Chitosan/Silver Nanoparticles Composite: Molecular Relaxations Investigation by Dynamic Mechanical Analysis and Impedance Spectroscopy

J. BETZABE GONZALEZ-CAMPOS,1,2 EVGEN PROKHOROV,3* GABRIEL LUNA-BARCENAS,1 ISAAC C. SANCHEZ,4 2 3 OR,5 LORENZO GUEVARA-OLVERA5 JAVIER LARA-ROMERO, M. E. MENDOZA-DUARTE, FRANCISCO VILLASEN
1 2

CINVESTAV Queretaro, Libramiento Norponiente 2000, Fracc. Real de Juriquilla, Queretaro, Queretaro 76230, Mexico

Universidad Michoacana de San Nicolas de Hidalgo, Facultad de Ingeniera Qumica, Ciudad Universitaria, Morelia, Michoacan 58060, Mexico Centro de Investigacion En Materiales Avanzados, Chihuahua, Chihuahua 31109, Mexico Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712 Department of Biochemical Engineering, Instituto Tecnologico de Celaya, Celaya, GTO 38010, Mexico

3 4 5

Received 10 August 2009; revised 25 November 2009; accepted 20 December 2009 DOI: 10.1002/polb.21941 Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: By impedance spectroscopy, Gonzalez-Campos et al. J Polym Sci Part B: Polym Phys 2009, 47, 932943, reported the first evidence of a glass transition in a polysaccharide. To gain a better understanding on the molecular relaxations in polysaccharides, we study composites of chitosan (CS)/silver nanoparticles (AgnP) films by dynamic mechanical analysis (DMA) and dielectric spectroscopy in the 2250  C temperature range. CS/AgnP films conductivity increases in two orders of magnitude in comparison with pristine CS. Three relaxation processes ascribed to the a-relaxation, r-relaxation, and degradation process have been observed for the first time. Molecular dynamics and conductivity strongly depends on moisture content; since a plasticizing effect on the glass transition temperature is observed, similarly the increase in AgnP

weight percent leads to a glass transition temperature decrease and also increases CS thermal stability. Infrared spectroscopy analysis reveals the AgnPs interaction with OH, NH2, CO.NH2, and CAOAC groups implying an evident redistribution of the vibration bands for these groups. These new bonds affects the molecular dynamics of the CS chain bearing important changes in relaxations processes when compared CS/AgnP C composite with pristine CS. V 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 739748, 2010
KEYWORDS: chitosan; dielectric properties; dielectric relaxation;

dynamic mechanical analysis; glass transition; impedance spectroscopy; molecular dynamics; nanocomposites; polysaccarides; silver nanoparticles

INTRODUCTION In recent years, silver nanoparticles (AgnPs) have received special attention because of their unique properties that include inhibiting transmission of HIV and other viruses1 and antibacterial qualities that offers greater hygiene and control odor. They have been used in biosensors, given that they possess unique electric properties and can change their environment to enhance biosensor sensitivity.2 Recently, these nanoparticles have been combined with polymers as the matrix material in nanocomposites,3,4 due in part to the ease processing of the nanocomposite into useful forms. One way to enhance the antibacterial property of AgnPs preserving the easy handling and at the same time contributing to increase the wide range of applications is the use of a low cost, abundant, and environmentally friendly in nature biopolymer like chitosan (CS).

CS is a polysaccharide derived from chitin; it has a striking combination of properties such as biocompatibility, biode-

gradability, and nontoxicity. The latter features joined to its antibacterial characteristic makes it an exceptional material for biomedical applications.5,6 CS/metal nanoparticles combination is not new; this biomaterial has been combined with gold nanoparticles in sensing ions of heavy metals7 and silver, platinum, and palladium prepared by chemical reduction of the corresponding salt.8 The antimicrobial activity of CSbased composites has been previously studied;6,9 however, their mechanical and dielectric characterization have not been reported. By means of a fully material characterization, a complete understanding of its nature can be done and new potential applications can be established. Dielectric spectroscopy and dynamic mechanical analysis (DMA) are powerful tools that can fulfill this issue. CS possesses a several polar groups (OH, NH2) in its structure that makes it an ideal candidate to be use in dielectric spectroscopy and together with

*On leave from CINVESTAV, Unidad Queretaro (Sabbatical). Correspondence to: G. Luna-Barcenas (E-mail: gluna@qro.cinvestav.mx) C Journal of Polymer Science: Part B: Polymer Physics, Vol. 48, 739748 (2010) V 2010 Wiley Periodicals, Inc.

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its chelating characteristic its combination with AgnPs is feasible. Recently, molecular relaxations in chitin10 and pristine CS11 have been investigated using dielectric spectroscopy; these results show evidence of the low frequency a-relaxation present in dry annealed films. This relaxation process is related to the glass transition and a glass transition temperature is assigned by fitting the experimental data to the VogelFulcherTammann model. The purpose of this work is twofold; to synthesize CS/AgnP composites and to investigate the influence of AgnPs on the physical and mechanical properties of CS as well as on its molecular dynamics. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier transformed infrared spectroscopy (FTIR) were used to complement the study.
EXPERIMENTAL

Each sample was left at each measurement temperature for 3 min to ensure thermal equilibrium. Dynamic Mechanical Analysis DMA was made with a TA Instruments Dynamical Mechanical Analyzer model RSA III. The heating rate was 5  C/min at the frequency 0.1 Hz and an initial strain 0.1%. These measurements were carried out under the same heat treatment condition as for TGA measurements. Thermal Measurement Free water content was determined by TGA. The amount of free water may be evaluated by the decrease of sample weight during the heating scans with heating rate 5  C/min. DMA measurements were carried out in the experimental cell under dry air flow atmosphere during three consecutive scans: the first scan on wet samples (taken from room temperature and humidity conditions) was carried out from 30 to 80  C (samples annealed at 80  C) with a subsequent cooling to room temperature in the measurements cell. The second scan was performed on annealed at 80  C samples from 30 to 120  C (samples annealed at 120  C); afterward a second cooling to 30  C was done. Finally, the third scan was carried out on annealed at 120  C samples from 30 to 350  C. Using the same annealing methodology and measurements conditions as in DMA measurements, the moisture content can be monitored by TGA. As well as in DMA, dielectric measurements were carried out on wet, annealed at 80  C and annealed at 120  C samples. TGA measurements performed under the same heat treatment conditions but in argon atmosphere have shown that the moisture content in annealed at 120  C films is lower than 0.3%.11
RESULTS

CS/AgnP Composite Film Preparation Chitosan medium molecular weigh (Mw 150,000 g/gmol) and 82% of degree of deacetylation, reported by the supplier, was purchased from SigmaAldrich. Carbon-coated AgnPs powder, 25-nm average particle size, was purchased from nanotechnologies, and acetic acid from Baker was used as received. CS/AgnP films were obtained by dissolving 1 wt % of CS in a 1 wt % aqueous acetic acid solution with subsequent stirring to promote dissolution. Because of the films preparation technique, the CS films have the amino side group protonated (NH groups) and in this state, CS is called chito3 san acetate. This solution is poured into a Petri dish and allowed to evaporate at 60  C to obtain a pristine CS film. The proper quantity of AgnPs powder (1, 3, 5, and 10% w/w respect to CS dry based) was poured into a 1 wt % aqueous acetic acid solution and further sonicated during 30 min to obtained the nanoparticle solution. Afterward, the pristine CS film prepared before was dissolved into the AgnP solution and further sonicated for 10 min to eliminate bubbles formation. CS/AgnP films were prepared by the solvent cast method by pouring the final solution into a plastic Petri dish and allowing the solvent to evaporate for 24 h at 60  C. A thin layer of gold was vacuum deposited onto both film sides to serve as electrodes. Rectangular small pieces (5 mm 4 mm) of these films were prepared for measurements. Infrared Measurements and Morphology Analysis Chemical analysis of CS/AgnP composites was performed by FTIR on a PerkinElmer spectrophotometer using an ATR accessory in the range 4000650 cm1, resolution was set to 4 cm1, and the spectra shown are an average of 32 scans. CS/AgnP films morphology was analyzed by JEOM JSM7401F Field emission scanning electron microscope. Dielectric Measurements Dielectric measurements in the frequency range from 100 Hz110 MHz were carried out using an Agilent Precision Impedance Analyzer 4294A. The amplitude of the measuring signal was 100 mV. A peltier and a resistance heating element were used to perform measurements from 2 to 250  C.

Structural Analysis The solvent cast method used for the CS/AgnP synthesis allows obtaining self-supported, stable, and flexible cellophane-like appearance films with 30 lm of thickness. A change from transparent to gray, dark gray, and black color ascribed to the presence of AgnPs is noticeable when compared to pristine CS films with CS/1, 3, 5, and 10 wt % AgnP composites. SEM micrographs show a homogeneous distribution of AgnPs [Fig. 1(a)] along the films embedded into the biopolymeric matrix in a CS/1 wt % composite. However, for higher AgnP loadings, particles tend to agglomerate; this tendency is strongly reduced by the film preparation method for up to 3 wt % AgnP [see Fig. 1(b)]. To assure reproducibility of sample preparation, a simple SEM imaging analysis was performed on all samples in the following fashion: a samples SEM micrograph was digitized and the % of agglomerates was calculated (area-wise). For 1 wt % AgnP samples, no agglomerates (mean particle size, 25 nm) were observed, for 3 wt % AgnP is about 5% agglomerates (mean size, 200 nm). For 5 and 10 wt % AgnP samples, there is significant agglomeration producing about 10% (mean size, 400 nm) and 50% (mean size, 4000 nm) agglomerates,

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FIGURE 1 (a) CS/(AgnP) composites with 1 wt % of silver nanoparticles, (b) CS/(AgnP) composites with 3 wt % of silver nanoparticles. Note about 2% agglomerates (area-wise) are formed. See text for more details of sample preparation.

respectively. The effect of these agglomerates is discussed in the next section. Infrared Spectroscopy The Infrared spectra for pristine CS and CS/AgnP (1, 3, 5, and 10 wt %) composites are shown in window insert of Figure 2, a clear difference lies in the stretching and bending vibrations bands corresponding to amine and hydroxyl groups. In pristine CS, the characteristic 30003500 cm1 vibrational bands corresponding to the amine and hydroxyl groups, as well as peaks at 1654 cm1 (amide I group), 1594 cm1 (bending vibrations of NH2), 1383 cm1 (amide III) as well as the 1326 and 1261 cm1 (OH bending vibrations), 1157 cm1 (for antisymmetrical stretching of CAOAC bridge), 1084 and 1028 cm1 (for skeletal vibration of CAO stretching) distinctive for its polysaccharide structure can be identified.12 As it is shown in the magnified part of the spectra from 1800 to 800 cm1 in Figure 2, all these vibration bands change in position, amplitude, and intensity, indicating that the NH2 and OH groups bear new interactions with silver affecting their vibration characteristics. The 1654 and 1383 cm1 vibrations ascribe to CO.NH2 groups decrease their intensity after AgnP bonding and they shift to 1641 and 1373 cm1 wave numbers, respectively, with the AgnP wt % incorporation. At the same time, the vibrations bands at 1157 cm1 for the CAOAC bridge and 1084 and 1028 cm1 for skeletal vibration of CAO stretching shift to 1152, 1060, and 1021 cm1, respectively, for all AgnP weight percents. CS amides can be bound to silver via coordinate bond,13 and the reduction of vibration intensity is related to the attachment of AgnP owing to heavier molecule weight after Ag binding.14 It is important to note that pristine CS shows its characteristic bands at 1654 cm1 and 1594 cm1 related to amide and amine groups. As AgnP loadings increase, these
CHITOSAN/SILVER NANOPARTICLES COMPOSITE, GONZALEZ-CAMPOS ET AL.

vibration bands are shifted to lower wavenumbers (lower energies). Note that this shift is markedly observed from 1 to 3 and 5% AgnP and then to 10% AgnP. This result may suggest that agglomerates are playing a role in the films molecular architecture. TGA Measurements Thermogravimetric spectra (not shown) for a wet CS/AgnP (1 wt %) composite kept at normal ambient conditions before TGA, DMA, and dielectric measurements shows a weight loss of $8.5%. This weight loss is recognized and related to a water evaporating effect;10 this value is lower than that measured for pristine CS (11.5 wt %) and the previously reported in literature for chitin and CS (above 10 wt %).10,15,16

FIGURE 2 IR espectra for (a) pristine chitosan, (b) CS/AgnP (1 wt %), (c) CS/AgnP (3 wt %), (d) CS/AgnP (5 wt %), and (e) CS/AgnP (10 wt %). Note: Silver nanoparticles associate with amide, amine, and hydroxyl groups.

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FIGURE 3 (a) Moisture content in CS and CS/AgnP films with 3 wt % of Ag degradation temperature increase by AgnP incorporation (see details in text); (b) Ag nanoparticles weight percent dependence on moisture content in wet films. Note: moisture content decreases as AgnP increases.

For DMA and dielectric measurements, as mentioned earlier, three scans were performed to obtain different moisture content. For wet CS/AgnP (1 wt %) samples (measured by TGA analysis under the same annealing treatment than for DMA measurements), moisture content is about 8.5%. After the first scan and cooling to 30  C, a second scan to 120  C allows obtaining films with the moisture content about 4% (annealed at 80  C). Finally, after the second scan and cooling to 30  C, the third scan to 350  C reveals moisture content about 1.3% (annealed at 120  C). The degradation process in the biopolymer and bionanocomposite is denoted by a second weight loss above 240  C as it is shown in Figure 3(a) and observed in all TGA measurements. This mentioned weight loss has been reported by other authors and is related to CS thermal degradation.17,18 It is worthnoting that thermal stability of pristine CS is clearly affected by AgnP addition, since an evident increase of the degradation temperature by 20  C is distinguished by TGA analysis shown herein. It has been observed that moisture content on wet samples depends on Ag nanoparticles weight percent and it is shown in Figure 3(b); the higher the Ag nanoparticles weight percent, the lower the moisture content. As it was shown by FTIR analysis in the preceding section, the NH2 and OH groups can be bond with AgnPs affecting their vibration characteristics; this effect is related to the formation of a polymeric composite structure with nanoparticles9 and decrease the water absorption ability with increasing AgnP concentration in composites. This lower weight loss by increasing AgnP concentration has been previously observed in polymethyl methacrylate (PMMA)/Ag nanocomposites19 Dynamic Mechanical Analysis Figure 4 shows the tan d versus temperature curve for wet pristine CS and CS/AgnP (10 wt %) films. Pristine CS and all CS/AgnP investigated films exhibit three tan d peaks and its location depends on AgnP weight percent; the location of the first and second peaks obtained from fitting DMA experimen-

tal data according to AgnP weight percent are shown in Figure 5. Both peaks shift to lower temperature with increasing AgnP weight percent and it is noteworthy that the third peak located above 290  C slightly depends on Ag concentration. We propose that there exists a saturation threshold depending upon AgnP concentration. The addition of AgnP screens CSCS interactions thus reducing Tg. A saturation threshold occurs about 5 wt % AgnP when 200-nm agglomerates form and likely form a segregated phase. At 10 wt % AgnP, big 4000 nm agglomerates form. When this happens, the influence of AgnP is minimized and the dielectric response is not affected. Besides the effect of Ag nanoparticles weight percent presented on Figures 4 and 5, DMA measurements have shown that the position of the first peak is strongly affected by moisture content. This effect is clearly seen in Figure 6; the

FIGURE 4 Tan d versus temperature curves for pristine CS (open circles) and CS/AgnP (10 wt %) (open triangles) films. Note: the tan d peak depends on AgnP wt %.

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quency) and related it to the glass transition of CS; they point out a plasticizing effect on this relaxation peak with increasing glycerol content in CS/glycerol blends. Lazaridou et al.23 observed a similar effect on CS damping factor (tan d) peak below 100  C. This relaxation peak was assigned to the glass transition of CS and CS blends (with starch and pullulan); this relaxation process shifts to lower temperatures as water content increase, suggesting a plasticizing effect of water. The peak in the tan d curve at 150190  C has already been observed;20,2426 it has also been designated as the a-relaxation associated to the glass transition which is related to the molecular motion in the amorphous region. Sakurai et al.20 described the third peak (about 203  C) as the glass transition of CS; however, they performed a heat treatment up to 180  C before measurements and at this point, thermal degradation takes place. Our TGA results show a second weight loss beginning about 240  C pointing out the degradation process. This value is closely related to the degradation temperature previously reported for CS.24,25,27 From our knowledge, this is the first investigation about the relaxation processes in CS/AgnP composites films. In this case, an explanation about the nature of these relaxation processes based only on DMA measurements is ambiguous. Complementary dielectric spectroscopy measurements are needed to fully characterize relaxation processes in CS and CS/AgnP films. Dielectric analysis will allows us to support our DMA results and it is the focus of the next section. Dielectric Analysis The complex impedance spectra (Z00 vs. Z0 plot) for wet CS/ AgnP (3 wt %) film is shown in Figure 7; the interfacial polarization and contact effects discussed elsewhere28 are well identified and for the subsequent fitting treatment in both CS and CS/AgnP composites, it is important to consider

FIGURE 5 First and second peaks dependence on AgnP weight percent (see Fig. 4). Note: both peaks shift to lower temperature as AgnP weight percent increases.

three scans in a row for a CS/AgnP (10 wt %) film corresponding to 6.2, 3.2, and 0.7 wt % moisture content for the first, second, and third scan, respectively, are shown. As it can be seen this peak shifts to higher temperatures as moisture content decreases until vanishing at 0.7 wt % showing the strongly dependence of this relaxation process on water. This moisture content effect on the first relaxation peak has been observed in pristine CS and in composites with 1, 3, 5, and 10 wt % of AgnP. It is noteworthy that for pristine CS, these three peaks have been previously reported by other authors; the first peak about 100  C has been observed in DMA measurements,20,21 but there is no theoretically sound explanation and relation to moisture content. Quijada-Garrido et al.22 reported this relaxation peak between 88 and 99  C (depending on fre-

FIGURE 6 Tan d versus temperature curve for CS/AgnP (10 wt %) film during first (moisture content 6.2%) second (moisture content 3.2%) and third (moisture content 0.7%) scans.

FIGURE 7 Impedance spectra for CS and CS/AgnP (3 wt %) films at 35  C. Silver nanoparticles drastically increase the conductivity of dry chitosan samples (see text for details). Note: the Ro calculation is the intersection of fitting at Z00 0. See text for detail.

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only the so-called depressed semicircle that does not include contact polarization effect. The Havriliak and Negami (HN) model was used to calculate the relaxation time in the entire temperature range. The fitting of the complex permittivity in samples were carried out using the HN empiric correlation: e*e1 (ese1)/[1(jxs)a]b described elsewhere.29 To avoid the large conductivity contribution in the low frequency range, a direct conductivity (dc) correction has to be done in all samples before experimental data fitting to the HN relation.10,16,30 This dc conductivity strongly affects the modified loss factor e00 and it can be masking the low frequency relaxations.10 In our case, dc conductivity (rdc) cannot be calculated by the real component of the complex conductivity (see ref. 10 for details) because the experimental data do not resolved the plateau commonly observed in the low frequency side of the spectra.16,31 Therefore, Rdc is taken from the intersection of high frequency of the semicircle and the real part of impedance (Fig. 7) and with the thickness and the area of the sample, the rdc can be calculated (see ref. 10 for details). Once this correction has been done, low frequency relaxations are now disclosed and an accurate fitting can be performed (see Fig. 8 and ref. 10). If dc conductivity correction is not performed, a misleading interpretation of the molecular dynamics of CS/AgnP composites can be made especially in the low frequency side of the spectra.10,30,32 The addition of AgnPs increases dc conductivity of pristine CS about two orders of magnitude. It increases as AgnP weight percent increases, reaching saturation at 5 wt % as it is shown in Figure 9, and the higher dc conductivity values of CS/AgnP films in comparison to pristine CS are ascribed to the motion of Ag mobile charge carriers. Figure 10 shows the log rdc vs. 1/T plot for a CS/AgnP (10 wt %) wet film (moisture content 6.2 wt %) and after annealing in vacuum at 120  C for 1 h in vacuum cell (mois-

FIGURE 9 Conductivity in function of AgnP weight percent for wet CS/AgnP composites at 25  C.

ture content about 0.3 wt %). Let us focus on the 280  C temperature range; wet films show a non linear behavior well described by the VogelFulcherTammann (VFT) relationship,27 r r0exp(D/TTo) where r0 is the pre-exponential factor, D is a material constant, and T0 is the socalled Vogel temperature. Nevertheless, after obtaining the minimum moisture content (0.3 wt %), this nonlinear behavior vanishes after water evaporation by annealing at 120  C (annealed at 120  C film). At this point, a change to linear behavior has been observed from 2  C until the onset of degradation and it can be well described by the Arrhenius equation r r0exp(Ear/RT), where Ear is the activation energy. This change from VFT for wet films to an Arrhenius behavior for annealed at 120  C films was observed in pristine CS as well as in CS/1, 3, and 5 wt % of AgnP films. For pristine CS and CS/AgnP composites films annealed at 120  C, the activation energies calculated from the Arrhenius

FIGURE 8 Loss curves of CS/AgnP (1 wt %) films (annealed in vacuum at the temperature 120  C) in the 3890  C temperature range. Note: low frequency relaxations are disclosed after dc conductivity correction.

FIGURE 10 Log conductivity versus 1000/T for CS/AgnP (10 wt %) film. Wet and annealed in vacuum at 120  C for 1 h samples. Window insert: AgnP weight percent effect on Vogel temperature (T0) calculated by the VFT equation.

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FIGURE 11 (a) Relaxation time versus 1000/T for CS/AgnP (10 wt %). Note: the VFT behavior is observed in wet samples after fitting experimental data to the HN model. (b) HN parameters for CS/AgnP (10 wt %), VFT gives a 1 has in DavisonCole model, (c) Vogel temperature (T0) and Tg calculated from the 100 s rule; both temperatures decrease as AgnP wt % increases.

equation (moisture content % 0.3 wt %) in the whole temperature range (from 2  C to the onset of thermal degradation) are between 80 and 86 kJ/mol, this linear behavior is also observed in wet films above 70  C and is related to ion motion as described elsewhere.31,33 Above 170  C for pristine CS and CS/AgnP (1 wt %) films and 190  C for CS/AgnP (3, 5, and 10 wt %) composites, a change in the slope from negative to positive is also observed in Figure 10. This change is recognized as the beginning of the degradation.10 It is noteworthy that CS thermal stability increases by about 20  C when AgnP weight percent is above 3%, the same increasing effect on thermal stability has been previously observed in PMMA/Ag composites.19 Quijada-Garrido et al.22 showed a four stage process for CS thermal degradation according to TGA measurements. They stated that the first stage has a maximum at 187  C and represents a weight loss of methane and ammonia. The second stage has a maximum at 260  C and it is ascribe to the decomposition of the main chain with production of H2O, CO, and CO2 and some others fragments from the glucosaminic ring. The third stage with a maximum at 357  C is probably originated by the formation of a carbonaceous residue from the remaining degraded structure. And finally, the fourth stage with a maximum at 527  C involves the formation of methane. According to CS thermal degradation explained earlier, different degradation temperatures can be detected depending upon the technique used for thermal analysis. Dielectric spectroscopy seems to be the most sensitive technique to detect the first stage related to thermal degradation as it is present at around 190  C; however, no further measurements can be done because the sample brakes down and there is no contact above this temperature, so the remaining stages can not be detected. On the other hand, both DMA
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and TGA measurements are likely more sensitive to the decomposition of the main chain degradation stage detecting it at around 290  C. It was also shown by DMA measurements that AgnP weight percent has a significant effect on the glass transition temperature. Relaxation times for CS/AgnP (10 wt %) composites obtained by the fitting procedure described earlier are shown in Figure 11(a). As well as for conductivity dependencies, relaxation times in the 280  C temperature range for wet films show the non linear behavior described by the VogelFulcherTammann (VFT) relationship: s s0exp(D/ TTo), the Vogel temperature is $236.4 K, and it is in agreement with that obtained by fitting the conductivity data to the VFT model showed in Figure 10. It is worthnoting that the a-relaxation process is not detected in annealed at 120  C (moisture content <0.3%) films. This is because the Arrhenius type behavior is present in the whole temperature range before thermal degradation (190  C). The activation energy for this linear relaxation process is about 7985 kJ/ mol and is related to ion motion as reported elsewhere.16,30,33 The a and b shape parameters of the HN function representing the broad and symmetry of relaxations processes, respectively, for a CS/AgnP (10 wt %) composite are shown in Figure 11(b). A similar behavior was observed for all AgnP contents; this a-relaxation is asymmetric and can be well described by the DavisonCole equation as the a parameter is very closed to unity and it is independent of temperature for the 280  C range. The b parameter shows a weakly dependence on temperature when increasing from 0.2 to 0.38 as temperature increases; a similar behavior for these parameters in diethyl phthalate was reported elsewhere.34 Figure 11(c) shows the comparison of Tg calculated from the VFT analysis and from the 100 s rule. The 100 s is a common definition for obtaining the Tg from dielectric
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measurements, that is, the temperature at which the dielectric relaxation time is equal to 100s.35 Both predictions show Tg decreases as AgnP wt % increases. A possible scenario for this observation is now addressed. AgnP bonds to the primary amine groups or possibly hydroxyl groups screening the intermolecular, strong CSCS interactions, thus facilitating main-chain mobility. The final result is a Tg depression. However, more studies are needed to shed light into this argument. The VFT parameters calculation includes the Vogel temperature (T0) obtained by fitting the experimental data (conductivity and relaxation time) to the VFT model. As it is shown in window insert of Figures 10 and 11(c), the higher the AgnP weight percent, the lower T0. The D and log s0 parameters do not have a clear trend depending upon AgnP content, as D values are 214.42, 136.91, 224.98, 300.65, and 255.49 and log s0 values are 5.052, 4.60, 4.42, 4.901, and 4.19 for 0, 1, 3, 5, and 10 AgnP wt % respectively. A similar trend has been reported elsewhere.36 The aforementioned values for log s0 for the VFT behavior extrapolate to values between 105 and 106 s for the studied temperature range and not to 1014 s (i.e., the approximate vibration time of single molecules) as normally observed for bulk nonpolymeric materials. This fact is not uncommon as reported elsewhere.29,36 Jansson et al.36 proposed a hypothesis for the earlier observations based upon the strong molecular interactions present in gels and carbohydratewater systems. The water molecules move collectively with slower dynamics than that of molecular vibrations. Thus, s0 no longer extrapolates to the vibration time of a single water molecule, but rather to these slower collective modes. The high frequency secondary b-relaxation, which has been reported in the literature for pristine CS and other polysaccharides,16,31,33 has not been observed in films containing AgnP by dielectric spectroscopy. b-relaxation is related to segmental motion via the glucosidic bond16,31,33 and as it was previously shown by infrared spectroscopy, AgnPs can be bond to OH, NH2, CONH2, and CAOAC groups. The 1157 cm1 band corresponding to an antisymmetrical stretching of CAOAC bond has significant changes in position, broad and intensity ascribe to AgnPs and glucosidic linkage interaction that produce a redistribution of the former vibration band. This new interaction restricts the glucosidic linkage mobility making the b-relaxation weaker and difficult to detect.
DISCUSSION

16  C is obtained. This relaxation process is highly dependent on moisture content as it was shown by dielectric measurements. Thus, the first relaxation process observed by DMA analysis (Fig. 6) that shows analogously the moisture effect is related to this nonlinear behavior which is the glass transition phenomenon. The difference between the glass transition temperature obtained in DMA and this from dielectric spectroscopy measurements could be related to the fact that dielectric spectroscopy is sensitive to dipole moments fluctuations and mechanical relaxation monitors the fluctuations of internal stresses. According to the literature, for many polymers mechanical relaxation processes are observed at temperatures different from that obtained by dielectric relaxation.22 The a-relaxation process is strongly dependent on both moisture content (Figs. 6 and 10) and AgnP weight percent (Fig. 5 and window insert of Fig. 10). Our results suggest a plasticizing effect of water on CS composites shifting the glass transition temperature to lower values as moisture content increases. On the other hand, the addition of AgnP screens CSCS intrachain interactions facilitating segments motion and thus reducing the glass transition temperature as AgnP wt % increases. The AgnP dispersion in the polymer matrix alters the characteristic properties of the host polymer matrix including the glass transition temperature and thermal degradation.21 In the CS and CS/AgnP films, annealed at 120  C (moisture content lower than 0.7% in DMA and 0.3% in dielectric spectroscopy measurements) the a-relaxation process vanishes and a glass transition is not detected. This fact entails that a plasticizer effect of water undergoes a glass transition. A decrease in moisture content leads to increasing the glass transition temperature as it was shown by DMA measurements in Figure 6. If moisture can be completely eliminated (<0.3%), the mobility of polymer chains decreases and the glass transition phenomenon can not be observed; therefore, the a-relaxation process vanishes (see Figs. 6, 10, and 11). In wet samples, for the 70190  C temperature range, in both conductivity and relaxation time plots, an Arrheniustype behavior (Figs. 10 and 11) is present in wet and annealed samples; the activation energies are between 79 and 86 kJ/mol. These values are in agreement with previous reports for CS and other polysaccharides.16,31,33 This process is associated with the hopping motion of ions in the disordered structure of the biomaterial and is called r-relaxation.31,33 The r-relaxation process has been widely discussed for polysaccharides31,33 and especially for CS.16 According to DMA (second peak) and dielectric results, the r-relaxation does not depend on moisture content. However, DMA measurements showed that this relaxation process shifts to lower temperatures with increasing AgnP weight percent (see Fig. 5). This effect can be related to an increase of Ag ions that effectively increases conductivity of CS/AgnP films (Fig. 9). The results obtained by dielectric spectroscopy measurements allow to conclude that the second peak at 160  C in

The nonlinear VFT behavior observed in conductivity and relaxation time versus 1000/T plots is a well known feature of the a-relaxation process related to the glass transition. In many polymers, the Vogel temperature T0 (sometimes called the ideal glass transition temperature37) is usually 50 K lower than the glass transition temperature Tg.29 In this case, for the CS/AgnP film (10 wt %) presented in Figures 10 and 11(a), T0 is 236.4 K. Once a T0 is calculated, a Tg
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the tan d curve for a CS/AgnP(10 wt %) film, can be related to the r-relaxation process which does not depend on moisture content. The change in the slope at 190 C and above in dielectric measurements can be related to the third peak above 200  C in DMA measurements and they are ascribed to the beginning of biopolymer degradation.


3 Zhan, Z.; Zhang, L.; Wang, S.; Chen, W.; Lei, Y. Polymer 2001, 42, 83158318. 4 Xiang, Y.; Chen, D. Eur Polym J 2007, 43, 41784187. 5 Muzzarelli, R. A.; Biagini, G. In: Chitinenzymology, Muzzarelli, R. A. A. Ed.; European Chitin Society: Ancona, 1993; pp 187196. 6 Xu, H.; Ma, L.; Shi, H.; Gao, C.; Han, C. Polym Adv Technol 2007, 18, 869875. 7 dos Santos, D. S., Jr.; Goulet, P. J. G.; Pieczonka, N. P. W.; Oliveira, O. N., Jr.; Aroca, R. F. Langmuir 2004, 20, 1027310277. 8 Huang, H.; Yuan, Q.; Yang, X. Colloids Surf B 2004, 39, 3137. 9 Rhim, J. W.; Hong, S. I.; Park, H. M.; Perry, K. W. J Agric Food Chem 2006, 54, 58145822. 10 Gonzalez-Campos, J. B.; Prokhorov, E.; Luna-Barcenas, G.; Mendoza-Galvan, A.; Sanchez, I. C.; Nuno-Donlucas, S. M.; Gar ca-Gaitan, B.; Kovalenko, Y. J Polym Sci Part B: Polym Phys 2009, 47, 932943. 11 Gonzalez-Campos, J. B.; Prokhorov, E.; Luna-Barcenas, G.; Fonseca-Garca, A.; Sanchez, I. C. J Polym Sci Part B: Polym Phys 2009, 47, 22592271. 12 Zhang, J.; Yuan, Y. L.; Shen, J.; Lin, S. C. Eur Polym J 2003, 39, 847850. 13 Zhang, X.; Yang, P.; Yang, W.; Chen, J. Mater Sci Eng 2008, C28, 237242. 14 Dongwei, W.; Weiping, Q. Colloids Surf B 2008, 62, 136 142. 15 Pizzoli, M.; Ceccorulli, G.; Scandola, M. Carbohydr Res 1991, 222, 205213. 16 Viciosa, M. T.; Dionisio, M.; Silva, R. M.; Mano, J. F. Biomacromol 2004, 5, 20732078. 17 Balau, L.; Lisa, G.; Popa, M. I.; Tura, V.; Melnig, V. Cent Eur J Chem 2004, 2, 638647. 18 Machado, A. A. S.; Martins, V. C. A.; Plepis, A. M. G. J Therm Anal Cal 2002, 67, 491498. 19 Chatterjee, U.; Jewrajka, S. K.; Guha, S. Polym Compos 2009, 30, 827834. 20 Sakurai, K.; Maegawa, T.; Takahashi, T. Polymer 2000, 41, 70517056. 21 Zong, Z.; Kimura, Y.; Takahashi, M.; Yamane, H. Polymer 2000, 41, 899906. 22 Quijada-Garrido, I.; Iglesias-Gonzalez, V.; Mazon-Areche derra, J. M.; Barrales-Rienda, J. M. Carbohydr Polym 2007, 68, 173186. 23 Lazaridou, A.; Biliaderis, C. G. Carbohydr Polym 2002, 48, 179190.

CONCLUSIONS

CS/AgnPs (AgnP) thin films were successfully synthesized by the solvent cast method. A cellophane-like gray color appearance and self-supported thin films were produced. New AgnPs interactions with the OH, NH2, CONH2, and CAOAC groups are observed when analyzing infrared spectra by the redistribution of these vibration bands. The dielectric and dynamic mechanical behaviors of CS/AgnP films have been investigated as a function of moisture and AgnP contents. For the first time, we have shown three relaxation processes: (1) First, a primary a-relaxation process, related to a glass transition is observed, in wet CS/AgnP films, it shifts to higher temperature with decreasing moisture content; however, in dry composites (less 0.30.7 wt % moisture content), the glass transition cannot be observed as previously reported by our group. This primary a-relaxation process is also affected by the AgnP weight percent; the higher the AgnP wt %, the lower the glass transition temperature. The addition of AgnP screens CSCS interactions and facilitates segment motion, thus the glass transition temperature shifts to lower values as AgnP wt % increases. (2) Second, a second low frequency relaxation process was observed from 70  C to the onset of thermal degradation (190  C) in wet films. This relaxation is identified as the r-relaxation often associated with ion mobility. In dry (annealed) films, the r-relaxation process seems to overcome the a-relaxation process in such a way that the glass transition is no longer detected from 2  C to the onset of degradation. The r-relaxation exhibits a normal Arrhenius-type temperature dependence with activation energy about 7986 kJ/mol independent of moisture content. Finally, a third relaxation process above 190  C related to thermal degradation has also been observed in agreement to previous studies on CS. This work was partially supported by CONACYT of Mexico. The authors are grateful to J.A. Munoz-Salas for assistance in electri cal measurements and to R.A. Mauricio Sanchez for FTIR measurements. G.L.-B. acknowledges support from CONACYT 58239 and 78798.

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