Thin Solid Films 284-285 ( 1996) 361-364

Surface rheology of monolayers

J. KrSgel ‘, G. Kretzschmar b, J.B. Li b, G. Loglio ‘, R. Miller b,*, H. Miihwald b
a UniversitiitPotsdam, lnstitutfiir Festbrperphysik, Potsdam, Germany
h Max-Planck-Institute fiirKolloid- und Gren.#ichenforschung, Rudower Chaussee 5, D-12489 Berlin, Germany
’ University of Florence, Florence, Italy

Abstract

The surface rheological behaviour of spread monolayers of DPPC (L-cY-dipalmitoyl phosphatidyl chinoline) and DMPE (L-a-dimyristoyl
phosphatidyl ethanolamine) on water has been investigated under shear and dilation/compression deformation. Harmonic area perturbations
are performed using an oscillating barrier method which provides information on the monolayer dilational elasticity and the relaxation
processes happening in the monolayers as a function of surface pressure. A surface shear rheometer has been used to measure the surface
shear viscosity and elasticity of the same monolayers. The shear and dilational rheological properties can be explained by the morphology of
the phospholipid monolayers as a function of surface pressure.

Keywords: Phospholipid monolayers; Surface shear rheology; Surface dilational rheology; Monolayer relaxation

1. Introduction In this work we use recently developed techniques in order

It is well-known that some materials, for example poly-
meric materials and proteins, form very stiff or extremely
viscous monolayers when they are spread on water [ l-6 I.
Their behaviour is obviously characterised by surface rheol-
ogy as they possess large shear viscosity and elasticity. This
information is of great help in understanding the stability of
such films during the transfer process to solid supports.
Phospholipids are organic amphiphilic molecule with two
aliphatic chains connected by a hydrophilic group. They can
be anchored at an air-water interface to form a well-defined
monolayer. Traditionally they are regarded as models for
biological membranes [ 71. Numerous investigations on these
monolayers or their mixture have been performed. Many
characterisations, such as isotherms at various temperatures
[ 81, surface nucleation in compression and expansion [ 93,
growth or decay of a phase [lo], morphology of domain
structure in the phase coexistence range [ 11,121, etc., have
been carried out.
Only very little work has been made so far in understanding
the mechanical properties of such monolayers. These prop-
erties are particularly important from an application point of
view. To know the surface viscoelastic behaviour of a film to
be transferred to a solid support for the purpose of various
optic and electronic devices would be advantageous.
* Corresponding author.
to characterise the mechanical behaviour of phospholipid
monolayers. A torsion pendulum instrument allows one to
determine the shear viscosity and elasticity of the monolayers
at varying surface pressure. A modification of a conventional
Langmuir trough equipped with a second barrier allows one
to perform harmonic area oscillations of the monolayers. The
response to such harmonic perturbation yields information
about the dilational elasticity and viscosity of lipid mono-
layers [ 13-171.
2. Experimental details
2.1. Sulfate shear rheometer
The measuring principle of the surface shear rheometer
ISRl (LAUDA, Germany) has been described elsewhere in
detail [ 181 and was used for different applications [ 19-211.
Briefly, it performs a simple pendulum experiment with a
small deflection of 0.5-3”, resulting in a free oscillation of
the ring which touches the interface under study. The curve
of the damped oscillation is recorded automatically by the
instrument and the important quantities, the damping coeffi-
cient and the circular frequency of the torsion oscillation, are
calculated from
r(r)=y,exp(-i)sin[$(r-b)]+c (1)

0040~6090/96/$15.00 0 1996 Elsevier Science S.A. All rights reserved

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362 J. Krligel et al. /Thin Solid Films 284-285 (1996) 361-364

where a is the decay time, T is the period of oscillation, to is
the phase shift and c is the offset. The parameters a and T
contain the surface shear viscosity and elasticity [ 18,221.
The shear rheology measurements were performed in the
following way. After a small Langmuir trough had been filled
with Millipore water, the monolayer was formed by spreading
the phospholipids from a chloroform solution. After evapo-
ration of the solvent the monolayer was compressed to a
definite film pressure 7~by moving the barrier. The film pres-
sure was measured by a Wilhelmy plate (,F 1 from LAUDA,
Germany). The surface shear viscosity is measured in
dependence on the film pressure. The Langmuir trough con-
sists of two compartments. The film pressure measurements
are carried out in the rectangular part while the surface shear
rheological measurement are made in a concentric ring sys-
tem. The shear stress acts in the slit between an outer fixed
Teflon ring and the inner ring which is the measuring body
of the surface shear rheometer. The fixed Teflon ring has two
gaps to allow the compressed monolayer flowing into the
concentric part of the trough. In that way the same film pres-
sure is established in the rectangular and concentric part of
the apparatus.
with 99% purity was purchased from MERCK. The water
used in all experiments was prepared in a Milliporeapparatus.
3. Results
The PA isotherms of DPPC and DMPE are shown in
Fig. 1. The shape of the two isotherms show differences as
discussed by other workers in the literature but both exhibit
a.well-established coexistence region.
The surface shear viscosity data for DPPC and DMPE are
show in Fig. 2 as a function of surface pressure rr. The deter-
mined shear elasticities were independent of the surface pres-
sure and close to zero and not shown here. At small surface
pressure the shear viscosity is close to zero. With increasing
r-values the viscosity increases first almost linearly and
then abruptly to reach a plateau value at very high surface
pressures.
40-

2.2. Langmuir trough with an oscillating barrier

For measuring the dilational rheological parameters we 30-

used the oscillating barrier method. The set-up has been 2.

described in detail elsewhere [ 13,14,23,24]. The oscillating 2
E zo-
barrier method permits a direct measurement of the surface
Y
pressure oscillation and the phase angle between generation
of the area oscillation and the resulting pressure oscillations. IO-

The complex elasticity modulus of the monolayer is given by

-drr
EC---_= Ed + iwr], (2) o-

d In A
+,.,.,.,.,.,.
40 50 60 70 80 90
The dilational elasticity Ed is obtained from the surface pres-
Area ( AZ/Molec.)
sure amplitude [ 171 and the surface dilational viscosity vd is
Fig. 1. T-A isotherms of DPPC (solid line) and DMPE (dotted line) at
given by [ 251
21 “C.

(3)

Here o is the circular frequency of the barrier oscillation, and

g 2000
0 is the phase shift between an extra peak produced by the
z
excenter moving the oscillating barrier and the maximum in t
the surface pressure response.
The phospholipids were spread OF the modified film bal-
ance as usual. 20 min after spreading the film was compressed
to a definite film pressure IT. Via an electromagnet a second
barrier was placed onto the monolayer at a definite distance
to the force balance. The second barrier is moved periodically
wilh an amplitude of 15 mm and a frequency of 0.1 Hz.

2.3. Material 0 5 10 15 20 25 30 3s 40 45

surface pressure [mN/m]

The phospholipid DPPC (99% + purity) purchased from Fig. 2. Surface shear viscosity of DPPC (0) and DMPE ( n ) in dependence
Sigma was used without further purification. Chloroform on 77.
 J. Kriigel et al. /Thin Solid Films 284-285 (1996) 361-364 363

140- . , n ( . , . , 9 , . , . r700 not been reported so far the shear viscosity rises up sharply.
Maybe the monolayer undergoes a phase transition which has
120- J
I
- 600 not yet been observed. X-ray reflection in this range of surface
a pressure should be best suited to give evidence of such a
- so0 f process if it exists.
B The dilational elasticity and viscosity of both monolayers
5.
- 400 :: show a strong dependence on surface pressure with a mini-
%. mum in the coexistence region. This behaviour can be
u"
b
:: 60- - 300 g explained as follows. As long as two phases coexists a mon-
z
2.
f
olayer compression does not result in a significant pressure
5
40- - 2olJ -i! increase but in a transfer of the liquid expanded (LE) into
the LC phase. During expansion of the monolayer the oppo-
20- - 100 site process hinders a surface pressure change. Thus almost
no phase shift and no elasticity is observed. Only below and
1 above the coexistence region surface pressure changes can
OI .,.,.,.I.( .I. 0
0 2 4 6 s 10 12 14 be generated by area changes so that a measurable dilational
pressure(mNlm)
elasticity and an increasing dilational viscosity are observed.
Fig. 3. Dilational elasticity E and viscosity ~7~of a DMPE monolayer as a
Both parameters increase and level off at a surface pressure
function of surface pressure, T=21 “C, L=7.5 cm, 0=0.628 S-I.
above the end of the coexistence region. From the present
experiments it is not possible yet to specify the mechanism
of the relaxation process in the monolayer which is respon-
sible for the observed dilational viscosity (phase angle).
Probably both a lateral relaxation along the monolayer and
an orientational relaxation happen simultaneously. Further
experiments with a different distance between the oscillating
barrier and the pressure balance and variation in the oscilla-
tion frequency are necessary to enable us to distinguish
between these two and possibly still more relaxation
processes [ 261.

Acknowledgements

The work was financially supported by a project of the

01 . 1 . , . , , . , . , . IJO
0 2 4 6 8 10 12 14 European Community (HCM ERBCHRXT930322) and the
pressure (mN/m) Fonds der Chemischen Industrie (RM 400429).
Fig. 4. Dilational elasticity E and viscosity ~7~of a DPPC monolayer as a
function of surface pressure, T= 20.5 “C. L = 7.5 cm, w = 0.628 s- ‘,

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