN]

120
110

ln( a T )

140
4
3
E a = 88 kcal / mol
2
1
0
-1
-2
-3
-4
-5
2.45 2.50 2.55 2.60

100

Tg Rubber Melt

2.65

2.70

1000 / T (K)

90

Glass

80
70
1

5
9
ln( a T * v [nm/s] )

13

The bell shape of F(v)|T originates from the

interplay of two dominating time scales
(Deborah Number):
e

De =

e extrinsic experimental time

m material intrinsic time
Ren Overney / UW

Phenyl
Rotation

-Segmental
Motion

although distinctively different origin for

dissipation, the qualitative difference (log vs.
bell-shaped) is not reflecting a fundamental
difference
Molecular Tribology

NME 498A / A 2010

15

Tribology Intrinsic Friction Analysis (IFA)

Superposition of Friction Rate Isotherms

poly(tert-butyl acrylate) (PtBA)

FF

Cooperative Motion

TS *
'

Side chain
relaxation

Energetics

zero
E1

high
for backbones

E2

Backbone
relaxation

R
Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Tribology Intrinsic Friction Analysis (IFA)

Mode Coupling
Slider couples with thermally active modes controlled externally with
Pressure and Temperature
E.g., Pressure addressed Mode Coupling

Backbone
Relaxation
Ea = 88 kcal / mol

Side Chain
Relaxation
Ea = 7 kcal / mol

Polystyrene

Backbone
Relaxation
Ea = 88 kcal / mol

Side Chain
Relaxation

Ea = 7 kcal / mol

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

16

Tribology Intrinsic Friction Analysis (IFA)

Mode Coupling
Slider couples with thermally active modes controlled externally with
Pressure and Temperature
E.g., Pressure addressed Mode Coupling

Backbone
Relaxation
Ea = 88 kcal / mol

Side Chain
Relaxation
Ea = 7 kcal / mol

Polystyrene

Backbone
Relaxation
Ea = 88 kcal / mol

Side Chain
Relaxation
Ea = 7 kcal / mol

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Coupling with Thermally Active Modes

TOP View

Slider Tip
Slider 1D motion couples with thermally
available mode(s) in sample
 Entropy Reduction a Energy Dissipative Process

 Heat generation follows (coupling of rotational with vibrational modes)

SIDE View

Thermally active modes

(rotational , translational, vibrational)

17

Related Topics
Millipede (NEMS) Project a Tribological
Challenge
Shear Force Analysis with Hot Tip of
Adhesive Forces in Nanocomposites
Flux and Transition Analysis using Friction
Forces

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

Summary

Discussed contact forces, in particular adhesion forces and capillary forces.

Introduced contact mechanics, which considers the deformation aspect of contact.

Limited discussion to elastic contact.

Addressed dry and lubricated friction in classical phenomenological terms.

Introduced the Eyring activation model a first step towards a molecular description
of friction dissipation.

Discussed Molecular stick-slip phenomena and logarithmic friction-velocity behavior

directed.

Considered molecular modes of rotation and translation that couple to the sliding
motion and extract energy from it.

We concluded that frictional heating is a consequence of a two step process:

(i) slider coupling with intrinsic modes, which leads to entropic cooling (alignment) of
molecular modes, which gives rise to energy dissipation,
(ii) followed by mode coupling of the entropically cooled modes with modes of
vibrations.

Ren Overney / UW

Molecular Tribology

NME 498A / A 2010

18

Thermomechanical Data Storage (TDS)

Indentation:

BIT INDENTATIONS
30-50 nm

Data storage via

small indents in
thin polymer films
CANTILEVERED
READ / WRITE
PROBE

POLYMER FILM

20-50 nm

A 2D Array of probes is
operated in a parallel /
multiplexed manner.

SUBSTRATE

Density well beyond the

superparamagnetic limit.
(Tb/in2 vs 100 Gb/in2)1
Data rates comparable to
todays magnetic devices.
(Mb/s)1
1

Vettiger, et al., IEEE Transactions on Nanotechnology, 1 (2002)

NanoScience & Information Storage

Millipede Storage Concept

A 2D ARRAY OF LOCAL
PROBES IS OPERATED IN
A PARALLEL / MULTIPLEX
FASHION.
Cantilever Array: (7 14 mm2)
32 32 (1024) Cantilevers
Vettiger, et al., IEEE Transactions
on Nanotechnology, 1 (2002)

2 mm

200 m

20 m

2 m

19

Glass Transition and Device Performance:

Thermomechanical Data Storage (Millipede)

Modulus vs. Film Thickness

Effective modulus profile compared to
glass transition profile.
(normalized with corresponding value
at =150 nm)

CANTILEVE
RED READ /
WRITE
PROBE

SUBSTRATE

DR
Di

15 nm

Modulus (PS-BCB)

1.05

Tg

1.04

30

MAX ~ 60 nm

Eeff = pm / tan

1.02

10
1.01
0

1.00
0

50

100

150

200

250

Film Thickness, (nm)

1.03

20

Relative T g

20-50 nm

POLYMER
FILM

1.06

Modulus (Si substrate)

40

Relative Modulus

Modulus and Tg profiles coincide.

250 nm

Adhesion Analysis of Silicon PTMSP Nanocomposites

adhesive interaction
energy per unit area
PTMSP 180 mJ/m2
TEMP
-2.0

Laser

T
L

-2.5

Lateral Displacement (nA)

Fmax

R
B

-3.0
-3.5
-4.0
-4.5
-5.0
-5.5
-6.0
-200

200

400

600

800

1000

1200

1400

1600

Distance (nm)

20

Water Transport in Proton Exchange Membrane (PEM)

Relaxations in PEM

Local Flux Measurements

A: poor water
transport
A/B: polymer reorganization
promotes
water transport
B: evaporation
B/C: Tg=116 oC

Membrane 1 (M1)

Friction
/ N2Gradient
Pressure
Force-Pressure
(nN/kPa)

Working principle illustrated on N2 diffusive

flux through a Ceramic Zeolite Membrane,
measured in-situ with surface morphology.

Water Transport Through Nafion (PEM)

M3

0.055

Fluid:
Humidified N2
(90% RH)

0.050

M2

0.045
0.040
0.035
0.030
0.025

M1

0.020
0.015

1 m

0.0001

0.0002

0.0003

0.0004

0.0005

Permeation Flux (mol*s *m *kPa )

Permeation
Flux
-1

-2

-1

J.H. Wei et al., J. Membr. Sci. 279 (2006) 60)

21