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Journal of Magnetism and Magnetic Materials 279 (2004) 184194

Characterization, electrical and magnetic properties of PVDF lms lled with FeCl3 and MnCl2 mixed llers
M. Abdelaziz
Department of Physics, Faculty of Science, Mansoura University, P.O. Box 19, 35516 Mansoura, Egypt Received 11 November 2003

Abstract Polyvinylidene uoride (PVDF)/(x) FeCl3 (20x) MnCl2 lms, where x=0.0%, 1%, 5%, 10%, 15%, 19%, and 20%, were prepared by the casting technique. Their thermal and crystalline structure, electric and magnetic properties, and ESR were examined. For thermal measurements, with increasing FeCl3 content, the melting temperature rarely changed while the thermal degradation temperature decreased. X-ray diffraction and infrared analysis show that the crystalline structure of PVDF changed drastically on addition of FeCl3, indicating that there are interactions between the PVDF matrix and FeCl3 and MnCl2. The optical and electrical measurements revealed a nearly monotonic behavior of optical gap and electrical resistivity as FeCl3 content increased. The direct current (DC) magnetic susceptibility indicates a predominantly ferromagnetic interaction between the magnetic ions at lower temperatures for all samples. The ESR spectra indicate the aggregated forms of Fe3+ and Mn2+ ions that conrm the results obtained from optical measurements and DC magnetic susceptibility. r 2004 Elsevier B.V. All rights reserved.
PACS: 71.20.R; 72.80.L; 75.50.P Keywords: Polyvinylidene uoride; FeCl3MnCl2 mixed llers; Optical spectra; DC electric conduction; DC magnetic susceptibility and ESR

1. Introduction Polyvinylidene uoride (PVDF) is a polycrystalline polymer started drawing scientic interest in the seventies, because of its extraordinary pyroend piezoelectric properties. These properties combined with both high elasticity and processing ability lend this material numerous technological applications [1]. Another feature that distinguishes PVDF from other polymers is its polymorphism, that is, it may present at least ve crystalline phases,
E-mail address: mabdelaziz62@yahoo.com (M. Abdelaziz).

namely a, b, d, g, and e [2]. Moreover, an increasing interest has been devoted to PVDF as electric and/or magnetic eld sensors. For this application, PVDF was lled with transition metal halides [3]. Fillers are used in polymers for a variety of reasons: cost reduction, improved processing, density control, optical effect, thermal conductivity, control of thermal expansion, electrical properties, magnetic properties, ame retardancy and hardness, and tear resistance [4]. For example, in optical, electrical and magnetic applications, llers such as FeCl3 and MnCl2 are used to provide better optical, electrical and magnetic properties.

0304-8853/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2004.01.091

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Most studies considered the FeCl3 ller as an efcient electron acceptor and this was attributed to the formation of Fe2Cl2 [5]. Manganese is well 4 known as a magneto-active multivalent element; thus its halides can be used as llers to modify the electric conduction, the optical absorption and magnetic properties of PVDF. On the other hand, MnCl2 is considered as a good candidate for oneor two-dimensional phenomena [6] and for optical memory device [7]. In our previous works, we investigated the physical properties of PVDF lms lled with FeCl3 [8] and MnCl2 [9]. These investigations revealed that the used llers modied the electric and magnetic properties of PVDF. However, a nonlinear (even nonmonotonic) lling level (FL) dependence of the contents of the active structural forms was found. This exerted a strong inuence on the electrical and magnetic properties of the lled PVDF lms. While searching for a linear (or monotonic) FL dependence of the electrical and magnetic properties, in a fair FL range, it was thought to use the intrasubstituted (x) FeCl3 (20x) MnCl2 mixed llers. Therefore, the present work was devoted to investigate the effect of lling PVDF with a mixture of FeCl3 and MnCl2 on crystal structure, optical, electrical and magnetic properties.

range of 20400 C and a heating rate of 5 C min1. The X-ray diffraction (XRD) scans were obtained using a Seimens type F diffractometer with CuKa radiation and LiF monochromator. UV/VIS absorption spectra were measured in the wavelength range of 200900 nm using a spectrometer (Perkin Elmer UV/VIS). The infrared (IR) spectrophotometer (Perkin Elmer 883) was used for measuring the IR spectra in the wavenumber range of 4000400 cm1. The direct current (DC) electrical resistivity was measured, by the twoprobe method, using an autorange multimeter (Keithley 175) with an accuracy of 0.2%. The DC magnetic susceptibility was measured using the Faraday pendulum balance technique that provides an accuracy of better than 3.0%. ESR spectra were measured with an X-band ESR spectrometer (Bruker, EMX) at room temperature using standard rectangular cavity (4102 ST) operating at 9.7 GHz with a 100 kHz modulation frequency.

3. Results and discussion 3.1. Differential thermal analysis The thermal behavior of PVDF lms lled with (x) FeCl3 (20x) MnCl2, where x=0%, 5%, 10%, 15% and 20%, was studied by DTA in the temperature range of 20400 C; see Fig. 1. From this gure, we observe that the lled PVDF lms displayed three transitions at about 30 C, 100 C, 175 C. In addition, another endothermic peak at B275 C is related to the thermal degradation of the polymer [10]. The observed transitions can be assigned as follows: the Tw B30 C endotherm is due to the small amount of water that is always present in the conventional polymer unless it is carefully vacuum dried [11]. The exothermic peak at Tc B100 C is attributed to the relaxation associated with the crystalline region. An endothermic peak is observed at Tm B175 C which is attributed to the PVDF melting. The order of reaction, n; at Tm peak is calculated using the Kissinger method [12] and the values of n; Tw ; Tc Tm and Td are listed in Table 1. For x 0:0; the small endothermic peaks, observed at temperature

2. Experimental 2.1. Sample preparation Films of PVDF lled with (x) FeCl3 (20x) MnCl2 were prepared by the casting method. Dimethylformamide was used to dissolve the used materials. Mixtures of the dissolved polymer with mixed halides was placed in a glass dish and kept in a dry atmosphere at 323 K for 2 weeks to remove the solvent traces. Different concentrations of the llers were obtained, where x 0:0; 1, 5, 10, 15, 19 and 20 wt%. The thickness of lms was in the range of 100150 mm. 2.2. Measurements DTA was carried out using an equipment type (Shimadzu DTA50) with a measuring temperature

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3.2. X-ray diffraction XRD patterns of the present system are shown in Fig. 2. Obviously, the XRD patterns indicate the presence of a semicrystalline structure. The assignments [16] of these crystalline peaks are listed in Table 2. It is clearly seen that all samples under investigation contain b- and a-crystalline phases except at x 5% and 20% contain the a-phase only. Interestingly, only the sample at x 10% contains a higher content of crystallinity. 3.3. Optical absorption The optical absorption spectra are carried out for PVDF lms lled with two mixed llers FeCl3 and MnCl2 and are shown in Fig. 3. The bands in the range of 370500 nm are due to crystal eld transitions of the tetrahedral isolated Fe3+ ions [17]. Some of the observed band positions and their assignments are given in Table 3. Moreover, the absorption coefcient an at various frequency (n) values was calculated using the following formula: an lnt1 n=t2 n=d1 d2 ; 1

Fig. 1. The DTA thermograms of PVDF lled with (x) FeCl3 (20x) MnCl2.

Table 1 FL dependence of: water (Tw ), crystalline (Tc ), melting (Tm ) and thermal degradation (Td ) temperatures and order of reaction (n) FeCl3 (wt%) 0.0 5 10 15 20 Tw ( C) 43.9 31.4 31.5 32.6 29.4 Tc ( C) 95.7 99.5 112.2 109.4 103.9 Tm ( C) 176.2 174.5 175.2 173.6 173.7 Td ( C) 375.5 330 310.4 267.8 n 1.1 1.02 1.02 1.06 1.02

oTm ; are assigned to the ferroelectric to paraelectric phase transitions [13]. The values of n were B1. This indicates that all the reactants melted at Tm : It can be observed from Table 1 that the values of thermal degradation temperature Td decrease as the FeCl3 content increases. It is suggested that the addition of FeCl3 decreases the thermal stability. This agrees with the results obtained by Zidan [14]. Moreover, for x 10% there are two endothermic peaks at B217 C and 253 C that may be attributed to the dehydration of MnCl2 4H2O and/or FeCl3 H2O [15].

Fig. 2. XRD patterns of PVDF lms with various mass fractions of (x) FeCl3 (20x) MnCl2.

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M. Abdelaziz / Journal of Magnetism and Magnetic Materials 279 (2004) 184194 Table 2 Assigned [16] X-ray diffraction peaks characterizing the crystalline PVDF phases FeCl3 (wt%) 0.0 2y (deg) 20.5 39.5 38.8 20.4 39.5 20.4 39.0 39.8 Assignments (1 1 0) b, (2 0 0) b (0 0 2) a (0 0 2) a (1 1 0) b, (2 0 0) b (0 0 2) a (1 1 0) b, (2 0 0) b (0 0 2) a 15 20 (0 0 2) a 187

Table 3 The observed band positions and their assignments [17] for the tetrahedral Fe3+ FeCl3 (wt%) 5 Observed wavelength (nm) 307 370 409 398 361 409 295 358 397 424 316 364 406 Transitions 6A1g(S)4 4

5 10

T1g(P) T2g(D) 4 Eg(G)

4 4

10

15

T1g(P) T2g(D) 4 Eg(G)

4 4

T1g(P) T2g(D) 4 Eg(G) 4 A1g(G)

4 4

20

T1g(P) T2g(D) 4 Eg(G)

energy hn (where h is Planks constant), we obtain the curves shown in Fig. 4. Each curve exhibits a linear portion characterizing an optical gap Eg according to the Davis and Mott formula [18] an Bhn Eg 2 =hn; 2

where B is a constant. The linear portion of Fig. 4 is used to obtain the value of the optical gap (namely Eg ). Fig. 5 depicts the dependence of Eg on the FeCl3 content. It is clear that Eg exhibits a rapid increase up to x 5%: Then Eg increases linearly as FeCl3 content increases, in which the data can be tted by the following relationship: Eg 0:01x 2:25; 3

where x is the percent of FeCl3 content. The change of Eg may be attributed to the change of induced energy states due to the change of chilation mode at FL=5% [19].
Fig. 3. The UV/VIS absorption spectra of PVDF lms lled with various FLs.

3.4. IR transmittance Fig. 6 shows the plots of infrared absorption spectra for PVDF lled with (x) FeCl3 (20x) MnCl2, where x=0%, 5%, 10%, 15%, and 20%, in the spectral range 4000400 cm1. The spectra of all samples are nearly similar. Main

where t1 and t2 are the transmittances of two lms (of the same concentration) with thicknesses d1 and d2 : Plotting ahn1=2 as a function of the photon

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Fig. 5. Dependence of an optical energy gap Eg on FLs.

assigned to the CQC stretching in the diuorinated alkenes [21] revealed minimum values at x 10%: The band at 750 cm1, which refers to the head-to-head (h2h) and tail-to-tail (t2t) defects [22], revealed a minimum value at x 10%: The change of the intensities of these certain IR absorption bands indicates a change of the chelation mode of FeCl3 and/or MnCl2 with the PVDF matrix. It is noteworthy that the CQC mode and the h2h defects are suitable sites for polarons and/or bipolarons formation in the PVDF matrix.
Fig. 4. (a, b) (ahn)0.5 vs. photon energy for various FLs: (1) 0.0%, (2) 5%, (3) 10%, (4) 15%, and (5) 20%.

3.5. DC electrical resistivity As a function of temperature, T; the electrical resistivity, r; of the prepared samples was measured in the range 293403 K. The temperature dependence of the electrical resistivity was examined according to two basic existing theories, which are Arrhenius and modied interpolaronhopping model. The obtained results can be concluded as follows: (a) In Fig. 8, an Arrhenius plot of resistivity vs. temperature is shown as follows: r r0 expEa =kT; 4

characterizing peaks of PVDF can be noted. Further, the IR vibrational modes due to the aphase are 670, 750 and 870 cm1 and the vibrational modes due to the b-phase are 508 and 840 cm1. The IR vibrational modes due to the g-phase are identied at 950 cm1 [20]. The structural modication can be identied by investigation of the FL dependence of certain IR absorption peaks 750, 840, 950, and 1650 cm1 depicted in Fig. 7. The intensities of the bands at 840 cm1 that refers to the b-phase, 950 cm1, which refer to the g-phase and 1650 cm1 that was

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Fig. 7. FL dependence of the IR peaks at: (a) 840 (J) and 1650 cm1 (n), (b) 750 (n) and 950 cm1 (J).

Fig. 6. IR transmission spectra of PVDF lled with various FLs.

where r0 is the pre-exponential rate corresponding to 1=T 0:0; Ea the activation energy for this thermal activated process and k the Boltzmanns constant. The variation in the logarithmic scale electrical resistivity values as a function of the reciprocal absolute temperature for samples is represented in Fig. 8. The values of electrical resistivity, r0 ; and activation energy Ea of the sample are determined through

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Fig. 9. Dependence of activation energy Ea (J) and log r (n) on various FLs.

Fig. 8. (a, b) Reciprocal temperature dependence of log r on various FLs: (1) 0.0%, (2) 1%, (3) 5%, (4) 10%, (5) 15%, (6) 19%, and (7) 20%.

monotonic decrease as FeCl3 content increases. (b) The diuorinated alkenes (detected by IR analysis) indicating the presence of conjugated polyene and h2h defects may evidence the formation of polarons in the polymeric matrix. Therefore, the present results can be discussed on the basis of Kuivalainen et al.s [24] modied interpolaron-hopping model, in which the conduction is attributed to phonon-assisted hopping between polaron and/or bipolaron-bound states in the polymer. According to this model, the electrical resistivity can be expressed as   kT R2 yp ybp 2 2BR0 0 r exp ; 5 yp ybp x Ae2 gT2 x where A 0:45; B 1:39; yp and ybp are the concentrations of polarons and bipolarons, respectively; R0 3=4pCimp 1=3 is the typical separation between impurities whose concentration is Cimp ; z zJ z2 1=3 is the average > decay length of a polaron and bipolaron wave function; and zJ and z> are the decay lengths parallel and perpendicular to the polymer chain, respectively. Bredas et al. [25] reported that the extension of defect should be the same for polarons and bipolarons. The electronic transition rate between polaron and bipolaron

Eq. (4) and are plotted in Fig. 9. It can be clearly seen that all samples have semiconducting property because their resistivity decreases with an increase in temperature [23]. In this temperature region, the electrical activation energy of all samples has a positive value and has a maximum value at x 10%: Moreover, the logarithm of r0 shows a

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states can be expressed as gT 1:2 1017 T=300 K11 : 6 Using a computer-aided program, the order of magnitude of r in the present system was adjusted with the impurity concentration Cimp ; which actually was the tting parameter. The parameter zJ 1:06 nm while z> 0:22 nm [26], which depends on the interchain resonance energy and the interchain distance. Taking yp ybp for simplicity, which is an acceptable approximation [27], using Eqs. (5,6), we can obtain the values of the hopping distance R0 : A linear decrease of R0 as the temperature increases, for various FLs, can be noted in Fig. 10. This indicates that the concentration of thermally activated polarons (acting as hopping sites for the charge carriers) increases gradually as the temperature increases. Fig. 11 shows the FL dependence of log r measured (and R0 calculated) at T 373 K. The log r and R0 have a slight change up to x 5% and a rapid decrease as FeCl3 content increases. It is remarkable that the logarithm of resistivity is in the range of 6.79.1, indicating a semiconducting order. On the other hand, the obtained values of R0 were in the range of 0.94.4 nm, which were 418 times the monomer length (B0.25 nm [28]). This indicates that the electrical conduction is an interchain one-dimensional hopping type. 3.6. DC magnetic susceptibility The temperature dependence of the reciprocal values of the DC magnetic susceptibility, w; measured in the temperature range of 95285 K for various FLs is shown in Fig. 12. It is clear that w obeys CurieWeiss law [29] in which w C=T yp ; 7
Fig. 10. (a,b) Temperature dependence of hopping distance R0 for various FLs: (1) 0.0%, (2) 1%, (3) 5%, (4) 10%, (5) 15%, (6) 19%, and (7) 20%.

equation meff 2:839wm T yp 1=2 8

where C is the Curie constant and yp is the paramagnetic Curie temperature. Positive yp values, shown in Table 4, obtained for all samples under study suggest a ferromagnetic exchange interaction between the magnetic centers. The CurieWeiss plots were used, together with the

to calculate the effective magnetic moment, meff ; where wm is the molar susceptibility of the used sample. The FL dependences of meff are shown in Fig. 13. It is remarkable that meff has a symmetric behavior for 0:0pxp10 and 10oxp20 which exhibits two minima at x 5% and 15% and a

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Fig. 11. FL dependence of log r (K) and R0 (J) at T 373 K.

maximum value is observed at x 10%: The values of meff were in the range of 2.84.2 BM, which correlated to the existence of Fe3+ and Mn2+ [29]. These ndings support the results obtained from optical measurements. 3.7. ESR The ESR spectra of PVDF lled with various fractions of FeCl3 and MnCl2 are observed in Fig. 14. The main characterizing features of PVDF, previously reported in Ref. [30], are not observed in the present spectra. The PVDF hyperne spectra disappeared and strong Lorentzian signals were observed which may be ascribed mainly to the Fe3+ and/or Mn2+ cluster coupled by strong spinspin interaction. Moreover, for the case of x 0:0% and 1% the spectra are characterized by unresolved 6-weak hyperne lines superimposed on the lower eld side of the Lorentzian signal arising from the hyperne structure of the manganese nucleus (I 5=2) with an unpaired electron, indicating isolated Mn2+ in the ionmer [31]. The FL dependence of the ller local structural can be claried more explicitly with the aid of peak-to-peak separation (DH) of the Lorentzian signal and the symmetry factor (A), which is the ratio between the two halves of the Lorentzian signal. The FL dependences of A and DH are

Fig. 12. Temperature dependence of the reciprocal magnetic susceptibility for variously lled PVDF lms: (1) 0.0%, (2) 1%, (3) 5%, (4) 10%, (5) 15% (6) 19%, and (7) 20%.

shown in Fig. 15. It may be seen that A shows a monotonic increase as FeCl3 content increases for xX5%: On the other hand, DH also shows a monotonic increase as FeCl3 content increases for

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M. Abdelaziz / Journal of Magnetism and Magnetic Materials 279 (2004) 184194 Table 4 FL dependence of paramagnetic Curie temperature yP FeCl3 0.0 1 5 10 15 19 20 yp (K) 45.2 34 59.5 1.5 41.6 37.3 39.2
x(wt%) 20

193

(x)FeCl3(20-x)MnCl2

Intensity (a.u.)

19 15 10 5 1 0

1000

2000

3000

4000

5000

6000

Magnetic field (Gauss)

Fig. 14. ESR spectra of PVDF lled with various FLs.

Fig. 13. FL dependence of meff (n).

x > 0%; indicating the increase of dipolar interactions between the magnetic ions [13].

4. Conclusion
Fig. 15. FL dependence of A (J) and DH (n).

Based on the results of the present work, PVDF+(x) FeCl3 (20x) MnCl2, it could be concluded that the mixture of Fe3+ and Mn2+ ions enhanced the magnetoactivity of PVDF. The fair intrasubstituted range of 0:0oxo20% revealed a linear or monotonic FL dependence on most of the investigated parameters such as optical energy gap (Eg ), electrical resistivity (r0 ), activation energy (Ea ), asymmetry factor (A) and peakto-peak separation (DH).

The linear dependence of an optical gap, Eg ; on FL indicates the improvement of an optical response. These lms can be used as microwave sensors. The sample of x 10% contains minimum structural defects, maximum content bphase, tetrahedral Fe3+ and maximum effective magnetic moment meff : Thus, it can serve as a piezoelectric and paramagnetic semiconductor

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194 M. Abdelaziz / Journal of Magnetism and Magnetic Materials 279 (2004) 184194 [15] D. Nicholls, Complexes and First Raw Transition Elements, The Whitefriars Pree LTR, London and Tonbridge, 1974. [16] R. Gergono, N.C. Perera, J. Phys. D 28 (1995) 432. [17] B. Hannoyer, M. Lenlet, R. Corles, J. Non-Cryst. Solids 151 (1992) 209. [18] E.A. Davis, N.F. Mott, Philos Mag. 22 (1970) 403. [19] A. Tawansi, A.H. Oraby, H. Zidan, M.E. Dorgham, Physica B 126 (1998) 254. [20] A. Tawansi, A.H. Oraby, H.I. Abdelkader, M. Abdelaziz, J. Magn. Magn. Mater. 262 (2003) 203. [21] J. Fleming, D.H. Williams, Spectroscopic Methods in Organic Chemistry, McGraw-Hill, New York, 1966. [22] M. Kobayashi, K. Tashiro, H. Tadokoro, Macromolecules 8 (1975) 158. [23] Y. Aydogdu, F. Yakuphanoglu, A. Aydogdu, E. Tas, A. Cukurovoli, Solid State Sci. 4 (2002) 879. [24] P. Kuivalainen, H. Stubb, H. Isotalo, Phys. Rev. B 31 (1985) 7900. [25] J.L. Breads, R.R. Chance, R. Silbey, Phys. Rev. B 26 (1982) 5843. [26] N.F. Mott, R.W. Gurrey, Electronic Process in Ionic Crystals, Oxford University Press, London, 1940. [27] A. Tawansi, S.I. Badr, M. Abdelaziz, J. Mater. Des. Appl. (2002) 57. [28] R. Hazegaw, Y. Takahashi, Y. Chatwi, H. Tadakoro, J. Polym. 13 (1972) 600. [29] R.L. Dutta, A. Syamal, Elements of Magnetochemistry, S. Chand & Company Ltd., New Delhi, 1982. [30] A. Tawansi, H.I. Abdelkader, M.I. Ayad, E.M. Abdelazek, J. Mater. Sci. Technol. 13 (1997) 194. [31] M. Abdelaziz, The effect of silver nitrate diffusion on some physical properties of polyvinylidene uoride lms containing some halides, M. Thesis, Mansoura University, Egypt, 1998.

that can be used to produce surface acoustic wave with variable frequency, acting as a diffraction grating of variable order for laser beams. This type of grating is very important for modern optical communications.

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