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POLYMERS FOR ADVANCED TECHNOLOGIES Polym. Adv. Technol.

2005; 16: 262268 Published online 18 January 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pat.570

Polycarbonate/SiC nanocompositesinuence of nanoparticle dispersion on molecular mobility and gas transport{


Martin Bohning*, Harald Goering, Ning Hao, Reinhard Mach and Andreas Schonhals
Bundesanstalt fur Materialforschung undprufung (BAM), Unter den Eichen 87, D-12205 Berlin, Germany

Plasma synthesized silicon carbide (SiC) nanoparticles were dispersed in dichloromethane/poly(bisphenol-A-carbonate) (PC) solutions by high power ultrasonication. Samples were then prepared by lm casting under well adapted preparation conditions. The inuence of the SiC nanoparticles on the molecular mobility of the PC is studied by dielectric relaxation spectroscopy. No effect on the cooperative segmental mobility (glass transition) was detected. But the relaxation region corresponding to localized uctuations is strongly broadened and the activation energy is reduced with increasing nanoparticle concentration. The most signicant change was observed in the relaxation region between a- and b-process. The gas transport properties of these nanocomposite lms are characterized in terms of permeability, diffusivity and solubility. Results can be interpreted based on an altered local free volume distribution and a change of molecular mobility of the polymer matrix near the nanoparticle surface which is in agreement with the dielectric results. Concentration dependent CO2 permeation experiments reveal a signicant reduction of plasticization effects in the nanocomposites compared to the pure PC. Copyright # 2005 John Wiley & Sons, Ltd.
KEYWORDS: nanocomposites; nanoparticles; polycarbonates; dielectric properties; gas permeation

INTRODUCTION
Polymer based nanocomposites continue to receive tremendous attention for application such as microelectronics, organic batteries, optics and catalysis but also for conventional engineering purposes.1 The small size of the ller particles incorporated in polymeric matrix materials results in remarkable property improvements like increased tensile properties, decreased gas permeability, decreased solvent uptake, increased thermal stability and ame retardance etc. when compared to conventionally scaled composites. Up to now there has been a lack of knowledge about the relationship of the properties of the incorporated nanoparticles (their shape, their surface properties, etc.), and the resulting morphology of the nanocomposite and its macroscopic behavior. Especially the role of the interface regions between the nanoparticle and the polymer matrixwhich are present in large fractions due to the high surface to volume ratio of the nanosize ller particleshas hardly been discussed in the literature. This interface region (interphase) is directly inuenced by an adjacent nanoparticle surface and can play a decisive role for the performance of the nanocomposite
*Correspondence to: M. Bohning, Bundesanstalt fur Material forschung undprufung (BAM), Unter den Eichen 87, D 12205 Berlin, Germany. E-mail: Martin.Boehning@bam.de { Selected paper presented at the 7th International Symposium on Polymers for Advanced Technologies, 2124 September 2003, Fort Lauderdale, Florida, USA.

material, especially for the transport of small penetrant molecules (gases or vapours). Furthermore the length-scale of interaction between ller particle and polymeric matrix, which may be considerably smaller than that in conventional composite materials, leads to modications in packing structure and dynamics of the polymer. Resulting subtle changes in the free volume distribution can give rise to property changes of the whole composite. For example recently Merkel et al.2 reported an unexpected increase in permeability for small penetrant molecules (methane) combined with an unusual permselectivity for large organic molecules over small permanent gases for membranes of glassy nanocomposite materials based on poly(4-methyl-2-pentyne) (PMP) lled with nanoscale fumed silica particles. In this contribution nanocomposites based on poly (bisphenol-A carbonate) (PC) as host polymer and silicon carbide (SiC) nanoparticles as nanoller were prepared. Their properties were studied with regard to molecular mobility and gas transport properties by dielectric spectroscopy as well as permeation and sorption experiments. These studies were accompanied by transmission electron microscopy (TEM).

EXPERIMENTAL Materials
PC (Sigma-Aldrich) was used as host polymer. Its number average molecular weight (22,000 g/mol, polydispersity
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index 1.23) was determined by size exclusion chromatography (SEC) (polystyrene standard calibration) and its glass transition temperature (Tg 428 K) was measured by differential scanning calorimetry (DSC). The SiC nanopowders were synthesized via gas phase condensation reactions by a thermal rf induction plasma at atmospheric pressure. The custom-made plasma torch used is of standard design with a quartz plasma connement tube. The plasma was generated in an argon/hydrogen mixture

(10% H2) at a plate power of 30 kW. Silicon tetrachloride was diluted with H2-carrier gas, and directly injected into the plasma tail. Reactive quenching with C2H4 as carburizing agent was applied. The produced SiC nanopowders were collected in an electrical lter where the particles were charged and separated by a negative wire corona. The primary particles consist of a crystalline SiC core and an amorphous outer shell. Carbon species are also formed during the reaction. Fig. 1(A) shows a TEM image of the

Figure 1. (A) TEM image of the as synthesized SiC nanoparticles. (B) TEM image of the nanocomposites with 5 wt% of SiC.
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particles as synthesized. Herefrom a size distribution between 20 and 60 nm can be estimated for the primary particles. Moreover it can be seen that these primary particles form frog spawn-like agglomerates with a length between 200 and 500 nm. The nanocomposites were prepared via a solution casting route. The SiC nanopowder, described earlier, was dispersed in a 4.5 wt% solution of PC in dichloromethane by 5 min of ultrasonication (Bandelin Sonopuls HD200/ UW200 homogenizer with KE76 titanium tapered tip, pulsed mode). The dispersion was cast into a petri dish. During the rst stage of evaporation of the solvent at room temperature the atmosphere (air/nitrogen/dichloromethane vapor) was controlled to get fully amorphous lms and to minimize the sedimentation of the nanoparticles. Subsequently the lms were further dried at 363 K in a vacuum oven for 24 hr resulting in samples of about 50 mm thickness. The SiC concentration was varied from 0.5 to 5.0 wt%. Figure 1(B) shows a TEM image of the obtained composite containing 5 wt% SiC. The TEM samples were prepared using the focussed ion beam (FIB) cutting technique3 and the pictures therefore represent a view at the cross-section of the nanocomposite lms near the surface. The frog spawn-like structure of the nanoparticles is maintained but no further agglomeration of these aggregates was found for the prepared lms.

sure; p0 1.013 bar; (dp2/dt)s, steady state downstream pressure increase. Permeability coefcients are given in Barrer:   cm3 STPcm 1Barrer 1010 cm2 cmHg sec From the extrapolation of p2(t) in the steady state region to p2 0 the time-lag t was determined which characterizes the initial transient state and allows the estimation of an effective diffusion coefcient Deff by: Deff 2 6 2

Gas sorption was measured gravimetrically using an electronic high pressure microbalance (Sartorius 4406) placed in a temperature controlled air-bath and also equipped with a turbomolecular vacuum pump for degassing. Sorption isotherms in the pressure range from 1.0 to 50 bar were determined from the sum of mass uptakes (corrected for buoyancy effects) in successive steps of pressure increase in the system. The recorded sorption kinetics of individual mass uptake steps allows furthermore the calculation of diffusion coefcients.6

RESULTS AND DISCUSSION


The properties of PC/SiC-nanocomposites revealed by both experimental techniquesdielectric relaxation spectroscopy as well as gas sorption and permeation measurementsare primarily determined by local structural features of the polymeric matrix (such as free volume distribution) and its dynamic behavior on local and segmental length scales. In the context of this study both experimental approaches address similar characteristics of the nanocomposite materials from different points of view and different application perspectives. Furthermore this concomitant assessment of changes induced by introduction of nanoparticles to a glassy polymer matrix will contribute to a better general understanding of such polymer based materials.

Dielectric relaxation spectroscopy


The complex dielectric function e(f) e0 (f) i e00p fre(f) (f, quency; e0 (f), real part; e00 (f), imaginary part, i 1) was measured in the frequency range from 102 to 106 Hz by a frequency response analyzer Schlumberger FRA 1260 interfaced to a buffer amplier of variable gain (Chelsea Dielectric Interface). For more detail see ref. 4. Samples (20 mm in diameter; thickness of about 50 mm) were placed between gold-plated stainless steel electrodes. The temperature of the sample T was controlled by a custom-made gas jet heating system operated with liquid nitrogen. The sample was thermally equilibrated at the selected temperatures with a stability of 0.05 K.

Dielectric relaxation spectroscopy


Figure 2 shows the dielectric spectra for pure polycarbonate in a three-dimensional representation versus frequency and temperature. Two relaxation processes can be identied by peaks in e00 : A b-relaxation at low temperatures or high frequencies and an a-process (dynamic glass transition) at high temperatures or low frequencies. It is generally believed that the b-relaxation is due to localized uctuations. The dielectric b-relaxation of PC is probably due to uctuations of the ester groups supported by uctuations of the phenyl ring,7 whereas the a-relaxation is related to the segmental dynamics which is responsible for the glass transition. Mostly the glass transition is considered as a process which originates from cooperative uctuations. For PC the intermediate relaxation region between b- and a-relaxation is still under controversial discussion with regard to its molecular assignment (see for instance refs. 810). However, one has to state that according to the uctuation dissipation theorem the dielectric loss in this intermediate relaxation region corresponds to molecular uctuations taking place on a spatial length scale between the localized b- relaxation and the cooperative a-relaxation.
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Gas transport measurements


To measure the permeation of permanent gases the time-lag method5 was applied in the upstream pressure range from 1.0 to 20 bar using a temperature controlled setup. The samples were degassed prior to measurements using a turbomolecular vacuum pump system (<105 mbar). The pressure increase due to permeating gas molecules in the closed downstream volume (p2) was determined by a temperature controlled MKS Baratron gauge (10 mbar range). The lms had a diameter of 40 mm and a thickness between 40 and 70 mm. The permeability coefcient P was calculated from the linear pressure increase in the steady state region of the recorded curve using eq. (1):   VT0 dp2 P 1 ATp1 p0 dt s with V, downstream volume; , membrane thickness; T0 273.15 K; A, membrane surface area; p1 upstream presCopyright # 2005 John Wiley & Sons, Ltd.

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Figure 2. Dielectric loss e00 of pure polycarbonate versus frequency and temperature in a three-dimensional representation.

Figure 3. Dielectric loss e00 versus temperature at 10 KHz of PC and PC/SiC-nanocomposites for the labelled concentrations. Lines are guides for the eyes. A comparison of the temperature dependent dielectric spectra at 104 Hz of pure PC and those of nanocomposites with different concentrations of SiC particles is presented in Fig. 3. As for pure PC the three discussed relaxation regions can be also identied for the different nanocomposites. The most pronounced effects are a broadening of the b-relaxation and an increase of the dielectric loss in the intermediate relaxation region with increasing SiC concentration. The cooperative a-relaxation is not inuenced by the nanoparticles. As the b-relaxation peak is quite broad and weak (especially for the nanocomposites) from the measured isothermal data isochronal plots at a xed frequency versus temperature were constructed. From these charts the respective temperatures of maximal loss were taken at the selected frequency. The resulting relaxation map then allowed a quantitative analysis of the b-relaxation. The temperature dependence of the relaxation rate (frequency of maximal dielectric loss) fp,b can be described
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Figure 4. Relaxation fp,b versus 1/T for the b-relaxation for the labelled concentrations. The lines are ts of the Arrhenius equation to the data.

by an Arrhenius law (Fig. 4). fp;   EA; f1 exp kB T 3

where EA,b, activation energy; f1, pre-exponential factor; kB, Boltzmann constant; T, temperature. With increasing concentration of the SiC nanoparticles EA,b decreases systematically (see Fig. 5). This means that the nanoparticles increase the molecular mobility of these localized uctuations which have to be assigned to parts of the polymer chain situated close to these nanoparticles. This can be interpreted by an altered local free volume. The simplest model in which this dependence can be discussed is a two phase-model which is of course a strong simplication of the real structure. It is assumed that a boundary layer is formed around a nanoparticle having a higher molecular mobility with respect to localized uctuations than the bulk phase. So within the
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modes taking place on a length scale larger than the b-process but smaller than the a-process. A more detailed discussion requires additional investigations and is therefore beyond the scope of this study.

Gas transport properties


The driving force for gas transport is a concentration gradient across the membrane layer due to a pressure difference between its upstream and downstream side. The transport of small penetrant molecules through non-porous amorphous polymer layers is generally described in terms of a solution-diffusion mechanism consisting of: (1) the sorption of penetrant molecules at the upstream side (described by the solubility coefcient S), (2) the diffusive transport across the membrane layer (diffusion coefcient D) and (3) the desorption at the downstream side. The overall transport, characterized by P is given by: PDS 4

Figure 5. Activation energy of the b-relaxation versus the concentration of the SiC nanoparticles. The line is a linear regression to the data. investigated nanocomposite samples there are bulk-like regionsbecause the concentration of the nanoparticles is rather lowand regions belonging to the boundary layer. The observed b-peak is just a superposition of these two contributions whereas the contribution to the b-relaxation of the interfacial region is located at lower temperatures or higher frequencies than that of bulk PC. With increasing concentration of the SiC particles the contribution of the interfacial regions to the whole b-process increases. As a consequence of the increasing contribution of the interphase behavior to the relaxation, the b-peak broadens on the low temperature side and shifts to lower temperatures (compare Fig. 3). It should be mentioned that in the framework of the two phase model the estimated activation energies are effective ones. The a-relaxation (dynamic glass transition) is not affected by the presence of the nanoparticles (compare Fig. 3). This can be discussed in several ways. In the framework of the free volume picture, this means that the nanoparticles introduce free volume changes on a localized scale which is not big enough to have an impact on glass transition. On the other side it is widely agreed that the glass transition is a cooperative process in which a characteristic correlation length is involved. At Tg this length scale is in the order of a few nanometers (1. . .3 nm).11 From the observation that the a-process is not changed it could also be concluded that the interfacial regions do not have a glass transition. Then it can be furthermore concluded that the extension of the interfacial regions around the embedded nanoparticles can be expected to be below the characteristic correlation length of the glass transition (<3 nm) and that the length scale of interactions between nanoparticle and polymer matrix is also in this range. As already mentioned earlier a nite value of e00 (not just a peak) corresponds according to the uctuationdissipationtheorem to motional processes (for details see ref. 12). Therefore the intermediate relaxation region in the dielectric spectra in between the b- and a-process has to be assigned to molecular uctuations taking place on a length scale between localized (b-relaxation) and cooperative uctuations (arelaxation). The signicant increase of the dielectric loss in this relaxation region observed for increasing concentrations of the SiC-nanoparticles points to an acceleration of motional
Copyright # 2005 John Wiley & Sons, Ltd.

For glassy polymers the gas transport is usually interpreted in the framework of the dual mode sorption-model5,13 describing the sorbed penetrant concentration C as the sum of a Henry-type solubility (CD) and a Langmuir-type sorption (CH) resulting in sorption isotherms convex to the pressure axis (characteristic for glassy polymers) and a decrease in S and P with increasing pressure/concentration. One gets: C C D C H kD p C0H b p 1bp 5

where kD is the Henry coefcient, CH0 the Langmuir capacity and b the Langmuir hole afnity constant. Based on a simplied free volume-interpretation, the Henry contribution to the sorption can be related to the uctuating fraction of the free volume whereas the Langmuir part can be assigned to the frozen fraction. Figure 6 shows the gas sorption isotherms of CO2 at 358C for pure PC and two concentrations of SiC. A signicant change in the shape of the sorption isotherms for the nanocomposites in comparison to pure PC is observed. Equation (5) can be tted to the data and the dual sorption parameters can be estimated (Table 1). The values of b and C0 H are reduced in the nanocomposite materials compared to the pure PC whereas the kD value is remarkably increased which in turn can be interpreted as an increase of uctuating free volume fraction. This corresponds to a higher molecular mobility in the vicinity of the dispersed SiC nanoparticles and is in agreement with the results from dielectric relaxation spectroscopy.

Table 1. Dual mode sorption-parameters of the sorption isotherms of CO2 measured at 358C in the pressure range between 1 and 50 bar
Sample Pure PC PC/1.5 wt% SiC PC/5.0 wt% SiC kD 0.27 0.53 0.57 b 0.33 0.14 0.13 CH0 15.2 13.6 13.9

Units: [kD] 1 cm3(STP)/(cm3(polymer) bar); [b] 1 bar1, [CH0 ] 1 cm3(STP)/cm3(polymer).


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values for P as well as for Deff versus P which both strongly increase above 10 bar for pure PC. In the nanocomposite P exhibits the normal dual modebehavior, i.e. a decrease of permeability with increasing pressure which can be ascribed primarily to the decreasing S value. For Deff values in this case only a slight increase with increasing CO2-pressure is observed. So the supression of the distinct increase of permeability due to CO2 sorption-induced plasticization is mainly due to the changes of diffusivity in the nanocomposite. Therefore the incorporation of nanoparticles can be a promising strategy to improve the performance of polymer based membrane materials.

Figure 6. Sorption isotherms of CO2 at 358C for pure polycarbonate and two nanocomposites at the labelled concentrations. The lines are ts of the dual sorption model (eq. (5)) to the data. For highly sorbing gases (e.g. CO2) and vapors often a plasticization of a glassy polymeric matrix is observed leading to an increase of P and S above a plasticization pressure p*. This effectfor PC previously described in the literature14is found for pure PC membranes investigated in this study (see Fig. 7A) for p > 10 bar. This phenomenon is often connected with a signicant loss in permselectivity and mechanical stability which is especially critical for applications such as gas separation membranes. Therefore several attempts have been made to suppress plasticization in polymeric materials.15 17 In contrast to the pure PC the nanocomposite lm containing 5.0 wt% SiC does not exhibit this pronounced plasticization behavior. Figure 7(b) shows

CONCLUSION
Three different relaxation regions could be identied in the pure PC matrix as well as in the investigated nanocomposites. The a-relaxationcaused by cooperative segmental uctuationsremains unaffected by the presence of the SiC nanoparticles which can be ascribed to either a general limitation of the local inuence exerted by the ller particles on a small length scale or a limited extension of the modied interfacial boundary layer around the nanoparticles which may be considered too small to exhibit a glass transition or cooperative a-relaxation on its own. In contrast to this the b-relaxation and the intermediate relaxation region in between the b- and the a-process are strongly affected in the nanocomposite materials. The broadening of the b-relaxation as well as its decreasing activation energy can be described by a two-phase model based on a higher molecular mobility of the interfacial regions. The signicantly higher level of dielectric loss observed in the intermediate relaxation regionwhich is assigned to accelerated molecular motions on length scales between those of a- and b-processessupports this interpretation. The changed shape of the CO2 sorption isotherms of the nanocomposites compared to pure PC is analyzed in terms of the dual mode sorption model for glassy polymers. The distinct increase of the Henry sorption mode together with a slight decrease of the Langmuir sorption mode is ascribed to a higher fraction of highly uctuating free volume and less frozen-in microvoids present in the nanocomposite materials which is in agreement with the discussion of molecular mobilities resulting from dielectric relaxation spectroscopy. Although a comprehensive interpretation of the plasticization behavior of the nanocomposites compared to pure PC is beyond the scope of this study, the suppression of the pronounced CO2 plasticization of the polymer matrix can be understood in the framework of the above picture if it is assigned to the frozen-in free volume fraction. As this fraction is reduced in the nanocomposite materials in favor of the free volume fraction with a rather high mobility the sensitivity to plasticizing inuences due to sorbed gases has to be lower.

Figure 7. Pressure dependent permeability coefcient P (A) and diffusion coefcient Deff (B) of CO2 at 358C in pure PC (open circles) and the nanocomposite lm containing 5.0 wt% SiC (lled squares). The lines are guides for the eyes.
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Acknowledgments
The authors would like to thank I. Dorfel, I. Urban and W. Gesatzke (BAM) for the preparation of TEM pictures of the
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nanopowder and the nanocomposites. The nancial support of N. Hao in the framework of the Ph.D. program of BAM is highly acknowledged.

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Polym. Adv. Technol. 2005; 16: 262268