PAPER CODE NO.

EN4630/ENT630

MOCK 20XX EXAMINATIONS

Fundamentals of Nanomechanics

TIME ALLOWED : Two Hours

INSTRUCTIONS TO CANDIDATES

Full marks can be obtained for FOUR complete answers.

Only the first FOUR answers will be taken into account.

ANSWERS

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 1. Nanoindentation.
(a) Give a description of depth-sensing nanoindentation process and
specific requirements of nanoindentation tests.

(a) Depth-sensing indentation (DSI) is the continuously monitoring

the displacement of the indenter into the sample surface for both load-
ing and unloading branches. The load-displacement P − h diagram at
loading reflects both elastic and plastic deformations of the material,
while it is generally accepted that the unloading is taking place elasti-
cally. Nowadays researchrts extract mechanical properties of materials
(hardness, elastic modulus, ...) from P − h diagrams obtained during
nanoindentation. P − h diagrams are considered by materials science
community as a ”mechanical fingerprint” of the tested material.
Normally special nanoindenters are used for the tests. However, AFMs
having an indentation testing function are also used. One has to note
that nanoindenters drive the indenting tip perpendicular to the sur-
face, while the pyramidal tip of a usual AFM is attached to a bending
cantilever and, hence, its vertical indentation is accompanied also by
some lateral movement.
The indentations can be split onto micro (0.1-20N) and nano (1mN-
500mN). Tips are mainly made of diamond. The advantages of dia-
mond come from its exceptional properties of hardness, thermal con-
ductivity and chemical inertness. However, sapphire is the second ma-
terial usually used for indenters because diamond anisotropy is a dis-
advantage for spherical or conical indenters.
The specimen surface has to be normally flat. Another basic require-
ment is the total absence of surface contamination which would affect
the indenter performance and damage the indenter tip. The floor noise
level has to be minimal. Tip shape characterisation is also very impor-
tant for quantitative analysis in nanoindenting applications.
X marks

(b) A diamond tip of Vickers indenter is probing a flat film. The

maximum of the external load was Pmax = 4 mN. The measured depth
of indentation under this load is 100 nm. Estimate the nanohardness
of the film.

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 (b) As an approximation of the projected contact area (the area
function), one can take the pure geometric Area -function relation for
a Vickers diamond tip
A(h) = 24.5h2 .
Then for h = 100 nm, one obtains Aproj = 24.5 · 10−14 m2 . Hence,

P 4 · 10−3
Hnano = = = 1.63 · 1010 P a = 16.3GP a.
Aproj 24.5 · 10−14

X marks

(c) Estimate the contact modulus (E ∗ ) of the film if the stiffness S

of the upper part of P − h diagram under unloading was 1.25 · 105 N/m.

(c) Using BASh formula

√
dP 2 A ∗
S= = √ E ,
dh π
one obtains
r
S π 1.25 · 105 3.14
r
∗
E = = = 0.224 · 1012 = 224GP a.
2 Aproj 2 24.5 · 10−14

X marks

(d) For diamond indenter Ed = 1200 GPa and νd = 0.2. Assuming

νf ilm = 0.25 calculate Young’s modulus of the film.

(d) From definition of the contact modulus of the contacting mate-

rials
1 1 − ν12 1 − ν22
= + ,
E∗ E1 E2
one has
1 1 − 0.22 1 − 0.252
= + .
224 · 109 1.2 · 1012 E2

0.9375
4.46 · 10−12 = 0.8 · 10−12 + .
E2
1/E2 = 3.904 · 10−12
The Young modulus of the film is E2 = 256 · 109 Pa.
X marks

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 (e) Describe the degree of bluntness of the indenter if area-depth
A − h function for h ≤ 70 nm is approximated as a power-law function
with exponent 0.83, i.e. A ∼ h0.83 ?

(e) If a blunt indenter tip is described in polar coordinates (r, φ) as

a power-law function of degree d

z = B(φ)rd , z < 70nm,

then it follows from the lecturer’s scaling formula that

A ∼ h2/d

independently of the work hardening exponent κ. Hence, we have 2/d =

0.83 or d = 2/0.83 = 2.41 Thus, the tip can be approximated as a
power-law function

z = B(φ)rd = B(φ)r2.41 , z < 70nm.

X marks

2. Carbon Based Materials. Nanotubes and polymer based nanocom-

posites.
(a) What are a − C, a − C : H, and ta − C? How can they be
characterised? What is DLC?
a − C means amorphous carbon. It is a disordered three-dimensional
material: (i) there is no long-range order, i.e. no large regions in which
atoms are arranged in a periodic array and there are no crystallites of
an extended size; (ii) the sp2 and sp3 hybridizations are both present
randomly in a − C films.
a − C : H means amorphous hydrogenated carbon coatings with a
predominance of sp2 bonds.
ta − C means tetrahedral amorphous carbon. It contains at least 80-
85% sp3 . ta − C : H is hydrogenated tetrahedral amorphous carbon
with a predominance of sp3 bonds (like diamond).
Characterisation. Since amorphous carbon (a − C) has no exact
geometric configuration, the characteristics of a − C samples are (i) the
density of a sample; (ii) the predominating C − C-bond type and their
amount of sp3 , sp2 , or even sp1 ; and (iii) the hydrogen concentration.

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 DLC means diamond-like carbon. This is a − C such that the density
and sp3 are high, and the hydrogen concentration is low (up to 30%).

X marks

(b) Give a plausible explanation why the strength of a−C : H having

very high amount of sp3 hybridization may be rather low.

(b) It is known that the soft plastic, polyethylene is made from carbon
that is bonded purely by the sp3 bonds. However, the sp3 also includes
chemically bonded hydrogen. The strength of C − H bonds are much
lower than the strength of any C − C bond. Hence, it is not surprising
to learn that fractions of hydrogen remaining in DLC films degrade
their strength almost as much as do residues of sp2 bonded carbon.

X marks

(c) Give a description of carbon nanotubes. What are SWCNT and

MWCNT? What are two main cases of CNT chirality?
(c) CNT is an allotrope of C. Single walled carbon nanotubes (SWCNT)
is a huge carbon molecule that can be considered as a single layer of
graphite (graphene) that is rolled up in a tube. The multiwalled car-
bon nanotubes (MWCNT) can be considered as a graphite sheet of few
layers that is rolled up in a tube.
The important characteristics of the SWCNT is it chirality that char-
acterises the axis around which the graphene sheet has been rolled
up. The main configurations of NTs are Armchair NT (n, m) = (5, 5),
θ = 30o ; Zig-Zag NT (n, m) = (9, 0), θ = 0o .
X marks

(d) What are typical geometrical characteristics of SWCNT: diame-

ter, length, distance between C atoms? What is the distance between
layers of MWCNT? What can be taken as the effective thickness of a
SWCNT and a MWCNT ?

The inner diameter of NTs is usually in the range from 0.5 to 10 nm.
The length of NTs can be over several cm.
The distance between C bonds in the lattice is about 0.14 nm.

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 The distance between layers of MWCNT is approximately the same as
in graphite δ = 0.34 nm.

The effective thickness of a SWCNT should be taken as 2 pi bond =

2 · 0.066nm = 0.132nm. The effective thickness of a MWCNT with n
layers is (n − 1) · 0.34nm + 0.132nm ≈ n · 0.34nm.

X marks

(e) Consider an idealised model of an aligned nanotube/epoxy matrix

composite where it is assumed that (i) the applied load can be com-
pletely transfered to the NT, and (ii) the NTs are perfectly straight and
parallel to each other. Give a theoretical estimation of the elastic mod-
ulus of this idealised nanocomposite E|| in the case when the applied
load is parallel to the NTs and the NT volume fraction vf is 0.5. The
elastic modulus for NT and epoxy are 1000 and 5 GPa respectively.
Calculate the density of the composite if the density of NTs ρf and the
density of epoxy ρm are 1.5 and 1.2 Mg/m3 respectively.

Using the Rule of Mixture, we obtain that modulus of composite along

the tubes direction is E|| = vf Ef + vm Em and its density is ρc =
vf ρf + vm ρm .
Hence, we have for the epoxy/nanotube system
E|| = 0.5 · 1000 + 0.5 · 5 = 500 + 2.5 = 502.5 GPa;
ρC = 0.5 · 1.5 + 0.5 · 1.2 = 1.35 g/cm3
X marks

(f) What are the main factors that do not allow researchers to get a
composite with the theoretical E?

There are several factors.

1. The NTs are very flexible (the length - diameter ratio can be many
thousands). Hence, the assumption that the NTs are perfectly straight
is not correct, in fact the NT are crumpled.
2. The bonds of C atoms are connected to each other and the side of a
NT molecule is rather inert. The connection between matrix and the
NT is not due to chemical bonds but due to weak van der Waals forces.
Due to poor interfacial bonding, tubes can easily be pulled out of the
matrix.

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 3. It is also difficult to distribute NTs homogeneously through out
matrix.
X marks

3. Molecular mechanics.
(a) Sketch the L-J potential; show ρ and .
It was suggested to use the Lennard-Jones 6-12 interaction potential
with  = 3.87 · 10−22 J and σ = 0.3 nm to describe interaction between
carbon atoms   
σ 12  σ 6
ULJ (r) = 4 − (1)
r r
i) Derive a formula for the equilibrium distance ρ between two atoms.
Find ρ.

(a) The system is at equilibrium when the potential has minimum

value (the interaction force F = −dU/dr is equal to zero at r = ρ).
 
dULJ (r)  σ 12
−1
 σ 6
−1
0 = −FLJ (r) = = 4 −12 r +6 r ,
dr r r
 σ 12  σ 6
2 r−1 = r−1
r r
or
ρ = 21/6 σ = 1.122462σ = 1.122 · 0.3 = 0.3366nm.

X marks

(ii) Find the binding energy of the system.

Substituting ρ into ULJ (r), we find the binding energy ULJ (ρ) = − =
−3.87 · 10−22 J.
X marks

(b) Find K in the Hooke’s (harmonic) approximation of the Lennard-

Jones 6-12 interaction potential at the equilibrium distance
K
ULJ (r) = − + (r − ρ)2 .
2

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 (b) Using the Taylor decomposition

f 0 (a) f 00 (a)
f (x) = f (a) + (x − a) + (x − a)2 + . . . ,
1 2!
we obtain
36
ULJ (r) = − + (r − ρ)2 .
ρ2
We have used the following calculations.
At r = ρ = 21/6 σ ⇒ σ/r = 2−1/6
   
d dULJ (r)   σ 12
−2
 σ 6
−2
= 4 (−12)(−13) r + 6(−7) r =
dr dr 
r=ρ r r r=ρ
h
12
6 i
4 (12 · 13) 2−1/6 ρ−2 − 42 2−1/6 ρ−2 =
72
4[(12 · 13)(1/4)ρ−2 − 42(1/2)ρ−2 ] = 4[39 − 21]ρ−2 = .
ρ2
0
Therefore, at r = ρ: ULJ (ρ) = −, ULJ (ρ) = 0, and

00 72
ULJ (ρ) = .
ρ2
Comparing this with the Hooke’s approximation
K
ULJ (r) = − + (r − ρ)2 ,
2
we obtain
72 72 · 3.87 · 10−22
K= = = 0.2459N/m.
ρ2 (0.3366 · 10−9 )2

X marks
(c) Let us consider vdW interactions between a one-atom-thick sur-
face and a molecule located at distance z from the surface. Let N1
be the number of atoms per unit area of the surface. Let us as-
sume that the interaction between the molecule and each atoms of the
surface is described by the Lennard–Jones [6, 12] potential (1) where
ULJ [6, 12](l) = ULJ (l).
Show that the interaction between the molecule and the one-atom-thick
surface is described by the Lennard–Jones [4, 10] potential ULJ [4, 10](z).
Find the equilibrium distance z0 .

Solution.

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 1) Consider the Lennard-Jones interaction potential
  
σ 12  σ 6
ULJ [6, 12](l) = 4 − (2)
l l

For an atom located at the distance z from a surface, the potential is

the sum of the interaction potentials between the atom and each of the
atoms of the 2D surface. Hence we have to integrate the potentials in
a cylindrical system of coordinates taking into account that the polar
angle φ, changes from 0 to 2π and the polar radius r from 0 to ∞. In
polar system of coordinates an elementary area dA = rdrdφ. Then one
has
Z 2π Z ∞ √
ULJ (z) = ULJ [6, 12](l)N1 rdrdφ, l = z 2 + r2
0 0
Z ∞    σ 6 
σ 12
ULJ (z) = 2π · 4N1 − d(r2 /2)
0 l l
Because rdr = d(r /2) = d[(r + z 2 )/2], we have
2 2

Z ∞  12  6 
σ σ
ULJ (z) = 8π · N1 − d[(r2 + z 2 )/2]
0 l l

or denoting ξ = l2
" 6 3 #
∞
σ2 σ2
Z 
ULJ (z) = 8π · N1 − d[ξ/2].
z2 ξ ξ

or
∞
σ 12 σ6 σ 12 σ6
  
ULJ (z) = 8π·N1 − + = 8π·N1 − = ULJ [4, 10](z).
10ξ 5 4ξ 2 z2 10z 10 4z 4

2) The system is at equilibrium when the potential has minimum value

(this is because the interaction force F = −dU/dz is equal to zero at
the equilibrium distance z = z0 )
 12
σ6

dULJ [4, 10](z) σ
0 = −FLJ (z) = = 8πN1 − 11 + 5 ,
dz z z
or
σ 12 σ 6 1 σ6
− + = 0 ⇒ = ⇒ z011 /z05 = σ 6 ⇒ z0 = σ.
z 11 z5 z5 z 11

X marks

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 4. Adhesion of solids.
(a) Consider the Tabor-Muller parameter
1/3
Ref w2

µ=
(E ∗ )2 z03

Explain the meaning of the components.

w is the work of adhesion of the contacting pair of materials. If

materials are the same then w = 2γ where γ is the surface energy,
1/Ref = 1/R1 + 1/R2 where R1 and R2 are the radii of curvature of
contacting spheres, E ∗ is the effective contact modulus of contacting
pair. If materials are the same then E ∗ = E/2(1−ν 2 ), z0 is the equilib-
rium distance between atoms of contacting pair, usually it is between
0.3 - 0.5 nm.
X marks

(b) What is the Derjaguin approximation?

The Derjaguin approximation can be formulated as follows:

(i) instead of the pairwise summation of the interactions between the
elements of solids, the volume molecular attractions are reduced to
surface interactions;
(ii) the surface interactions are taken into account only between closest
elements of the surfaces laying on vertical straight lines, and
(iii) the interaction energy per unit area between small elements of
curved surfaces is the same as this energy between two parallel infinite
planar surfaces.
X marks

(c) Derive the expression for adhesion between a rigid sphere Pc and
an elastic half-space using the Derjaguin approximation.

Using the Hertz approximation, one can replace a sphere of radius R

by a paraboloid of revolution z = f (r) = B2 r2 , where B2 = 1/(2R).
Then applying the Derjaguin approximation, one obtains
Z 2π Z ∞ Z ∞ Z ∞
Pc = pa [z(r)]rdrdφ = 2πR pa (z)·dz = 2πRw, w= pa (z)dz.
0 0 0 0
(3)

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 Here pa (z) is the adhesive force per unit area between flat surfaces
separated by a distance z.
X marks

(d) In an engineering laboratory surface energy measurements have

been carried out on nanoparticles coated with different types of organic
compound. It was found that for 0.3 % weight percent of Siloxane coat-
ing the surface energy was γ = 22 · 10−3 J/m2 while for 0.8 % weight
percent of Silane coating the surface energy was γ = 2 · 10−3 J/m2 .

Find the force of cohesive interaction between a fine spherical particle

of radius R and a surface of half-space. Both materials are a titanium
dioxide whose surfaces have the same coating. Young’s modulus and
Poisson ratio of coated titanium dioxide are E = 110GP a and ν = 0.33,
respectively.
(i) Radius of the particle is R = 300nm and it is coated by Silane.

The effective radius 1/Ref = 1/R1 + 1/R2 where R1 and R2 are the
individual particle radii. Since R1 = 300nm and R2 = ∞, we have
Ref = R.
The effective modulus is E ∗ = E/[2(1−ν 2 )] = 110/[2(1−0.332 )] = 61.7
GPa. Hence the Tabor-Muller parameter is (w = 2γ)
1/3
300 · 10−9 · (2 · 2 · 10−3 )2


1/3
µ= = 19.7 · 10−3 · 10−1 = 0.027
(61.7)2 · 1018 · 43 · 10−30

µ = 0.027 < 1 , hence, we have to use DMT model. For DMT pull of
force is FDM T = 4πRef γ = 2πRef w = 2 · 3.14 · 300 · 10−9 · (4 · 10−3 ) =
7.536 · 10−9 N.
X marks

(ii) Radius of the particle is R = 200µm and it is coated by Siloxane.

The effective radius Ref = R = 200µm.
The effective modulus is E ∗ = E/2(1 − ν 2 ) = 110/2(1 − 0.332 ) = 61.7
GPa. Hence the Tabor-Muller parameter is
1/3
200 · 10−6 · (44 · 10−3 )2

µ= = (1.563)1/3 = 1.16
(61.7)2 · 1018 · 43 · 10−30

µ = 1.16 > 1 , hence, we have to use JKR model. For JKR pull of force
is FJKR = 3πRef γ = 3/2πRef w = 3/2 · 3.14 · 200 · 10−6 · (44 · 10−3 ) =
41.4 · 10−6 N.

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 X marks

5.
(a) Using Lagrange equation of the second type, derive the equation
of free horizontal oscillations for a mass m that is attached to a spring
of stiffness k?
Answer. This is a system with one-degree-of-freedom because the
horizontal coordinate x characterises the system. We chose x = 0 at
the equilibrium point. The kinetic energy of the mass is T = mẋ2 /2,
the potential energy of the spring is Π = kx2 /2 and the Lagrange
function L = T − Π = (mẋ2 − kx2 )/2.
   
d ∂L ∂L
− =0
dt ∂ ẋ ∂x

Substituting L, we obtain
   
∂L ∂L
= mẋ, = −kx
∂ ẋ ∂x

Putting these values into the Largange equation, we obtain

d2 x
m + kx = 0
dt2

What is the general solution to the equation?

x(t) = A sin(ω0 t) + B cos(ω0 t)

p
where A and B are arbitrary constants, and ω0 = k/m is the eigen-
frequency of the system.
How many initial conditions one needs to get a particular solution of
oscillations?
One needs two initial conditions to get constants A and B, and, hence,
the particular solution of oscillations.
(b) Consider an AFM cantilever beam (CB) of a rectangular cross
section. What is eigenfrequency of a cantilever with elastic modulus
E = 200 GPa, density ρ = 4 g/cm3 , length l = 300µm, width w =
20µm and thickness t = 2µm?
Answer. The value of the elastic modulus is given in GPa. Let us
recalculate it in N/µm2 . E = 200 GPa=200·109 N/m2 = 200·109 ·10−12
N/µm2 = 0.2 N/µm2 .

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 wt3 20·23
The moment of inertia of the CB cross-section is I = 12
= 12
=
160
12
= 13.3 µm4 .
The spring constant estimated by using beam theory is given by

3EI Ewt3
k= 3 =
l 4l3
Hence, we have
3 · 0.2 · 13.3 8
k= 3
= · 10−6 N/µm = 0.296N/m.
300 27

The mass of the CB is m = w · t · l · ρ = 2 · 20 · 300 · 4 · 10−12 g=48 · 10−9

g = 48 · 10−12 kg.
The effective mass of the CB m∗ is m∗ = 0.24 · m = 0.24 · 48 · 10−12 =
11.52 · 10−12 kg The resonant frequency is
r r
1 k 1 0.296
f0 = ∗
= −12
= 2.55 · 104 sec−1
2π m 6.28 11.52 · 10

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 (c) Consider a CB with the spring constant k = 6 · 10−3 N/m. A
virus of unknown mass mv sticked to a cantilever beam at the free
end. Calculate the mass of the virus if the eigenfrequency of the CB
is f0 = 1.26 · 106 Hz and the eigenfrequency of the CB with additional
mass is f1 = 1.2 · 106 Hz.
Answer. The resonant frequency of the CB is
r
1 k
f0 = .
2π m∗
The resonant frequency of the CB with added mass is
r
1 k
f1 = ∗
2π m + mv
Hence,
k 1
m∗ =
(2π)2 f02
and
k 1
m∗ + mv = .
(2π)2 f12
From the above equations, we have

k 
(f1 )−2 − (f0 )−2 = 1.52 · 10−4 (1.2)−2 − (1.26)−2 · 10−12
  
mv = 2
(2π)

mv = 9.8 · 10−18 kg = 9.8f g.

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