Synthesis and Surface Observation of Montmorillonite / Polyaniline Composites

Polyaniline (PANI) is synthesized in the presence of montmorillonite (Mt). Mt has small spaces between its layers. This interlayer spacing functions as a reaction field for the production of PANI with an organized structure. Mt/PANI composites thus synthesized were characterized by the IR and the UV-Vis optical absorption spectroscopy measurements. Scanning electron microscopy observation showed that the PANI is covered by the flake structure of the Mt. A cylindrical structure was also observed in the sample. X-ray diffraction analysis indicated that the composite of the PANI and the Mt had an ordered structure, suggesting that the macroscopic structure of the natural clays can provide a unique reaction field for polymerization reactions.


Introduction
Researchers have recently employed microporous materials to create reaction fields [1,2].This study suggests that small spaces in materials can effectively function as reaction fields.We recently engaged in liquid crystal (LC) polymerization.Resultant polymers obtained showed that LC-like aggregations form due to transcriptions of the LC matrix.In this report, we carry out polymerization in the presence of montmorillonite (Mt) with a layer structure as a micro-reaction field.
Many studies have been performed on conductive polymers.Polyaniline (PANI) is promising for its low cost and good stability.PANI composites can be prepared in the presence of metals, minerals, and organics [3,4].Studies on conducting polymer/inorganic layer clay have been conducted [5,6].Mt is an interesting inorganic clay.Mt consists of layered silicates with negative charges [7,8].The multiple layers absorb water and organic compounds.Polymerization can be carried out between the layers of Mt, which act as reaction fields [9,10].Mt can be also used as filler for composite formation.
Many kinds of oxidants, dopants, and surfactants have been used to develop functional composites [11,12].Here, we carry out the polymerization of aniline in the presence of Mt as an inorganic reaction field for the production of organized polymers.

Materials
Aniline was purchased from Wako Chemical (Tokyo, Japan) and purified by distillation.Ammonia/water solution and ammonium persulfate (APS, (NH 4 ) 2 S 2 O 8 ) were purchased from Kanto Chemical (Tokyo, Japan), and used as received.Sulfuric acid, N-methyl-2-pyrrolidine (NMP), and methanol were purchased from Nacalai tesque (Tokyo, Japan) and used as received.

Instruments
Infrared (IR) absorption spectra were obtained with an FT/IR-4600 spectrometer (Jasco, Tokyo, Japan) by the KBr method.UV-Vis absorption spectra were measured with a V-630 UV-Vis optical absorption spectrometer (Jasco, Tokyo, Japan).Electrical conductivity was obtained with a Lowrester-GP and MCP-TP06P probe by the four-probe method (Mitsubishi, Tokyo, Japan).Surface structure of the samples was observed with a JSM-5510 SEM (JEOL, Tokyo, Japan).X-ray diffraction data was obtained with X'pert (PANanalytical, Almelo, The Netherlands).ESR measurement of the solid sample packed into a 5 mm quartz tube was carried out with a JEOL JES TE-200 spectrometer (Tokyo, Japan).

Preparation of PANI Composites
Aniline (0.30 g, 3.2 mmol), montmorillonite (0.3 g, 0.6 g) or sulfuric acid (H 2 SO 4 ) (0.66g, 6.1 mmol) was added to distilled water (16 mL) in a vial.The solution was stirred and cooled to 0 • C in an ice bath.APS (1.4 g, 6.4 mmol) in distilled water (16 mL) was added to the vial to initiate oxidative polymerization.After 24 h, the solution was washed with a large volume of distilled water and methanol, filtered and dried in a vacuum to obtain product.These composites were abbreviated as Mt/PANI-1 and Mt/PANI-2 (Table 1).Polymerization schemes and PANI structures are shown in Figure 1.

Instruments
Infrared (IR) absorption spectra were obtained with an FT/IR-4600 spectrometer (Jasco, Tokyo, Japan) by the KBr method.UV-Vis absorption spectra were measured with a V-630 UV-Vis optical absorption spectrometer (Jasco, Tokyo, Japan).Electrical conductivity was obtained with a Lowrester-GP and MCP-TP06P probe by the four-probe method (Mitsubishi, Tokyo, Japan).Surface structure of the samples was observed with a JSM-5510 SEM (JEOL, Tokyo, Japan).X-ray diffraction data was obtained with X'pert (PANanalytical, Almelo, The Netherlands).ESR measurement of the solid sample packed into a 5 mm quartz tube was carried out with a JEOL JES TE-200 spectrometer (Tokyo, Japan).

Preparation of PANI Composites
Aniline (0.30 g, 3.2 mmol), montmorillonite (0.3 g, 0.6 g) or sulfuric acid (H2SO4) (0.66g, 6.1 mmol) was added to distilled water (16 mL) in a vial.The solution was stirred and cooled to 0 C in an ice bath.APS (1.4 g, 6.4 mmol) in distilled water (16 mL) was added to the vial to initiate oxidative polymerization.After 24 h, the solution was washed with a large volume of distilled water and methanol, filtered and dried in a vacuum to obtain product.These composites were abbreviated as Mt/PANI-1 and Mt/PANI-2 (Table 1).Polymerization schemes and PANI structures are shown in Figure 1.

UV-Vis Absorption Spectra
UV-Vis absorption spectra of PANI (H 2 SO 4 ) and Mt/PANI composites in the NMP solution are shown in Figure 3.The solubility of Mt/PANI is similar to that of PANI, indicating that Mt provides no drawback in solubility.Two characteristic absorption bands appeared for PANI (H 2 SO 4 ) and the Mt/PANI composites.The absorption bands at 300-400 nm are derived from the π-π* transition of the benzenoid structure of PANI in the main chain [14,15].The typical absorption bands at 550-600 nm are due to the π-π* transitions of the quinoid structure of the main chain [14,15].Absorption bands of the Mt/PANI composites, as opposed to those of the pure PANI, were slightly blue-shifted.
bands of the Mt/PANI composites, as opposed to those of the pure PANI, were slightly blue-shifted.

Conductivity
The PANI(H2SO4) and the Mt/PANI composites were pressed into thin pellets and their thicknesses were measured.Next, the electrical conductivity of the samples was measured by the four-probe method.Conductivities of the PANI(H2SO4) and the Mt/PANI composites are summarized in Table 3.The PANI(H2SO4) shows electrical conductivity of 1.5 × 10 −3 S/cm, Mt/PANI-1 1.6 × 10 −6 S/cm, and Mt/PANI-2 2.1 × 10 −5 .A decrease in conductivity is related to the blue shift in the UV-Vis spectroscopy measurement results, and this shift is due to the decrease in the effective conjugation length.The undoped sample showed conductivity of 10 −10 S/cm, which is low.An electrical interaction between PANI and Mt with negatively charged layers occurred for the undoped sample [16].

Electron Spin Resonance
The vapor phase iodine doping process of the Mt/PANI composite was obtained via electron spin resonance (ESR) spectroscopy measurements.The ESR observes unpaired electrons as radicals of polarons (radical cations (charge carriers)).Mt/PANI-2 was treated with ammonia/water to obtain a reduced state (undoped state).However, complete dedoping was not achieved because the sample prior to iodine doping shows the ESR signal.This may be due to the fact that the PANI component in the interlayer of the Mt can not completely contact with ammonia/water in the reduction treatment.Therefore, the sample at 0 min (no doping with iodine) was still partly doped

Conductivity
The PANI(H 2 SO 4 ) and the Mt/PANI composites were pressed into thin pellets and their thicknesses were measured.Next, the electrical conductivity of the samples was measured by the four-probe method.Conductivities of the PANI(H 2 SO 4 ) and the Mt/PANI composites are summarized in Table 3.The PANI(H 2 SO 4 ) shows electrical conductivity of 1.5 × 10 −3 S/cm, Mt/PANI-1 1.6 × 10 −6 S/cm, and Mt/PANI-2 2.1 × 10 −5 .A decrease in conductivity is related to the blue shift in the UV-Vis spectroscopy measurement results, and this shift is due to the decrease in the effective conjugation length.The undoped sample showed conductivity of ∼10 −10 S/cm, which is low.An electrical interaction between PANI and Mt with negatively charged layers occurred for the undoped sample [16].

Electron Spin Resonance
The vapor phase iodine doping process of the Mt/PANI composite was obtained via electron spin resonance (ESR) spectroscopy measurements.The ESR observes unpaired electrons as radicals of polarons (radical cations (charge carriers)).Mt/PANI-2 was treated with ammonia/water to obtain a reduced state (undoped state).However, complete dedoping was not achieved because the sample prior to iodine doping shows the ESR signal.This may be due to the fact that the PANI component in the interlayer of the Mt can not completely contact with ammonia/water in the reduction treatment.Therefore, the sample at 0 min (no doping with iodine) was still partly doped with sulfate ions in the polymerization reaction.The sample was measured at every 2.5 min with iodine doping (Figure 4).The ESR line shapes are a Lorentz-type symmetric form, as shown in the inset of Figure 4.After doping, a radical concentration slowly increased due to the progress of the doping with iodine, confirming that polarons as radical cations were produced in the main chain of the PANI.This result confirms the iodine doping process of Mt/PANI [17].
with sulfate ions in the polymerization reaction.The sample was measured at every 2.5 min with iodine doping (Figure 4).The ESR line shapes are a Lorentz-type symmetric form, as shown in the inset of Figure 4.After doping, a radical concentration slowly increased due to the progress of the doping with iodine, confirming that polarons as radical cations were produced in the main chain of the PANI.This result confirms the iodine doping process of Mt/PANI [17].

SEM Observation
The surface structure of PANI(H2SO4) and Mt/PANI composites were observed via SEM (Figure 5).A bulky structure is often observed when PANI is prepared via chemical oxidative polymerization with sulfuric acid.Mt/PANI composites showed a flake structure [5].This result implies the occurrence of the self-aggregation of aniline (monomer) in the interlayer of the Mt prior to polymerization.The resultant PANI forms an ordered structure.A cylindrical fiber structure was also observed in the SEM.The structure may be of a hollow fiber form [18,19].

X-Ray Diffraction
X-ray diffraction results of PANI (H2SO4), montmorillonite, and Mt/PANI composites are shown in Figure 6 and Table 4. PANI exhibits characteristic signals at 2θ = 14.9°, 20.6°, and 25.5° [20,21].The signals at 2θ = 20.6° and 25.5° were assigned to be (1 1 0) and (2 0 0) of PANI [18].Mt has diffraction signals at 2θ = 8.0, 20.3°, and 22.2° (4.0 .).Mt/PANI composites have both signals from the PANI and the Mt, indicating the formation of an inorganic/conducting polymer composite.The signal at 6.2° corresponds to 14 .The small distance may be due to the formation of the molecular layer of PANI in the interlayer of Mt. [7,8].The signal at 6.2° could also cause the formation of a hollow nano-tube [18,19] with good PANI aggregation [20].Further, polymerization between Mt layers may improve PANI ordering through the interaction of the aniline monomer and Mt layers.
Figure 7 shows the possible polymerization mechanism and resultant structure of PANI/Mt.First, aniline was adsorbed in the Mt layers.Subsequently, the monomers were polymerized in the interlayer to form an ordered polymer.

SEM Observation
The surface structure of PANI(H 2 SO 4 ) and Mt/PANI composites were observed via SEM (Figure 5).A bulky structure is often observed when PANI is prepared via chemical oxidative polymerization with sulfuric acid.Mt/PANI composites showed a flake structure [5].This result implies the occurrence of the self-aggregation of aniline (monomer) in the interlayer of the Mt prior to polymerization.The resultant PANI forms an ordered structure.A cylindrical fiber structure was also observed in the SEM.The structure may be of a hollow fiber form [18,19].

X-Ray Diffraction
X-ray diffraction results of PANI (H 2 SO 4 ), montmorillonite, and Mt/PANI composites are shown in Figure 6 and Table 4. PANI exhibits characteristic signals at 2θ = 14.9 • , 20.6 • , and 25.5 • [20,21].The signals at 2θ = 20.6 • and 25.5 • were assigned to be (1 1 0) and (2 0 0) of PANI [18].Mt has diffraction signals at 2θ = 8.0, 20.3 • , and 22.2 • (4.0Å.).Mt/PANI composites have both signals from the PANI and the Mt, indicating the formation of an inorganic/conducting polymer composite.The signal at 6.2 • corresponds to 14 Å.The small distance may be due to the formation of the molecular layer of PANI in the interlayer of Mt. [7,8].The signal at 6.2 • could also cause the formation of a hollow nano-tube [18,19] with good PANI aggregation [20].Further, polymerization between Mt layers may improve PANI ordering through the interaction of the aniline monomer and Mt layers.Figure 7 shows the possible polymerization mechanism and resultant structure of PANI/Mt.First, aniline was adsorbed in the Mt layers.Subsequently, the monomers were polymerized in the interlayer to form an ordered polymer.

Conclusions
We synthesized PANI in the presence of montmorillonite (Mt).A flake structure of PANI was observed in the SEM images.Mt/PANI composites are expected to have industrial applications, for example, as an anti-corrosion material [22,23].From a basic viewpoint, the present study found that the macroscopic structure of natural clays provides a unique reaction field that yields the Mt/PANI composite.This composite's macroscopic form may increase its potential applications.

Conclusions
We synthesized PANI in the presence of montmorillonite (Mt).A flake structure of PANI was observed in the SEM images.Mt/PANI composites are expected to have industrial applications, for example, as an anti-corrosion material [22,23].From a basic viewpoint, the present study found that the macroscopic structure of natural clays provides a unique reaction field that yields the Mt/PANI composite.This composite's macroscopic form may increase its potential applications.

Figure 4 .
Figure 4.In situ electron spin resonance (ESR) spectroscopy measurement of Mt/PANI with vapor phase doping of iodine.Inset shows the ESR signal shape of the Mt/PANI prior to iodine doping (0 min) and after doping (30 min).

Figure 4 .
Figure 4.In situ electron spin resonance (ESR) spectroscopy measurement of Mt/PANI with vapor phase doping of iodine.Inset shows the ESR signal shape of the Mt/PANI prior to iodine doping (0 min) and after doping (30 min).

Figure 7 .
Figure 7. Possible polymerization of aniline between Mt layers.

Figure 7 .
Figure 7. Possible polymerization of aniline between Mt layers.

Table 2 .
IR absorption bands of Mt/PANI composites.

Table 2 .
IR absorption bands of Mt/PANI composites.