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

1. Introduction
It is well-known that some materials, for example polymeric 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 rheology 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 properties 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.

relaxation

In this work we use recently developed techniques in order

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 monolayers [ 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 coefficient and the circular frequency of the torsion oscillation, are
calculated from
r(r)=y,exp(-i)sin[$(r-b)]+c

* Corresponding

author.

0040~6090/96/$15.00
0 1996 Elsevier Science S.A. All rights reserved
SSDIOO40-6090(95)08342-l

(1)

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

362

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 evaporation of the solvent the monolayer was compressed to a
definite film pressure 7~by moving the barrier. The film pressure 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 consists 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 system. 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 pressure 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 determined shear elasticities were independent of the surface pressure 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

30-

For measuring the dilational rheological parameters we

used the oscillating barrier method. The set-up has been
described in detail elsewhere [ 13,14,23,24]. The oscillating
barrier method permits a direct measurement of the surface
pressure oscillation and the phase angle between generation
of the area oscillation and the resulting pressure oscillations.
The complex elasticity modulus of the monolayer is given by
-drr
EC---_=
d In A

Ed + iwr],

2.
2

E zoY
IO-

o-

(2)

+,.,.,.,.,.,.

The dilational elasticity Ed is obtained from the surface pressure amplitude [ 171 and the surface dilational viscosity vd is
given by [ 251

40

50

60

70

Area

Fig. 1. T-A isotherms

21 C.

80

90

( AZ/Molec.)

of DPPC (solid line) and DMPE (dotted line) at

(3)
Here o is the circular frequency of the barrier oscillation, and
0 is the phase shift between an extra peak produced by the
excenter moving the oscillating barrier and the maximum in
the surface pressure response.
The phospholipids were spread OF the modified film balance 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

2000

z
t

10

15

20

25

30

3s

40

45

surface pressure [mN/m]

The phospholipid DPPC (99% + purity) purchased from

Sigma was used without further purification. Chloroform

Fig. 2. Surface shear viscosity of DPPC (0)

on 77.

and DMPE ( n ) in dependence

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

140-

r700

J
I

120-

- 600

a
so0

B
5.
- 400 ::
%.
u"
- 300 g
z
f

b
:: 602.
5
40-

- 2olJ -i!

20-

- 100

OI

.,.,.,.I.(

.I.

6
s
pressure(mNlm)

10

12

14

Fig. 3. Dilational elasticity E and viscosity ~7~of a DMPE monolayer

function of surface pressure, T=21 C, L=7.5 cm, 0=0.628 S-I.

as a

363

not been reported so far the shear viscosity rises up sharply.

Maybe the monolayer undergoes a phase transition which has
not yet been observed. X-ray reflection in this range of surface
pressure should be best suited to give evidence of such a
process if it exists.
The dilational elasticity and viscosity of both monolayers
show a strong dependence on surface pressure with a minimum in the coexistence region. This behaviour can be
explained as follows. As long as two phases coexists a monolayer compression does not result in a significant pressure
increase but in a transfer of the liquid expanded (LE) into
the LC phase. During expansion of the monolayer the opposite process hinders a surface pressure change. Thus almost
no phase shift and no elasticity is observed. Only below and
above the coexistence region surface pressure changes can
be generated by area changes so that a measurable dilational
elasticity and an increasing dilational viscosity are observed.
Both parameters increase and level off at a surface pressure
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 responsible 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 oscillation frequency are necessary to enable us to distinguish
between these two and possibly still more relaxation
processes [ 261.

Acknowledgements

01

10

12

The work was financially supported by a project of the

European Community (HCM ERBCHRXT930322)
and the
Fonds der Chemischen Industrie (RM 400429).

IJO

14

pressure (mN/m)

Fig. 4. Dilational elasticity E and viscosity ~7~of a DPPC monolayer

function of surface pressure, T= 20.5 C. L = 7.5 cm, w = 0.628 s- ,

as a

References
The dilational elasticity and the phase angle, expressed as
dilational viscosity, of DMPE and DPPC are given in Fig. 3
and Fig. 4, respectively. All measurements were performed
at 21 C which allows a direct comparison of the results.

4. Discussion
The shear viscosity is only insignificantly changed up to
the end of the coexistence region. Beyond this point the shear
viscosity increases linearly. For the DMPE an abrupt further
increase to very high viscosity values is observed after the
transition point from a liquid condensed (LC) to a solid-like
state at a pressure of about rr= 21 mN m-i. For the DPPC a
similar behaviour is observed. Although a transition from the
LC phase to a solid-like film at about r= 32 mN m- has

[ I] M. Joly, KolloidZ.. R9 ( 1939) 26.

[21 B.M. Abraham, K. Miyano and J.K. Ketterson, Ind. Eng. Chem. Prod.
Rex Dev.. 23 ( 1984) 245.
[31
[41
[Sl
[6]
[7]

B.M. Abraham and J.K. Ketterson, Langmuir, 1 (1985) 461.

B.M. Abraham and J.K. Ketterson. Langmuir, 2 (1986) 801.
J.B. Peng, G.T. Barnes andB.M. Abraham, Lungmuir, 9 (1993) 3574.
B.A. Noskov, ColloidPolym. Sci.. 273 (1995) 263.
H. Mohwald,Ann. Rev. Phys. C/tern., 41 (1990) 441.

[81 0. Albrecht, H. Gmler and E. Sackmann, J. Phys., 39 (1978) 301.

[91 C.A. Helm and H. Mohwald, J. Phys. Chem., 92 ( 1988) 1262.
[ 101 N.R. Pallas and B.A. Pethica, Langmuir, I (1985) 509.
[ II] S. Kirstein, H. Mohwald and M. Shimomura, Chem. Phys. Lerr., 154
(1989) 303.
I121 D. Honig and D. Mobius, 1. Phys. Chem., 95 ( 1991) 4590.
[ 131 G. Kretzschmar and K. KSnig, J. Signal Am., 9 (1981) 203.
[ 141G. Kretzschmar, Pragr. Colloid Polymer Sci., 77 ( 1988) 72
1151 G. Loglio, R. Miller, A.M. Stortini, U. Tesei, N. Degli-Innocenti and
R. Cini. Colloids Surfaces A: Physicochem. Eng. Aspects, 90 (1994)
251.

364

.I. Krtigel et al. /Thin Solid Films 284-285 (1996) 361-364

[161G. Loglio, R. Miller, A.M. Stortini, U. Tesei. N. Degh-Innocenti and

R. Cini. Colloids Surfaces A: Physicochem. Eng. Aspects, 95 (1995)
63.
[ 171 S.S. Dukhin, G. Kretzschmar and R. Miller, Dynamics ofAdsorption
at Liquid Inter$aces: Theory, Experiment, Application, in Studies of
Interfiice Science,

D. Mobius and R. Miller (eds.), Elsevier,

Amsterdam, 1995.
[181J. Kriagel, S. Siegel, R. Miller, M. Born and K.-H. Schano, Col1oid.s
Surfaces A, 91 (1994)

169.

[I91 J. Kragel. S. Siegel and R. Miller, Progr. Colloid folym. Sci., 97

(1994) 183.
[2OI J. K&gel, R. Wtistneck, D. Clark. P. Wilde and R. Miller, Colloids
Surfaces A: Physicochem. Eng. Aspects, 98 ( 1995) 127.

[21] J. Kragel, A.M. Stortini, N. Degli-Innocenti, G. Loglio. R. Cini and R.

Miller, Colloids Surfaces A: Physicochem. Eng. Aspects, ( 1995); IO1
(1995) 129.
[22] N.W. Tschoegl, KolloidZ.. I82 (1961) 19.
[23] J. Lucassen and G.T. Barnes, J. Chem. Sot. Faraday Trans. 1. 68

(1972) 2129.
[24] J. Lucassen, and D.J. Giles, Chem. Sot. Faraday Trans. 1.71 ( 1975)
. .._
Ll/.

[25] E.H. Lucassen-Reynders, in E.H. Lucassen-Reynders (ed.), Surface

Elasticity and Viscosity in Compression-Dilation. Surfactant Science
Series. Vol. 1 I. Anionic Surfactant-Phvsical Chemistrv.
<I Marcel

Dekker, Base], 1981, pp. 173-216.

[26] P. Joos, M. Van Uffelen and G. Serrien, J. Colfoid Interface Sci.. 152
(1992) 521.