Eur. Phys. J. Special Topics 141, 235241 (2007) c EDP Sciences, Springer-Verlag 2007 DOI: 10.

1140/epjst/e2007-00046-6

THE EUROPEAN PHYSICAL JOURNAL

SPECIAL TOPICS

Chain dynamics in mesoscopically conned polymer melts. A eld-cycling NMR relaxometry study
R. Kausik1 , C. Mattea1 , R. Kimmich1 , and N. Fatkullin2
1 2

Universit at Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany Kazan State University, Department of Molecular Physics, Kazan 420008, Tatarstan, Russia

Abstract. Polymer chain dynamics were studied with the aid of eld-cycling NMR relaxometry (time scale: 109 s . . . 104 s) supplemented by eld gradient NMR diusometry (time scale: 104 s . . . 100 s). Three sorts of samples of mesoscopically conned polymer melts were examined. In the rst sample series, linear poly(ethylene oxide) was incorporated in strands embedded in a quasi-solid and impenetrable methacrylate matrix. The strand diameters ranged from 10 to 60 nm. It was shown that chain dynamics becomes dramatically dierent from bulk behavior. This so-called corset eect occurs both above and below the critical molecular mass and reveals dynamic features predicted for reptation. On the time scale of spin-lattice relaxation, the frequency and molecular weight, signature of reptation, T1 M 0 3/4 , that is limit II of the Doi/Edwards formalism corresponding to the mean squared segment displacement law r2 M 0 t1/4 , showed up. A tube diameter of only 0.6 nm was concluded to be eective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. The corset eect is traced back to the lack of the local uctuation capacity of the free volume under nanoscopic connements. The connement dimension at which the cross-over from conned to bulk chain dynamics is expected was estimated to be micrometers. Using the so-called roll-coating technique, micrometer thick polymer melt layers between Kapton foils were prepared. Perceptible dierences from the bulk materials were found. The polymer species studied in this case was peruoropolyether with Flory radii in the order of 7 nm. Remarkably, the connement eect was shown to reach polymer-wall distances of the order 100 Flory radii. As a third connement system, melts of peruoropolyether were lled into a porous silica glass (Vycor; 4 nm nominal pore size). In this case, a crossover from Rouse dynamics in the bulk to reptation in the Doi/Edwards limit III (T1 M 1/2 1/2 corresponding to r2 M 1/2 t1/2 ) was observed.

1 Introduction
Polymer chain dynamics can be discussed in terms of normal modes as solutions of equations of motion which represent certain model scenarios [1]. Popular formalisms of this sort are the Rouse model (free chains in a viscous medium without hydrodynamic backow eects) and the tube/reptation concept (chains conned in a tube with a diameter much shorter than the radius of gyration of the polymer random coil). In principle, these two classes of chain dynamics represent the extremes of no restriction at all on the one hand and maximum restraint under liquid conditions on the other. Characteristic laws have been predicted in either case [2]. The objective of the present study was to realize experimental conditions for both limits and to examine the crossover between them.

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Field-cycling NMR relaxometry (time scale: 109 s . . . 104 s) [3] and eld-gradient NMR diusometry (time scale: 104 s . . . 100 s) [4] turned out to be excellent tools for the probing of polymer chain dynamics. Based on these techniques, connement eects in three dierent samples have been studied. The connement length scale ranges from nanometers to micrometers. This is the mesoscopic range in which the crossover from the so-called corset eect to bulk chain dynamics was predicted [5].

2 Experimental methods and samples

Figure 1 schematically shows the connement scenarios considered in this study. In the rst sample series, linear poly(ethylene oxide), PEO (Mw = 1665, Mw /Mn = 1.08, RF = 4 nm and Mw = 6000, Mw /Mn = 1.03, RF = 7 nm) was embedded in the form of strands in a quasi-solid and impenetrable methacrylate matrix (compare Fig. 1A). The matrix material of a cross-linked mixture of methacrylate polymers. The strand diameters ranged from 10 to 60 nm. The preparation and characterization techniques are described in Ref. [6]. Field-gradient NMR diusometry [4] turned out to be a convenient tool for the determination of the strand diameters in agreement with electron microscopy. The PEO strands were studied with proton NMR. The matrix signal was found to be negligible in these experiments (see Ref. [7]). Using the so-called roll-coating technique [8, 9], micrometer thick layers of peruoropolyether, PFPE (Mw = 11000, RF = 7 nm) were prepared in rolls of Kapton. A schematic crosssection is shown in Fig. 1B. Preparation details can be found in Ref. [8]. As a third connement system, PFPE melts were lled into a porous silica glass (Vycor porous glass, no. 7930, 96% SiO2 , Corning Inc., Corning, NY 14831). For a schematic picture of the sample conguration see Fig. 1C. The average pore diameter was specied by the manufacturer as 4 nm (96% of the pore volume is within (4 0.6) nm, the porosity as 28%, and the specic surface as 250 m2 /g. Vycor tends to adsorb organic vapours from the air. In order to remove such impurities and following the recommendations of the manufacturer, the samples were boiled rst in 30% H2 O2 for 20 min and then in distilled water for another 20 min before drying them in vacuum and lling them with the polymer employing the bulk-to-bulk method. Both the polymers and Vycor porous glass were evacuated overnight at 130 C. After this treatment, the Vycor samples were considered to be completely dry. The porous glass rods were then made to dive in the polymer melt. The time taken for the polymer melt to percolate into the porous glass was varied from 12 hours to 1.5 weeks to have small dierences in the lling factor. After about 10 days the samples were saturated.

Fig. 1. Schematic representation of the three connement scenarios investigated. A) PEO melt strands of various molecular weights and diameters (10 . . . 60 nm) embedded in a solid methacrylate matrix. B) PFPE melt layers of various thicknesses (0.8. . . 1.6 m) between Kapton foils. C) PFPE melts lled into Vycor (4 nm) with various lling degrees.

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H or 19 F spin-lattice relaxation dispersions were studied with eld-cycling NMR relaxometry [3]. A STELAR relaxometer covering a proton frequency range 1 kHz to 10 MHz was employed. The range was supplemented by two conventional NMR spectrometers operating at 4.7 and 9.4 T.

3 Theoretical background
The relaxation connement eect is expected to be particularly strong for molecular masses in M Mc , where Ms is the molecular mass of a Kuhn segment and Mc is the the range Ms critical molecular mass dened by the crossover between free and entangled chain dynamics. In this range, chain dynamics in bulk melts can be described by Rouse modes, whereas the conned polymer should reveal the characteristics of reptational dynamics [2, 7, 13]. With respect to spin-lattice relaxation rates, these two limiting model theories are characterized by certain signatures. The prediction for the Rouse model in the Larmor angular 1 1 frequency range R s is [2], [1012] 1
Rouse T1

2 ln 0.63s M

0.95 s

2 +M .

(1)

1 The reptation model suggests for the limit R

1 e (Doi/Edwards limit II) [2]

1
rep,II T1 1 and for the limit d

2 s M b3 p 2 1/4 31/2 (5/4) 1 + 2 21/4 cos (/8) 3 , 1215 dHRP T (s )3/4

1 R (Doi/Edwards limit III) [2]

(2)

1
rep,III T1

2 s M b3 p 2 1/2 31/2 (1/2) cos (/4) 1 + 23/2 N 1/2 3 , 1215 dHRP T (s )1/2

(3)

where d is the so-called disengagement time [1]. Equation (2) was derived in Ref. [10] assuming conning tubes with harmonic radial potential. s is the local Kuhn segment uctuation time 2 is the second moment of the residual dipolar spin interactions after averaging over constant; M all fast uctuations occurring on the time scale t s ; e is the so-called entanglement time characterizing the time scale on which segments start to sense the tube constraint; R is the is the total second moment of the unaveraged dipolar longest Rouse relaxation time [1]; M 2 l is interactions; b is the Kuhn segment length; p l/dHRP T is a parameter of the order 1; the persistence length of the randomly coiled tube; dHRP T = d/2 is the tube diameter eective for the harmonic radial potential theory of the tube/reptation model [10]. The diameter of a tube with hard walls (assumed to be relevant in experiments) is designated by d. Eq. (3) was obtained analogously. N is the number of Kuhn segments per chain. Equations (2) and (3) depend on the eective tube diameter d. Anticipating that s is the same under bulk and connement conditions, this parameter d can be evaluated from relaxation 1 data [7]. Dividing the two expression valid for R , that is Eq. (2) by Eq. (1) leads to d 2b
rep,II p T1 2 1/4 31/2 (5/4) cos (/8) 1 + 2 21/4 Rouse 3/ 4 765 T1 (s ) ln (0.95/s ) 1/ 3

(4)

The eective tube diameter, d, can thus be evaluated by inserting the values of the spin-lattice relaxation times measured in bulk and in conned samples at the same frequency. Note that the condition that both data sets refer to a time scale shorter than the Rouse relaxation time is only fullled if limit II applies to the conned sample (which is not the case for PFPE in Vycor). Theoretically the eective tube diameter is given by [5] db s kB T T (5)

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where s is the number density of Kuhn segments, T is the isothermal compressibility, T is the absolute temperature, and kB is the Boltzmann constant. A theoretical estimation of the bulk limit where connement eects are no longer relevant suggests connement dimensions obeying dconf b3 kB T T
1/ 3

RF 10RF ,

(6)

where RF = bN 1/2 is the Flory radius of the polymer random coil under bulk conditions.

4 Results
Figure 2 shows the proton spin-lattice relaxation dispersion in strands of PEO melts in solid methacrylate matrices. The pore diameter varies from 10 to 60 nm. Two dierent molecular weights below and close to the critical value Mc have been investigated. Data measured in the bulk samples are also shown for comparison. The connement eect is obvious. While the data for PEO melts in bulk can be described by the Rouse model (Eq. (1)) for Mw = 1665 < Mc , chain dynamics in the material conned in the methacrylate matrices is compatible with the reptation model in limit II (Eq. (2)) above 105 Hz independent of the molecular weight and independent of the connement diameter as 0 0.75 far as studied here. The power law T1 Mw predicted for this limit is veried. This refers both to the frequency and the (vanishing) molecular weight dependences. At lower frequencies, a tendency versus a plateau is observed, which may be explained by the fact that then the standard relaxation theory is no longer applicable because the longest correlation times of spin interactions start to exceed the spin-lattice relaxation time. This contradicts the usual perturbation formalism [7, 13]. Note that the plateaus of the bulk data in Fig. 2 are of a dierent nature: They indicate a frequency range corresponding to a time scale longer than the longest correlation time in the system. Evaluating Eq. (4) for two PEO data sets recorded under the conditions for the Rouse model (bulk, Mw < Mc ) on the one hand and under connement leading to reptation dynamics, limit II, on the other, suggests an eective tube diameter of roughly d 0.6 nm dpore . The fact, that this value is far below the conning pore diameter dpore 10 . . . 60 nm is termed the corset eect [5, 7]. It is in accordance with an estimation based on Eq. (5). The essence of the corset eect is that chain modes are aected by conning walls many random coil diameters away. It is understood as a consequence of the nite size of the system reducing the free volume uctuations. Since the low compressibility typical for liquids does not allow for large free volume uctuations, conformational chain rearrangements are largely suppressed. According to Eq. (6), the inuence of connements on chain dynamics should be perceptible up to a length scale of several hundred nanometers, and bulk behavior should occur only beyond

Fig. 2. PEO melts with two dierent molecular weights Mw in bulk and conned in solid methacrylate matrices (porosity 20%) with channels of various diameters as indicated. The bulk data can be described by the Rouse model, those of the conned melts by the power laws given next to the straight lines.

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Fig. 3. Spin-lattice relaxation dispersion in PFPE melt layers conned in Kapton rolls. The layer thickness varies from 0.8 to 1.6 m. The uorine data refer to PFPE, the proton data to the Kapton foil. Relative to the melt in bulk, the relatively weak connement inuences chain dynamics perceptibly depending on the layer thickness. The much steeper proton T1 dispersion indicates that cross-relaxation between the proton and uorine reservoirs does not inuence the uorine relaxation of the PFPE in the frame of the experimental accuracy.

that length scale [5]. This prediction was veried with PFPE melts conned in layer form in Kapton rolls as demonstrated in Fig. 3. There is a small, but anyway clear reduction of the PFPE uorine spin-lattice relaxation times relative to the bulk data, and the eect depends on the layer thickness. At such thick polymer melt layers, the crossover from conned to bulk chain dynamics is almost complete. Note that the Kapton foils do not contain any uorine so that uorine NMR signals originate from the PFPE melts. However, there could be an indirect inuence of the foil material via cross-relaxation between the uorine nuclei in the PFPE melt and the protons in the Kapton foils. In order to test this, we have recorded the proton spin-lattice relaxation dispersion in addition (see Fig. 3). The dispersion slope of these data is totally dierent from the uorine T1 dispersion so that any perceptible cross-relaxation eect can be ruled out. This means, PFPE chains are conned but not bound on the Kapton surfaces. A further connement scenario was studied with the porous silica glass Vycor. PFPE again shows little anity for adsorption on the pore surfaces. This is manifested by the extremely long periods needed to saturate the pores. The experimental data are rendered in Fig. 4. The strong connement leads to a correspondingly strong reduction of the (uorine) spin-lattice relaxation times relative to the bulk data. The data shown in Fig. 4 reveal another phenomenon of interest in this context. The dierences at low frequencies show a clear tendency of decreasing relaxation times with increasing time the porous glass rods spent dipped in the polymer melt, that is, with increasing lling degree of the pores. Incomplete lling of the pores obviously means more motional degrees of freedom.

Fig. 4. Fluorine spin-lattice relaxation dispersion in PFPE melts in bulk and conned in a porous silica glass (Vycor). The mean pore dimension is 4 nm. The lling degree of the pore space is gradually approaching saturation in a period of about 10 days of exposing the glass to the polymer melt. Obviously chain dynamics is slowed down with increasing lling degree.

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Fig. 5. Fluorine spin-lattice relaxation times in PFPE melts conned in Vycor as a function of Mw at dierent frequencies. The pores were practically saturated after a period of about 10 days of exposing the glass to the polymer melt. The solid lines represent the proportionality given in the inset.

Unlike the conned PEO melts, which revealed limit II of the tube/reptation model via the II 0 0.75 power law T1 Mw (Fig. 2), the PFPE melts in Vycor appear to be subject to limit III of the formalism. That is, Eq. (3) is relevant in this case. Note that this refers not only to the III 0 . 5 0 . 5 dependence on the frequency but also on the molecular weight according to T1 Mw (see Fig. 5).

5 Discussion
Three dierent connement scenarios of polymer melts have been studied using eld-cycling NMR relaxometry. The length scale of the connement ranges from nanometers to micrometers, that is far beyond the length or random coil dimensions of the polymers under examination. The choice of the systems ensured that adsorption at the walls of the conning medium is irrelevant or negligible. The observed eects must therefore be considered to be solely due to the reduction in the available volume of the polymer component. A remarkable result is that connements on a length scale of even micrometers aect the dynamics of polymer chains as short as 10 nanometers. Actually this nding was predicted before on the basis of the corset eect [5, 7, 13]. In previous studies [1416], much thinner polymer layers were examined in diverse systems using techniques other than eld-cycling NMR relaxometry. The layers were bounded by a solid substrate surface on one side and by air on the other. Chain ordering relative to the surfaces was observed on a length scale of the order of 10 radii of gyration. Likewise the connement eects reported in Refs [1720] refer to constraints of the order of the coil diameter. This is much less than the almost macroscopic length scale of the phenomenon reported here. The fact that a connement eect was observed in 1 m thick layers between Kapton foils is remarkable since this is beyond any direct macromolecule/wall interaction length scale or even any sterical restriction eect of the chain conformation by the connement. The thickness corresponds to an order of magnitude of 100 random coil dimensions. Apart from the chemical inertness of the Kapton surfaces relative to PFPE, any modication of chain dynamics by direct interactions with the walls can be neglected since only a tiny fraction of the polymer chains are in direct contact with the walls. The eect is conrmed by diusion studies in thin lms where, under somewhat dierent experimental conditions, a slowing down was observed below several hundred nanometers [21, 22]. According to Eq. (6), bulk behavior can be expected for connement dimensions dconf 50 nm. In the case of the Kapton rolls, the width of the conning layer is 20 times larger than this estimated value. This demonstrates how far reaching the corset eect phenomenon acts. Chain dynamics in PFPE melts conned in layers measuring more than 100 Flory radii in thickness reveals already rst indications of the corset eect. On the other hand, the crossover from Rouse to reptation dynamics in the Vycor or methacrylate samples is almost complete as predicted in Ref. [5].

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The reptation characteristics of the T1 dispersion represented by Eq. (2) are well reproduced in the case of PEO melts conned in nanoscopic pores (see Fig. 2). The data for PFPE in Vycor shown in Fig. 4 also approach a much steeper T1 dispersion, but do not reach the power law 1 II 0 0.75 1 Mw predicted for the limit R e . Obviously this limit is violated, and T1 1 1 R , so that Eq. (3) the relevant frequency scale is more likely characterized by d becomes relevant. The expected molecular weight and frequency dependencies correspond then III 0 . 5 0 . 5 to T1 Mw . The frequency as well as the molecular weight dependences of this law are veried by the Vycor data. Note that the Rouse relaxation time, R , relevant in bulk and conned samples are not identical. The observation of limit III under connement suggests a shorter value than in the bulk melt. It should also be mentioned that limit III must generally be handled with care since there is some incompatibility with thermodynamic principles as outlined in Ref. [23].
We thank Hans Wiringer for technical assistance. This work was nancially supported by the VWFoundation, the DFG, and the RFST Program (grant # 02.445.11.7017).

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