Wear 222 1998.

2128

Macromodel approach to experimental study of polymer brushes rubbing

S.V. Kotomin ) , N.N. Avdeev
Topchie Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912, Leninskii, Prospect 29, Moscow, Russian Federation Received 20 February 1998; revised 2 July 1998; accepted 17 August 1998

Abstract For experimental studies of polymer brushes friction a simple macromodel approach using ordinary tooth brushes with different stiffness was proposed. Experiments were performed on pairs of brushes with various mutual penetrations and speed of displacement, and a force-displacement response during cyclic shift in two directions was studied. Experimental results reveal two mechanisms of friction, so-called slippingpulling and rake-on-rake. The attraction effect was observed at the beginning of the brushes moving cycle, connected with the friction of filament ends along axis. Controversial influence of friction between constituent elementary filaments of opposite brushes and their bend deformations during mutual displacement on normal reaction was shown. Contrasting with the shear force, the normal repulsive reaction for mild brushes is stronger than that for rigid brushes due to presence of different rubbing mechanism. q 1998 Published by Elsevier Science S.A. All rights reserved.
Keywords: Polymer brush; Toothbrush; Filament; Friction; Interpenetration

1. Introduction Recently, great attention was paid to study of polymer films and particularly polymer brush friction on molecular level w14x. In spite of numerous publications on this matter, most of them present theoretical speculations without essential experimental confirmation of theoretical points. Partially, this situation can be explained by narrow choice of polymers suitable for experiments and problems with a proper acquisition of data on surface force apparatus SFA. during dynamic two-dimensional nanometer scale oscillations. There is still no convincing experimental confirmation of interpenetration for layers of polymer brushes, but many authors at least in theory consider this penetration as quite feasible. As noted by Witten et al. w1x, the extent of penetration should be controlled by the competition between the translation entropy to be gained by penetration and the energetic cost of penetration. Joanny w3x predicted a critical velocity of the order of millimeters per seconds for sharp decrease of the sliding viscosity due to disruption of the bridge in the interpenetration zone. He also noted that in case of stickslip mechanism of brushes rubbing, the kinetics of entrance and extraction of filaments from the interpenetration zone could govern the period of arisen
)

oscillations. Semenov w4x considers the structure of the interpenetration layer as non-dependent on the velocity of displacement. The experiments with polymer brushes were fulfilled mainly on block-copolymer polystyrenepolyvinylpyridine PSPVP. w2x under restricted conditions. In view of this, a certain interest may be attributed to experimental modeling of the friction process on macromodels, the geometry of which to some extend simulates a structure of polymer brushes. Certainly in this case, the thermodynamic factors and relaxation phenomena cannot be considered directly, but their influence may be modeled further. The most simple and suitable samples for this purpose might be ordinary toothbrushes presented on modern consumer market with great variety of shapes, color and hardness. The color of the brush is not so crucial for experiments. In choosing proper samples for experiments, the most important properties of course are stiffness of consisting bristles and shape of holder for a proper fixation in the testing machine. This demand substantially restricts the choice, but still many types of brushes meet these requirements.

2. Samples and testing procedure Two types of toothbrushes were used for experiments: medium and hard type brushes obtained from the

Corresponding author

0043-1648r98r$ - see front matter q 1998 Published by Elsevier Science S.A. All rights reserved. PII: S 0 0 4 3 - 1 6 4 8 9 8 . 0 0 2 7 7 - 4

22

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

Kruidvat store in the Netherlands. Below we shall call medium as a mild, and hard as a rigid brush. The brushes had straight holders; each bristle of the brush consisted of 11 = 4 rows of buns containing in turn 15 nylon monofilaments with diameter 0.3 mm. The dynamic tests were carried out on a INSTRON 4301 testing machine in cycling mode with constant speed of up and down displacement. To fix the upper crosshead in a vertical position the special holders were designed, as shown in Fig. 1. The design of the holders allows changing the depth of the brush penetration, keeping them in the same time symmetrically regarding the middle crosshead axis. The speed of the crosshead displacement varied in the range 1500 mmrmin. The penetration depth was 1, 3 and 7 mm; the displacement range was 10 mm. For measurement of normal displacements, we use a capacitor measuring system, developed in the Groningen University. With the help of this system, a simultaneous recording of shear force and normal displacement response with accuracy of 0.2 m m was available. The one end of the brush basement was fixed in the holder; thus, it behaved during test as a console. Although on conducting the test, each brush slightly bends due to the normal reaction, the basements of the brushes remain parallel to each other.

3. Results and discussion The dependence of the axial force response on the brushes displacement from the very beginning is shown in Fig. 2. How it is seem from the shape of the curves in the figure, for all samples the force growth is nonlinear but

Fig. 1. Schematic image of the samples fixed in holders on tensile machine 1,2brushes; 3moving holder; 4immovable holder; 5 displacement sensor.

Fig. 2. Force response for mild 1,3. and rigid 2,4. brushes for 1 mm 1,2. and 3 mm 3,4. interpenetration for displacement velocity 1 mmrmin.

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

23

Fig. 3. Geometric model for filaments interaction in a. initial and b. separation position.

rather smooth up to certain displacement, after that a saw-like unsteady oscillations were observed. They in turn seem to be also modulated with low frequency oscillations. For low-penetrated brushes 1 mm., the amplitude after reaching maximum slightly decreases, that is probably connected with decreasing of the effective friction area during the displacement. For more deep penetration 3 mm., increasing of the force response is observed practically up to change in the moving direction. Naturally for rigid brushes the rate of force growth is higher, than for mild brush, thus this rate can be considered as characteristics of rigidity. The difference in the force growth for the same brushes with different penetration shall be discussed later. For an analysis of the process, let us consider the interaction of two single filaments of the opposite brushes

Fig. 3.. At the beginning of the shift, the entangled filament ends transfer the stress to the whole filament that led to its bending. The filament can be considered as a cantilever console. with an unmovable point of fixation. Because during the movement the effective length of the lever permanently increases along with diminishing of the friction contact between filaments, the rise of the force even at the constant displacement velocity is non-linear. The onset of unsteady force changes is certainly connected with the peculiarities of the filament separation. This disconnection may happen in two ways: 1. The sliding of bended filament ends along each other up to complete pulling off the brushes ends, we would call it slippingpulling mechanism; 2. The declination of the filament axis leading to slipping across common axis, we would call it rake-on-rake mechanism. Presumably, the first mechanism is more feasible in case of low penetration and for mild brushes, the second for stiff brushes with deep mutual penetration. For deeper level of penetration j 0 s 3 mm the nonlinear part of the response is shorter and for j 0 s 7 mm, we see practically no phase shift in force response Fig. 4.. As expected, the force amplitude for deeper penetration is considerably higher and mainly is ruled by rake-on-rake type of movement. Thus, we consider the most interesting behavior in our experiments is attributed to the low level of penetrationabout 10% of the single filament length or 5% of the gap between brushes basements.. In real polymer brushes, a deeper level of penetration is hardly possible, and as it was theoretically predicted by Klein w5x, for compressed brushes interpenetration zone only slightly varies with compression. In the present work, we shall focus mainly on the results of the experiments with initial

Fig. 4. Force response vs. displacement for penetration: 1 1., 3 2. and 7 3. mm for velocity 10 mmrmin.

24

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

Fig. 5. Force response vs. displacement for rigid a. and mild b. brushes at velocity 1. 1, 2. 10, 3. 100 and 4. 500 mmrmin.

brush interpenetration 1 mm. For lower depth of penetrations, the instrumental error in determination of force and displacement response drastically increases. For real brushes in case of slippingpulling mechanism up to the moment of separation, the brushes should be in symmetrically-bended state Fig. 3b.. Real shape of filaments in this case should be parabolic and dependent on the rigidity of the filament. Differential equation for the bend console: EJ s d2 y d x2 sM x.

where E flexural modulus, J moment of inertia, M torsion moment. The shape of the bended filament is described by the equation of cubic parabola: ys Fl 3 2 EJ

/
l

1 y 3

/
l

2.

where l half distance between brushes basements. From Eq. 2., the maximal critical. displacement sc s ymax at x s l y0 s Fl 3 3 EJ

1.

3.

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

25

at this the angle between slope at the touch point and the initial position of the filament axis is: tan u s

/
dx

dy

Fl s
xs l

moving agitation. For analysis of the force reaction in both directions during the motion it is necessary to note the vector character of the force. Fy s FN cos u q m sin u . Fx s FN m cos u y sin u .

2 EJ

4.

If we consider the case when both filaments remain in the same plane, and the separation occurs at the length of the curve is equal to length of the filament L provided a slight decline at d y .rd x . < 1. and from Eq. 3.: Ls

8.

where the m friction coefficient between filament ends, N normal force in the touch point.If we express FN using displacement, then Fy s 3 EJ l2 3 EJ l2 y

H0

1q 1 15

sl 1q

/ /
dx Fl EJ
2

dy

d xf
2

H0

1q

1 dy 2 dx

dx

5.
Fx s

in result from Eqs. 3. and 5., we have: Lsl 1q 3 Sc 5 l

2 l y 3 y 1q m 2 l

my

3 y

/ /

9.

6.

if we express interpenetration as j s 2 L y l ., then we get very simple expression:

js

2 6 Sc

5 l

7.

Knowing from the experiment the value of the critical displacement sc corresponding to sharp downfall of the force response. and assuming that l s constant, we can estimate the depth of the effective penetration je . It is worth noting that Eq. 7. does not contain the length of the filament. For both mild and hard brush, we have, as seen in Fig. 2, in the experiment with 1 mm penetration depth, sc f 3 mm. Thus, the calculated value of the penetration jef s 0.98 mm for l s 11.0 mm., that is very close to the real value of the initial penetration value j 0 s 1.0 mm. These results encourage us that this model works fairly well. The dynamics of normal displacement will be discussed below. At the end of the first cycle a kind of stress hysteresis is clearly seen obviously connected with the residual bend position of the buns. The frequency of modulated oscillations is connected with critical displacement and the velocity or the frequency. of crosshead

Table 1 Work numerator in J, =10y3 . and dissipated power denominator in W, =10y3 . in the process of brush rubbing Brush Pene- Velocity, mmrmin type tration 1 10 Rigid 1 3 7 1 3 100 500

10.75r0.0089 10.89r0.091 11.20r0.93 8.16r3.40 16.10r0.0134 19.70r0.16 20.90r1.74 14.33r0.12 11.17r0.93 9.09r0.0076 9.49r0.079 9.35r0.078 9.60r0.80 8.68r3.62 7.40r0.62 6.54r2.73

Mild

As it seen from Eq. 9., the sign of the Fx will change during the motion in one direction at the value of displacement y s 2 r 3m l but the sign of the Fy may not. If we compare the force response for different velocities shown in Fig. 5, it is seen that for both types of brushes for 1 mm interpenetration, it slightly increases from the velocity 1 mmrmin up to 100 mmrmin but then at the highest speed y500 mmrmin a noticeable decrease is observed. In view of the above one can conclude that the Joannys prediction of critical velocity for friction force is also valid for our model. It is interesting to consider the connected energetic charac-teristics of the rubbing process, presented in Table 1. The works at rubbing and corresponding dissipated power were calculated from the area and the period of the cycle curves, presented in Fig. 5. As it seen from the table, for 1 mm interpenetration the work of rubbing in the interval of velocities 1100 mmrmin is slightly increases, then for 500 mmrmin the significant drop, particularly for rigid brushes on 28%. is observed, that corresponds to the amplitude changes. In all cases the power dissipated on rubbing increases considerably proportionally to the frequency of oscillations. For deeper interpenetration 3 mm. the difference in the rubbing work between rigid and mild brushes is very high more than two times., and has different trends, probably connected with different rubbing mechanisms. For 7 mm interpenetration at least for the agitation amplitude of displacement 10 mm. we think it is not worth talking about brushes rubbing at all, because there is no complete draw out of filaments and the process is mainly governed by elastic bending of filaments. For comparison of the results under discussion with the observations in previous experiments on polymer brushes using SFA instrument, it is more convenient to present the above force response dependence in the time scale as shown in Fig. 6. Although the force response or the same displacement response. formally looks like oscillation with

26

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

Fig. 6. Force response vs. cyclic displacements for rigid brushes at 500 mmrmin.

a phase-shift relatively the agitation displacements, actually this shift should be considered as a consequence of slipstick movement. This suggestion is proved by the fact that this phase difference practically is not dependent on the frequency. The number of the full minor oscillation within the cycle in case of brushes with interpenetration 1 mm is independent of frequency and equal 3, that is exactly corresponds to the integer from division 10r3. The dynamics of displacement response to sine agitation for the polymer brush copolymer PVPPS. in SFA instrument is

shown in Fig. 7. One can see that despite of principal differences in sample types and instrumental base for experiments, both pictures surprisingly have very much in common. Let us consider that the position of the first maximum on the response curve corresponds to the critical displacement at the moment of disruption on the brush filaments. On the basis of our model, presumably it is possible to estimate the effective penetration of the filaments from the oscillation response, if it actually took place. Taking the

Fig. 7. Displacement response vs. sine agitation on SFA for polymer brush at 10 Hz.

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

27

Fig. 8. Normal displacement response vs. time for brushes for 1. rigid and 2. mild brushes at 1 mm interpenetration and velocity 10 mmrmin.

calculation from Fig. 5, the values l s 40 nm and sc s 7.5 nm, we get the value for jef s 1.7 nm. This value about 2% of the gap. is within the range of the interpenetration for the proposed model. The normal displacement of rubbing brushes is of particular interest, because in the literature, there are only few examples of such type tests for polymers w6x. As shown in Fig. 8, in our experiments, the amplitude of shear-plane force for the pair of rigid brushes was twice higher then that for the mild brushes. This is quite understandable because the axial consistent part of the vector of bending force is proportional to elasticity modulus of the filaments. From the other hand, the amplitude of normal displacement response for the couple of mild brushes is 380 m m or 38% of the initial value of the penetration 1 mm., and for rigid brushes these values are respectively 250 m m and 25%. For equal stiffness of the plastic basement it means that normal repulsive force in the case of mild brushes is on 52% higher than for rigid brush. This unexpected result can be explained from the position of the above mentioned different mechanisms of brush filaments moving. For mild brushes the slippingpulling mechanism prevails, for rigid brushesrakeonrake one. Thus, if we account the value of displacement in our calculation of the effective penetration for our model, the result will be even more encouraging. It is interesting to observe another, rather unexpected phenomenathe negative relatively initialzero position. normal displacement at the beginning of the cycle. It corresponds to attraction of rubbing brushes while moving. Certainly it is a consequence of friction force reaction along filament axis, the normal component of which acts as an attraction force. This force depends mostly on the friction coefficient between filaments that is why it is about the same for both types of brushes. When this force becomes equal to increasing opposite normal reaction of

the filament due to bending, the sign of the result force changes to opposite and the latter becomes repulsive. In the previous theoretical papers, the interaction was considered only in one-plane and the mechanism rakeon-rake was not predicted at all, as well as the attraction effect. Thus, the results of simple experiments on macrobrushes can help to understand possible behavior of polymer brushes in case of their penetration, and predict some effects, which probably may take place for real polymer brushes. It is reasonable to suggest that in case of some polymer brushes, back filaments of which are rigid like in some types of liquid crystalline polymers i.e., comb-like smectic type., this approach will be the most successful. In this work, the evidence of two mechanisms of rubbing and the difference in behavior of rigid and soft macrobrushes was experimentally shown. Further, we intend to simulate relaxation phenomena on this model by covering bristles with a proper viscoelastic liquid. Of course, every model has some limits and cannot include all properties of the real object either why we use it instead of the object itself?., but the real advantage of modeling approach is possibility to evaluate influence of separate factors on the general behavior, that is impossible or at least very difficult or expensive. to do with a real object.

4. Conclusions For experimental study of polymer brushes friction macromodel approach using ordinary tooth brushes proved to be useful. Experimental results revealed two mechanisms of frictionslippingpulling and rake-on-rake. The attraction effect was observed at the beginning of the moving cycle, connected with the friction of filament ends

28

S.V. Kotomin, N.N. Adee r Wear 222 (1998) 2128

along axis. Controversial influence of friction force between constituent filaments of opposite brushes and the elastic reaction on bending during mutual displacement was shown. Contrasting with the shear force along crosshead axis., the normal repulsive reaction for mild brushes is stronger than that for rigid brushes due to presence of different rubbing mechanisms. An existence of critical velocity for drop of friction force was proved and possible link of critical displacement with interpenetration level was estimated.

References
w1x w2x w3x w4x w5x w6x T.A. Witten, L. Leibler, P.A. Pincus, Macromolecules 23 1990. 824. S.T. Milner, Science 251 1991. 905. J.-F. Joanny, Langmuir 8 1992. 989. A.N. Semenov, Langmuir 11 1995. 3560. J. Klein, Annu. Rev. Mater. Sci. 26 1996. 581. A. Dhinojwala, S. Granik, Macromolecules 30 1997. 1079.

Acknowledgements We wish to thank Prof. G. Hadziioannou and Prof. G. ten Brinke for support and promotion of experimental part of this work in the Groningen University, the Netherlands, and also Amalia Stamouli for kind permission to use her SFA data. Special thanks to Mr. A.B. Verweij for the assistance in the experiment. We sincerely appreciate Prof. V.G. Kulichikhin for his encouragement in the basic idea of the work. This research was supported by the Netherlands Organization for Scientific Research NWO..

Dr. Serguei Kotomin graduated from the Russian University of Chemical Technology in Moscow in 1974. Obtained PhD degree in chemistry plastics technology. in 1983. From 1978 to 1991, he worked in the All-Russian Research Institute of Polymer Fibres in Mytischi near Moscow.. Since 1991, he has been working as senior researcher in the laboratory of Polymer Rheology at the Institute of Petrochemical Synthesis Russian Academy of Sciences.. He was a visiting scientist in 19921993 at the Liverpool University, UK, and in 1997 at the Groningen University, the Netherlands. His research interests covers physical chemistry of polymer composites and reinforced plastics, computer application for rheological analysis of polymer blends and composites. Dr. Nikolai Avdeev graduated from Moscow State University physics department. in 1966. He worked at the Institute of Crystallography and Institute of Physical Chemistry. After obtaining PhD physics. in 1992, he joined the Institute of Petrochemical Synthesis and since that time has been working as seniour researcher in the laboratory of Polymer Rheology. Main area of intereststhermodynamics and diffusion phenomena in polymer blends.