European Polymer Journal 44 (2008) 3409–3416

Contents lists available at ScienceDirect

European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Macromolecular Nanotechnology

Boëder PDF Brownian simulations for macromolecular rod-like

particles near uneven solid surfaces
Abbas Hijazi a,b,c,*, Antoine Khater a,*
a
Laboratoire de Physique de l’Etat Condensé UMR 6087, Université du Maine, Avenue Olivier Messiaen, 72000 Le Mans, France
b
Département de Physique, Université Libanaise, Hadath-Beyrouth, Lebanon
c
Département de Physique, Faculté des Sciences et des Arts, Université UIL, Khaldé, Lebanon

a r t i c l e i n f o a b s t r a c t

MACROMOLECULAR NANOTECHNOLOGY
Article history: A molecular dynamics simulation is presented to calculate the Probability Distribution
Received 7 April 2008 Functions (PDF) for the spatial positions and angular orientations of macromolecular
Received in revised form 19 June 2008 rod-like particles in dilute solutions, under hydrodynamic flow, in the vicinity of uneven
Accepted 5 August 2008
solid boundaries. The Brownian and hydrodynamic restitution model for ideally flat sur-
Available online 20 August 2008
faces is generalized to simulate the diffusive collisions between the macromolecular parti-
cles and an uneven solid surface. Two types of uneven surfaces are particularly considered:
the periodic grating and the random rough, with characteristic profiles of heights and lat-
Keywords:
Boeder PDF
eral variations. Different from ideally flat surfaces, the simulation results demonstrate that
Complex fluids uneven surfaces have characteristic depletion layers, and characteristic and variable PDF.
Numerical simulations This is the case under varying conditions of hydrodynamic flow, Brownian movement
Uneven surfaces and diffusive collisions. These characteristics uniquely identify Boeder PDF signatures for
Mesopore nanotechnology the uneven surface topography.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction solution containing dilute concentrations of suspended

Interest in the motion and average orientations of mac-
romolecules at dilute concentrations in the bulk of a flowing
liquid, stems from the physical effects that may arise when
these solutions flow, with their load of macromolecules, in-
side channels of mesoscopic dimensions [1]. The statistics
for the spatial positions of the centres of mass and for the
orientations of such macromolecules, under equilibrium
dynamics inside the flow, are then of particular interest.
The spatial positions and the orientations of such mac-
romolecules are determined, under flow conditions of the
solution, by two conflicting forces, the first is a hydrody-
namic force stemming from the shear flow, and the other
is thermal originating from Brownian diffusion.
Boeder [2], is the first to have studied this problem,
from the theoretical point of view, in the bulk of a flowing
* Corresponding authors.
E-mail addresses: abhijaz@ul.edu.lb (A. Hijazi), antoine.khater@univ-
lemans.fr (A. Khater).
macromolecular rod-like particles. He suggested an ordin-
ary differential equation that governs the Probability Dis-
tribution Functions (PDF), P(h), where h is the orientation
of a macromolecular rod-like particle. This differential
equation is derived in two dimensions in the plane of the
linear laminar flow, for macromolecular rod-like particles
of negligible cross-sectional area, in the form
2
P00 þ ½a sin ðhÞP0 ¼ 0 ð1Þ
This so called Boeder Differential Equation (BDE) as in Eq.
(1) is derived as a functional of the dimensionless a
a ¼ c_ =Drot ð2Þ
c_ is the shear rate in the hydrodynamic laminar flow, and
Drot is a diffusion coefficient for the Brownian rotational
motion of the macromolecular rod-like particle. The
number a is then a dimensionless measure for the ratio
of the shear hydrodynamic flow to the rotational diffusion
coefficient. For a given solvent, different macromolecules
have different values of Drot [3–5]. The shear rate c_ in the

0014-3057/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.08.007
 3410 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416
laminar flow of the solutions is in contrast characteristic of
the hydrodynamic flow conditions. For one and the same
macromolecule, low and high a correspond then, respec-
tively, to low and high flow.
Boeder gave a series mathematical solution valid for
only small values of a, and a Taylor series development
for the high values of a that suffered from the difficulty
of identifying the necessary boundary conditions. Some
improvements have been made, first to remove restrictions
on the cross-sectional areas of such macromolecules, and
secondly to be able to consider their rotational diffusion
in three dimensions [6–8], but these efforts have been lim-
ited to small values of a.
The analytical solution of the Boeder Differential Equa-
tion in the bulk has been obtained recently in general in
two dimensions, in the plane of the linear flow, for a wide
range of a [9]. Special analytical as well as numerical meth-
ods are developed in order to calculate accurately the PDF
distributions, for all arbitrary values of a. Turbulence ef-
fects, however, are known to take place for a P 104, and
the BDE equation ceases to apply in a strict physical sense
beyond this value.
MACROMOLECULAR NANOTECHNOLOGY
Furthermore, Brownian 2D simulations have been con-
structed to calculate the PDF probability distributions for
macromolecular rod-like particles in a flowing solution
near ideally flat solid surfaces, in open and bounded chan-
nels [10–12], for a wide range of a values.
For rod-like macromolecules in the solution, the
Brownian and hydrodynamic shear forces give rise to diffu-
sive collisions with the solid surface boundary. There is,
however, very little information available in the literature
concerning the nature and dynamics of these diffusive col-
lisions. An analytical solution in the depletion region, com-
parable to that in the bulk, is hence too complex since the
mathematical problem of the collisions is intractable.
In previous simulations which attempt to treat this par-
ticular problem, two algorithms have been tested [13]. The
so-called naive algorithm treats these collisions by ignor-
ing them, where if a particle should penetrate the solid sur-
face the corresponding simulation configuration is not
accepted. A second improved algorithm begins by estimat-
ing the random time at which a collision takes place during
a simulation time step with the use of a complicated time
bisection procedure. The particle is then left in the collision
configuration when it gets to it, with one extremity touch-
ing the surface, until a random event allows it to move
away in the remainder of the simulation time step. The
simulation results of this algorithm are dependent on the
choice of the time step leading to different results for dif-
ferent time steps. There is a literature on Brownian dynam-
ics simulations of polymer solutions [14,15], although this
is outside the scope of the present study.
To circumvent the problem encountered in Ref. [13],
and another which arises due to the absence of detailed
knowledge of the physical nature of the diffusive collisions
at the solid boundaries, mechanical restitution was intro-
duced for Brownian and the hydrodynamic collisions, in
order to develop an algorithm for the these collisions at
an ideally flat solid surface boundary [10,11]. The formal-
ism for surface simulations is developed in a similar man-
ner to that for bulk simulations, which results have been
found in agreement with the exact analytical solutions of
the bulk BDE. Furthermore, the assumptions of restitution
were tested experimentally and found valid for micro-
scopic macromolecular particles [12]. Surface PDF distribu-
tions, given as a function of the spatial positions of the
centres of mass and of the angular orientations of the mac-
romolecular rod-like particles, are thus calculated for the
physical range of possible values of the restitution.
The simulated surface spatial PDF distributions for
ideally flat surfaces are consistently concave in the deple-
tion layer as is physically expected. For small a i.e. low flow
conditions, these PDF distributions are shown to be the
result of a dynamic balance between competing Brownian
and hydrodynamic diffusive collisions. For large a, the
macromolecular particles are shown to be evacuated from
the depletion layer by the dominant hydrodynamic colli-
sions, which effect is consistent with experimental obser-
vations. On the other hand, the numerically simulated
surface angular PDF distributions for the depletion layer
show marked differences from their bulk counterpart.
The purpose of this paper is to perform Boeder Brown-
ian simulations to examine the angular and spatial Boeder
PDF distributions in the vicinity of uneven solid surfaces.
Theoretical models and experimental interpretations for
surface problems are often restricted to ideally flat surfaces
in a first approximation. This is justified provided the
probe wavelength is much greater than the standard devi-
ation of surface uneven heights for a given surface
topography.
From a nanoscopic perspective a perfectly smooth solid
surface does not exist [16–19]. Surfaces can be naturally
rough, due to growth, fracture, or erosion. And regardless
of the efforts to reduce the surface roughness during prep-
aration, it is impossible to totally eliminate this at different
length scales. A number of profiling techniques applied to
the finest optical surfaces [20,21], are capable of measuring
surface nanometer roughness. Ref. [16] gives the topogra-
phy of a rough solid surface with large microscopic inho-
mogeneities reconstructed using optical correlation
diagnostics, as in Fig. 1.
Uneven surfaces manifest themselves also under other
categories. Of particular interest are the manufactured grat-
ing surfaces important for a variety of applications [22–27].
Advanced technical methods allow one effectively to endow
surfaces with specific, regular patterns down to the nano-
meter scale [28,29]. Ref. [23] gives, for example, the topogra-
phy of a surface grating with characteristic spatial
dimensions that characterize its unevenness, as in Fig. 2.
In the present paper we examine specifically the simula-
tions of the Boeder PDF distributions for the rod-like macro-
molecular particles, in the neighborhood of the uneven
surfaces as the grating and the random rough. The paper is
organized as follows. In Section 2, the geometry and the
model are introduced and the basic elements of the simula-
tions are presented. In Section 3, the calculated PDF distribu-
tions for the uneven surfaces are analyzed and compared to
the PDF distributions for a flat solid surface. It is shown that
the surface unevenness strongly modifies the flat surface
PDF distributions. Further, these distributions are distinct
signatures for each type of uneven surface, and the corre-
sponding depletion layer is modified with respect to flat sur-
 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416 3411

Fig. 1. A typical topography of a rough solid surface at the microscopic scale, from Ref. [16].

MACROMOLECULAR NANOTECHNOLOGY
Fig. 2. A typical topography of a grating solid surface at the microscopic scale, from Ref. [23].

face results. It is seen that these PDF distributions are char-
acteristic of the unevenness of the solid boundary.
2. The model algorithm for simulations
In this section, we present the model for numerical
simulations. The notion of restitution is developed to
develop an algorithm for the diffusive collisions of the
macromolecular particles with the uneven grating and
the random rough surfaces. The joint PDF distributions,
P(h, n), are calculated as a function of the angular orienta-
tions h of the macromolecular particles and the normalized
distance of their center of mass n, measured from a refer-
ence plane at the boundary. The solution is considered sta-
tionary in contact with the uneven solid surface boundary,
and the shear rate field c_ is assumed to be uniform beyond
the uneven topography.
For the dynamics of the macromolecular particles, zc
shall denote the distance that separates their centre of
mass from a chosen reference plane in the boundary. In
the bulk it is possible to neglect the Brownian translation
diffusion, since this has no statistical incidence on the
angular PDF distributions, P(h). However, near a surface
boundary this translation diffusion contributes to deter-
mining the displacement of the particles from the bulk
towards the depletion layer and vice versa. Brownian diffu-
sion comprises hence both rotation and translation diffu-
sion in the neighbourhood of solid boundaries, and for
relatively low concentrations of the particles it is possible
to treat the diffusive collisions arising from both processes
separately.
Since, the detailed nature of the collisions is quite com-
plex, we introduce the notion of mechanical restitution for
both Brownian and hydrodynamic collisions. These colli-
sions take place in the algorithm following, respectively,
a Brownian or a hydrodynamic bulk movement that brings
a macromolecular extremity into contact with the solid
surface boundary. They are distinguished physically by
treating the Brownian collision as due to a Brownian ran-
dom event following which the macromolecule should
come away from the surface in an equally random manner;
in this sense a surface Brownian collision intercedes across
the same random Brownian movement. The hydrodynamic
collision in contrast is caused by the laminar flow before
and after such a collision; in this sense a surface hydrody-
namic collision intercedes across the causal flow, forma-
lised by the turning of the macromolecular rod-like about
 3412 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416
its extremity after the hydrodynamic collision. Two inde-
pendent restitution coefficients, e and e0 , are then consid-
ered to describe, respectively, the Brownian and hydrody
namic collisions. The two restitution coefficients, are both
defined on a [0, 1] measure interval, as detailed next.
The collisions algorithm is constructed next over a
sequence of events, named n, ncollision, n + 1, for a collision
arising due to translation diffusion. Note that n denotes
the event before collision, and n + 1 the event after colli-
sion and that near a surface boundary the extremities need
to be identified in order to distinguish and follow the col-
lisions of one or the other with the surface boundary. To
illustrate this see Fig. 3a for the case of the grating surface
and rod-like particle. Without loss of generality we con-
sider the grating spacing and the periodic microstructure
to be of equal lengths, namely a. The height of the micro-
structure is b, and L is the common length of the rod-like
macromolecules. It is assumed that
b < L << a
This is a general condition applying for macromolecules of
variable lengths provided they scale following Eq. (3).
MACROMOLECULAR NANOTECHNOLOGY
In a given simulation sequence for a Brownian transla-
tion diffusion, the limiting case e = 0 corresponds to stick-
ing, whereas e = 1 corresponds to the restitution of the
macromolecular particle to its previous position. The resti-
tution coefficient satisfies in general the conditions
0 6 e 6 1, and the simulations are investigated for different
possibilities.
b L/2 - b ran(0,1) - Zc(n)
Zc(n+1)
Variable height = Zc(n)
b ran(0,1)
Fig. 3. Basic algorithm elements for the collision configurations of the rod-like macromolecular particles with a grating surface in Fig. 3a, and with a rough
surface in Fig. 3b.
A generalized Brownian random variable, Dzc,tr is intro-
duced that displaces the particle in either sense normal to
the reference plane in the boundary. The ambiguities aris-
ing from the arbitrary simulation time steps are eliminated
in order to derive an expression for Dzc,tr = zc(n + 1)zc(n)
as a function of the simulation variable Dh = h(n + 1)h(n).
In the case when a random translation Brownian diffusion
event brings one of the extremities of the rod-like molecu-
lar particle into collision with the surface, we may write
that
zc ðn þ 1Þ ¼ zcollision þ e½zc ðnÞ  zcollision 
zcollision ¼ L=2 j sin hðnÞ j þbran ð0; 1Þ ð4Þ
L=2 sin hðnÞ j is the touch distance of the centre of mass of
the particle from a reference plane, here considered to be
the base plane for a grating surface. For such a periodic
grating surface, the algorithm element ran(0,1) is consid-
ered as a purely random integer that is either 0 or 1, with
ð3Þ equal probabilities. The touch angle for the present
sequence is h(n) = h(n + 1). This sequence determines Dzc,tr,
whereas the next event beyond n + 1, moves the particle
into other accessible configurations.
The Brownian rotation diffusion that brings one of the
extremities of the particle into collision with the boundary
may be characterized in a comparable manner. In this case
zc(n + 1) = zc(n) is the touch distance of the centre of mass
from the reference plane, and we have the rotation algo-
rithm for collisions as
L/2
2D profile of
rough surface
θ (n+1)
 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416 3413

hðn þ 1Þ ¼ hcollision  e j hðnÞ  hcollision j Z c ðn þ 1Þ ¼ L=2 þ b ranð0; 1Þ

hcollision ¼j arcsinf2½zc ðnÞ  branð0; 1Þg=L j
The choice of plus or minus sign in Eq. (5) depends on
which of the two extremities collides with the solid
boundary.
To construct an algorithm for the hydrodynamic colli-
sions we use an independent restitution coefficient, e0 , over
the acceptable range 0 6 e0 6 1, [10,11]. For the limiting case
e0 = 0, the rod-like particle is supposed to slide maintaining
its touch configuration, whereas e0 = 1 corresponds to its
rotation under the influence of the flow into a maximum
turning angle before losing contact with the solid boundary.
Both of these limiting cases have been investigated in a pre-
vious work, [12], where the theoretical model and the resti-
tution assumption is checked experimentally for dilute
solutions of microscopic rod-like fibers. The maximum turn-
ing angle has been identified as 3p/4. It is then possible to
introduce the following condition in the algorithm for e0 = 1
ð5Þ hðn þ 1Þ ¼ 3p=4 ð6Þ
In the present analysis the collisions arising due to the
hydrodynamic flow are characterized in the numerical
simulations by different values of e0 . The algorithm for
hydrodynamic restitution after a collision may be then
written in general for the position and orientation as
Z c ðn þ 1Þ ¼ zc ðnÞ þ e0½L=2 þ b ranð0; 1Þ  zc ðnÞ
hðn þ 1Þ ¼j arcsinf2½zc ðn þ 1Þ  b ranð0; 1Þg=L j ð7Þ
The algorithm presented in Eqs. (4)–(7) is also applied to
random rough surfaces. In this case the algorithm element
0 6 ran(0,1) 6 1 is, however, treated as a random real num-
ber having equally probable values between 0 and 1, over
the interval [0, 1]. Such purely random rough surfaces
are rare, because rough surfaces often present surface cor-
relations with Gaussian profiles. Nevertheless, the present

MACROMOLECULAR NANOTECHNOLOGY
a periodic grating surface α =2. e=0.5
0.004
P(ξ ) normalized

0.003

0.002 e'=0
e'=0.5
e'=1
0.001

0.000
0.0 0.2 0.4 0.6 0.8 1.0
ξ

b periodic grating surface α =50. e=0.5

0.005

0.004
P(ξ) normalized

0.003

e'=0
0.002 e'=0.5
e'=1
0.001

0.000
0.0 0.2 0.4 0.6 0.8 1.0
ξ

Fig. 4. Typical simulation results, for a surface grating, for the normalized PDF P(n), folded over the orientations, as a function of the normalized distance, n,
of the centre of mass of the macromolecular rod-like particles, measured from the reference plane. The P(n) are calculated in the depletion layer in the
vicinity of the surface grating, for a fixed choice of the restitution coefficient e = 0.5, and for variable e0 , at conditions of relatively low flow, a = 2, in Fig. 4a,
and of relatively high flow, a = 50, in Fig. 4b, for comparison.
 3414 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416

application of the model to such surfaces is useful to test
the algorithm.
In Fig. 3b the algorithm scheme of the diffusive colli-
sions of the rod-like particles with an uneven surface is
presented, for random rough surfaces. The reference plane
is a flat plane that corresponds to the base line in Fig. 3b.
Further, we assume that successive diffusive collisions
with the uneven surface are independent of surface topo-
graphic correlations, for the choice of b and L. This assump-
tion, however, is not applicable when the length of the
macromolecular particle is comparable to the mean height
of the uneven surface, for which b P L, when both lateral
and normal correlations of the uneven surface, become
important.
3. Simulation results and conclusions
The numerical simulations are applied next for two
uneven surfaces types, the periodic grating and random
rough. We consider in general that b = L/10 to satisfy the
MACROMOLECULAR NANOTECHNOLOGY
algorithm condition b << L, and go through N = 108 events
per Monte Carlo simulation run.
In Fig. 4, are presented, for the surface grating, typical
simulation results for the joint normalized PDF P(n), folded
over the orientations, as a function of the normalized dis-
tance of the centre of mass of the macromolecular rod-like
particles, n, from the reference base plane. The P(n) are cal-
culated, for a fixed choice of the Brownian restitution
e = 0.5, and for variable hydrodynamic restitutions e0 = 0,
0.5, and 1, at conditions of low hydrodynamic flow, a = 2,
in Fig. 4a, and high flow, a = 50, in Fig. 4b. The first obser-
vation is the existence of effectively two depletion layers,
the first in the interval 0 6 n 6 0.5, as for an ideally flat sur-
face, and the second in the interval 0.5 6 n 6 0.5 + 2b /L.
This is a new effect absent from the case of an ideally flat
surface. It may be readily understood in terms of the
cumulative effects of the collisions of the rod-like particles
relative to the reference plane between the grating ele-
ments, and to the height of the grating elements above
the reference plane. Note that P(n) is consistently concave
in the total depletion layer, with pinning at n = 0.5, and that

a 0.005
random rough surface α =15

0.004
P(ξ) normalized

0.003

0.002 e=e'=0
e=e'=0.5
e=e'=1
0.001

0.000
0.0 0.2 0.4 0.6 0.8 1.0
ξ
0.005
b
random rough surface α=100

0.004
P(ξ) normalized

0.003

0.002
e=e'=0
e=e'=0.5
0.001 e=e'=1

0.000
0.0 0.2 0.4 0.6 0.8 1.0
ξ

Fig. 5. Typical simulation results, for a rough surface, for the normalized PDF P(n), folded over the orientations, as a function of the normalized distance, n, of
the centre of mass of the macromolecular rod-like particles, measured from the reference plane. The P(n) are calculated in the depletion layer in the vicinity
of the rough surface, for variable values of e = e0 , at conditions of relatively medium flow, a = 15, in Fig. 5a, and of relatively high flow, a = 100, in Fig. 5b, for
comparison.
 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416
α=0. e=0. e'=0
0.0040
0.0035
0.0030
P(ξ ) normalized 0.0025
0.0020
0.0015
0.0010
0.0005
0.0000
0.0
Fig. 6. A comparison of simulation results for the PDF P(n), under identical conditions, for the flat, grating and rough surfaces, where the normalized n is
measured from a common reference plane. The P(n) are calculated for a stationary liquid, a = 0, and for e = e0 = 0.
it decreases with increasing a. This is expected and is due
to the hydrodynamic flow which tends to evacuate the par-
ticles with increasing a.
In Fig. 5, are presented, for the random rough surface,
typical simulation results for the joint normalized PDF
P(n). This is calculated for variable values of the Brownian
and hydrodynamic restitutions, e = e0 = 0, 0.5, and 1, at
conditions of medium flow, a = 15, in Fig. 5a, and high flow,
a = 100, in Fig. 5b. It is observed that the rough surface
washes away the trace of the two distinct depletion layers
observed in the previous case of a periodic grating surface.
For a random rough surface the depletion layer is effec-
tively a single homogeneous layer over the entire interval
0 6 n 6 0.5 + 2b /L. The second observation concerns the
concavity of the PDF P(n), in the depletion layer, for differ-
ent e and e0 . For the medium hydrodynamic flow, a = 15,
P(n) is convex for e = e0 = 0 and as such is the inverse of
the concavity for e = e0 – 0. The convex character is modi-
fied for the high hydrodynamic flow, a = 100, for which
conditions the differences between the individual PDF
P(n), for different e = e0 – 0, also become amplified. This
P(n) signature corresponds to a greater probability of find-
ing the rod-like particles in the depletion layer for
e = e0 = 0, as compared to the situation for e = e0 – 0. Note
that a critical nc1.3 signals the departure of the concavity
in one sense and another, which value is evidently charac-
teristic of the random rough surface at low hydrodynamic
flow. This signals for low Brownian and hydrodynamic res-
titutions the build up of the rod-like particles in the deple-
tion layer near the rough surface when sticking collision
events are allowed for e = e0 = 0. Furthermore, it is demon-
strated that the Brownian and hydrodynamic restitution
effects are of comparable magnitude for low flow condi-
tions, whereas the hydrodynamic restitution dominates
for high flow conditions.
Fig. 6 presents the simulation results for the PDF P(n),
for a solution at rest, a = 0, and for the Brownian and
hydrodynamic restitutions e = e0 = 0. The purpose here
3415
flat surface
grating surface
random rough surface
0.2 0.4 0.6 0.8 1.0
X
MACROMOLECULAR NANOTECHNOLOGY
is to compare under the same conditions the results for
three different surfaces. It is seen that the differences
in the PDFs are significantly enhanced in the depletion
layer under certain restitution conditions. The normal-
ized n is measured from a common reference plane for
all three surfaces.
In Fig. 7 we present simulation results for the normal-
ized PDF P(h), folded over the distances, n, of the centre
of mass of the particles in the depletion layer of the grat-
ing surface, as a function of the orientations, h, measured
with respect to the reference angle h = 0 parallel to the
flow. The P(h) PDF are calculated, for the variable condi-
tions of low hydrodynamic flow, a = 0, 2, 6, for
e = e0 = 0.5 in Fig. 7a, and for e = e0 = 1 in Fig. 7b. As ex-
pected these P(h) PDF are symmetric with a maximum
about the reference angle h = 0, for a stationary liquid
at rest. It is interesting to note that the P(h) PDF are
asymmetric with increasing flow a – 0. In particular
the peak displaces with increasing a in a monotonic
manner for full restitution e = e0 = 1, but has a varying
behaviour for partial restitution e = e0 = 0.5.
In this paper we have presented a model for numerical
simulations to determine the angular and spatial Boeder
PDF probability distributions for macromolecular rod-like
particles under equilibrium dynamics of Brownian motion,
hydrodynamic flow and diffusive collisions at uneven solid
surface boundaries. The simulation results indicate that
such surfaces have characteristic depletion layers and
characteristic PDF probability distributions, different from
those for ideally flat surface boundaries.
Acknowledgments
Antoine Khater wishes to thank Luc Barbier, Bernard
Salanon, and the Service de Physique et Chimie des
Surfaces et des Interfaces of the Commissariat à l’Energie
Atomique (CEA), Saclay, France, for their support during
his visit.
 3416 A. Hijazi, A. Khater / European Polymer Journal 44 (2008) 3409–3416

a grating surface e=0.5. e'=0.5

0.012
α=0
0.010 α=2
α =6

P(ξ) normalized
0.008

0.006

0.004

0.002

0.000
-80 -60 -40 -20 0 20 40 60 80
θ

b 0.014 grating surface e=1. e'=1

MACROMOLECULAR NANOTECHNOLOGY

0.012 α =0
α=2
0.010 α =6
P(ξ) normalisée

0.008

0.006

0.004

0.002

0.000
-80 -60 -40 -20 0 20 40 60 80
θ

Fig. 7. Typical simulation results for the normalized PDF P(h), folded over the distances of the centre of mass of the macromolecular rod-like particles in the
depletion layer of the grating surface, as a function of the orientations, h, measured with respect to the reference angle h = 0 parallel to the flow. The P(h), are
calculated, for the variable conditions of the relatively low flow, a = 0, 2, 6, for e = e0 = 0.5 in Fig. 7a, and for e = e0 = 1 in Fig. 7b, for comparison.

References [15] Brostow W, Drewniak M. J Chem Phys 1996;105:7135.

[16] Angelsky OV, Maksimyak AP, Maksimyak PP, Hanson SG. Opt Exp
2006;14:7299.
[1] Storm AJ, Chen JH, Ling XS, Zandbergen HW, Dekker C. Nat Mater
[17] Zhao YP, Yang H-N, Wang G-C, Lu T-M. Appl Phys Lett
2003;2:537;
1996;68:3063.
Kasianowics JJ, Nguyen TL, Stanford VM. Proc Natl Acad Sci
[18] Reiss G, Schneider F, Vancea J, Hoffmann H. Appl Phys Lett
2006;103:11431;
1990;57:867.
Fritz L, Ruebner J, Springer J, Wolff D. In: Brostow W, editor.
[19] Pignataro B, De Bonis A, Compagnini G, Sassi P, Cataliotti RS. J Chem
Mechanical and thermophysical properties of polymer liquid
Phys 2000;113:5947.
crystals. London: Chapman & Hall; 1998. Ch. 5.
[20] Song J, Vorburger T. Appl Opt 1991;30:42.
[2] Boeder P. Z Physik 1932;75:258.
[21] Creath K, Wyant J. Appl Opt 1990;29:3823.
[3] Berne B, Pecora R. Dynamic light scattering and applications to
[22] Franke AE, Schattenburg ML, Gullikson EM, Cottam J, Kahn SM,
chemistry, biology and physics. New York: Wiley; 1976.
Rasmussen A. J Vac Sci Technol B 1997;15:2940.
[4] Tanford Ch. Physical chemistry of macromolecules. J. Wiley & Sons; 1961.
[23] Blakely JM, Tanaka S. J Electron Microsc (Tokyo) 1999;48:747.
[5] Gedde UW. Polymer physics. Berlin, New York: Springer; 2002.
[24] Sano H, Kume M, Nakagawa H, Mizutani G. J Appl Phys
[6] Peterlin A. Z Physik 1938;111:232.
2002;91:4229.
[7] Peterlin A, Stuart HA. Z Physik 1938;112:129.
[25] Wei CY, Ye CC, James SW, Irving PE, Tatam RP. Opt Mater
[8] Doi M, Edwards SF. The theory of polymer dynamics. Oxford: Clarendon
2002;20:283.
Press; 1986.
[26] Chang C-H, Heilmann RK, Fleming RC, Carter J, Murphy E,
[9] Khater A, Tannous C, Hijazi A. Comp Mat Sci 2000;18:393.
Schattenburg ML, et al. J Vac Sci Technol B 2003;21:2755.
[10] Hijazi A, Khater A. Comp Mat Sci 2001;20:213.
[27] Vass C, Osvay K. Opt Exp 2006;14:8354.
[11] Hijazi A, Khater A. Comp Mat Sci 2001;22:279.
[28] Konkola PT, Chen CG, Heilmann RK, Joo C, Montoya JC, Chang CH,
[12] Hijazi A, Benyahia L, Khater A, Zoaeter M. Eur Polym J 2003;39:521.
et al. J Vac Sci Technol B 2003;21:3097.
[13] de Pablo JJ, Ottinger HCh, Rabin Y. AIChE J 1992;38:273.
[29] Han J, Li X, Bao H, Zuo G, Wang Y, Feng F, et al. J Micromech Microeng
[14] Brostow W, Drewniak M, Medvedev NN. Macromol Theory Simul
2006;16:198.
1995;4:745.