International Journal of Electronics, Communication & Instrumentation Engineering Research and Development (IJECIERD) ISSN 2249-684X Vol.

3, Issue 1, Mar 2013, 57-62 TJPRC Pvt. Ltd.

NONDESTRUCTIVE COMPLEX PERMITTIVITY MEASUREMENT OF PANI/PU CONDUCTING COMPOSITES USING COAXIAL PROBES
HOANG NGOC NHAN Electric Power University, 235, Hoang Quoc Viet, Hanoi, Vietnam

ABSTRACT
In regard to their physical properties, intrinsically conducting polymers are very good candidates for electronic applications. This paper describes and evaluates a method for determining complex permitivity, and presents results of permitivity measurement of polyanile / polyurethane conducting composites in microwave band. This is a nondestructive method based on reflection coefficient measurement of an open-ended coaxial line (with dimensions of SMA connector) attaching the conducting film under test. At the microwave frequencies, the permittivities follow the power law (proportional to f -s) in agreement with the hopping theory. For blends with 1% of Pani, the loss factor (tan ) had interesting value (tan = 3.2 at 1GHz) for using as microwave absorbing materials.

KEYWORDS: Complex Permittivity Measurement, Open-Ended Coaxial Probe, Polyaniline / Polyurethane, Percolation
Threshold, Absorbing Materials

INTRODUCTION
With metallic transport properties like in metal or semiconductors, conducting polymers have a lot of potential applications in microelectronics industry in recent years. The conducting polymers have been used in opto-electronic, sensor devices [1] , electrostatic discharge layers, printed circuit board [2], absorbing materials and electromagnetic interference shielding [3]Among the conducting polymers, Polyaniline (Pani) has emerged as one of the most promising materials due to the easiness of its synthesis, its environmental stability. To obtain a conducting material with good electronic and good mechanical properties, Pani is doped by a plasticizing dopant or Pani in its conducting form is blended with a thermoplastic [4]. In the second way, the conducting composite has a very low percolation threshold, low specific weight and low cost. To develop efficaciously the applications of this material, it is necessary to characterize their electromagnetic properties particularly at nearly percolation threshold where there is a change strongly from insulating state to conducting state. The measurement of electromagnetic properties (permittivity and conductivity) at a microwave band can provide information on the low frequency conduction mechanisme, polarisation and molecular dynamics in the material. The techniques of characterization may include the use of cavity resonators [5], free space transmission [6], transmission lines and open-ended coaxial probes [7]. Open-ended coaxial probes were developed for broadband measurement of the permittivity of biological substances [7]. However, they can also be used to measure complex permittivities of conducting materials. In this paper, we present the open-ended coaxial technique to measure the complex permittivities of Pani/PU conducting films in microwave band. The role of the plastifier in the blend will be presented. The microwave conductivities will be compared with the static conductivities

PREPARATION OF PANI/PU CONDUCTING FILMS

In the non-conducting form, Emeraldine Base (EB) is a type of polyaniline and the general structure is presented in figure 1

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Hoang Ngoc Nhan

H
N

H
N N

N 1-y

Figure 1: Schematic Representation of Emeraldine Base y=0.5 The conducting polyaniline is obtained by oxidation with camphor sulphonic acid (CSA) as described in literature [4]. EB was fully protonated by CSA with the 0.5 molecular radio (H+/PhN=0.5), it can be easily dissolved in dichloroacetic acid (DCAA) to concentrations of 2.85% w/w. Protonation reaction lasted minimum 3 days at room temperature. Finally, we have a 1.2g PAni in 100g PAni- (CSA) 0.5/DCAA solutions. Among the thermoplastics, the Polyurethane (PU) is flexible, has good mechanical properties and is easily soluble in DCAA. First, PU was dissolved in the DCAA solution in the mass ratio of 1 to 10 % and then blended with PAni-(CSA)0.5 solution with different mass fraction of PAni in the PU and CSA. The mixture was carefully homogenized by a magnetic agitator for 10 minutes. Finally, the PAni-CSA05/PU solution was spread out on a glass container (for the freestanding films). The solvents were evaporated under an infra lamp for a period minimum of 48h and then 6 h in a vacuum oven at 60C. The obtained films have a specific mass about 1g.cm-3. The freestanding films of PAni/PU are presented in the table 1. Table 1: Freestanding PAni/PU Conducting Films Samples p(%) PAni0.2/PU 0.2 PAni0.5/PU 0.5 PAni1/PU 1 PAni1+5Plast/PU 1+5% plastifier PAni4.7/PU 4.7 PAni8.8/PU 8.8 PAni16/PU 16 PAni44/PU 44 d(m) 150 150 150 150 160 155 145 130

OPEN-ENDED COAXIAL METHODS

Low Loss Capacitive Model End effect probes have been used in permittivity measurements or control since 1980 [7, 8, 9]. Several analytical models have been used with a view to calculating the S11 coefficient [10, 11]. Then after a measure of S11, the determination of the permittivity can be achieved by numerical inversion. But the procedure is difficult, time consuming and the accuracy of the result depend on the quality of the model. The simplest equivalent circuit is given by measurements of S11: the phase of S11 is always negative, directly proportional to the frequency (especially at low frequency), the magnitude of S11 is near 1 for non absorbing materials, and decreases when the absorption increases. These considerations lead to an equivalent circuit of the end effect represented by a capacity [7, 12]; we have chosen the expression: C = C0b S11 is given by: for the capacity.

S11 =

1 jC0 Z0 b 1 + jC0 Z0 b

(1)

The phenomenological parameters C0 and b cannot be calculated theoretically, they must be determined by measurements on a set of reference materials whose permittivity is known. The numeric inversion of formula (1) is then very easy and rapid. Figure 2 shows the determination of C0 and b from measurements of S11 with dielectrics in contact with a

Nondestructive Complex Permittivity Measurement of Pani/PU Conducting Composites Using Coaxial Probes

59

coaxial probe (3.5 mm diameter). The experimental values are C0 = 3.38 10-2 pF, b = 0.91, (0.93 value deduced from HFSS model). The values of C0 and b are frequency independent from 100 MHz to 5 GHz at least. Capacity C (in 10-2 pF)
200

150

100

50

0 0 10 20 30 40 50 60 70 80

Figure 2: Measurement of the Equivalent Capacity of the End Effect Probe (3.5 mm) as a Function of the Permittivity When the thickness of the sample is greater than the penetrating depth of the evanescent wave, the measured value of S11 does not depend on the sample thickness. But if not, a correction is needed: with a sample short-circuited (followed by a metal plate), the equivalent capacity is a function of the sample thickness d as shown in Figure 3. A fit of experimental values gives a d-1 behaviour: for a standard coaxial 3.5 mm the equivalent capacity is: Ceq = (2.01 + 0.89/d) 0.91 with d in mm. The same expression remains valid when the permittivity is complex (absorbing materials) [12]. This capacitive model works with low and medium conductivity samples (< 10 S/m). Reference dielectrics have permittivity ranging from 2 to 100. But extrapolations of the model to the determination of higher permittivity give satisfactory results up to 2000 in PLZT ceramics [13].

Capacity C (in 10-2 pF) 35

30

25

20

15 0 0,5 1 1,5 2 2,5 3 3,5

1/d in mm-1 Figure 3: Measurement of the Equivalent Capacity of the End Effect Probe (3.5mm) as a Function of the Inverse of the Thickness(1/d) of the Sample (Permittivity = 8.34 at 1 GHz)

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Hoang Ngoc Nhan

HIGH LOSS SURFACE IMPEDANCE MODEL

When the material under test is highly conductive (polyaniline films for example with > 100 S/m), the capacitive model fails. In this case, as the incident wave in the coaxial is a TEM mode, the condition at the interface is given by the surface impedance Zs of the sample if its thickness is greater than the skin depth. The equivalent circuit in this case is given by a complex impedance [5]:

Z s = (1 + j ) 0 f /
The reflection coefficient S11 is then given by the relation:

(2)

S11 =

Z S Z0 ZS + Z0

(3)

and in this case analytical solution is obtained [5] :

= 40 f (1 A)2 / (1 + A) (6 A 1 A2 )1/ 2
is in S/m, f is the frequency in Hz, A = |S11| 2

(4)

RESULTS
In the case of the samples which are presented in table I with Paniconcentration less than 1%, the conductivity is less than 10 S/m, the capacitive model is valid. Measurements of the permittivity and conductivity of these samples are given in figure 4 and 5. We observe the standard behavior of conducting polymers: The permittivity decreases and conductivity increases as the frequency increases. The addition of a plastifier in Pani1%/PU reduces the permittivity (50%) and increases the conductivity.
100

Eps'

10
1%+Plast 1% 0.5% 0.2%

1 0.1 1 F (GHz) 10

Figure 4: Permittivity of Composites Pani/PU (Percolation Threshold 0,2%) For a Pani concentration of 4,5%, 8,8% and 16%, conductivity is between 10 and 100 S/m, and the capacity model or the surface impedance model are not convenient. For 44% Pani (Pani film), the conductivity is high, and the impedance model applies, the conductivity [cfformula (2)] is 104 S/m, in good agreement with DC and waveguide (10 GHz) measurements.

Nondestructive Complex Permittivity Measurement of Pani/PU Conducting Composites Using Coaxial Probes

61

10

Sigma (S/m)

0.1

1%+Plast 1% 0.5%

0.01 0.1 1 F (GHz)

0.2%

10

Figure 5: Conductivity of Composites Pani/PU (Percolation Threshold 0,2%)

CONCLUSIONS
The open-ended coaxial technique described in this paper gives accurate values of complex permittivities of conducting composites in the microwave frequency range. Because this method is nondestructive, it can be used as a sensor for complex permittivity measurement under high temperature conditions. In the case of thin and flexible samples of Pani/PU with the conductivity less than 10 S/m, the capacitive model is valid. The permitivities follow the power law in agreement with the hopping theory. The result showed that the addition of a plastifier in Pani1%/PU reduces the permittivity and increases the conductivity so the loss factor is increased. These Pani/PU composites are interesting for use as microwave absorbing material.

REFERENCES
1. 2. 3. Basudam Adhikari, Sarmishtha Majumda, Polymers in sensor application, Prof. Polym. Sci. 29-2004 M. Angelopoulos, Conducting polymers in microelectronis, IMB, J. Res. Dev. Vol. 45, No.1, January 2001. Hoang Ngoc Nhan, Wojkiewicz Jean Luc, Miane Jean-Louis, Genetic Algorithm applied to the optimisation of the electromagnetic properties of conducting polymer composites in the microwave band Proc. ICMS, Marrakech, November 2005. 4. Thomas E. Olinga et all, Highly conducting and solution-processable polyaniline obtained via protonation with a new sulfonic acid containing plasticizing functional groups, Macromolecules 2000, 33, 2107-2113. 5. H. Rmili, J-L. Miane, H. Zangar, T.E. Olinga,Microwave conductivity measurement of high conductive polyaniline films, Eur. Phys. J. Appl. Phys. 2005, 29, 65-72. 6. D.K. Ghodagaonkar, V.V. Varadan, V.K. Varadan, Free-space measurement of complex permittivity and complex permeability of magnetic materials at microvare frequencies, IEEE Trans. Instr. Meas. Vol. 19, No.2 1990. 7. A.M. Stuchly, S.S. Stuchly, Coaxial line reflection method for measureing dielectric properties of biological substances at radio and microwave frequencies, IEEE Trans. Instrum. Meas., 1980, vol.29, n3, 176-183. 8. Tanabe E., Joines W. T. A non-destructive method for measuring the complex permittivity of dielectric materials at microwave