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Development of polyurethanetitania nanocomposites as dielectric and piezoelectric material

Cite this: DOI: 10.1039/c2ra22929c

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Suryakanta Nayak,a Banalata Sahoo,b Tapan Kumar Chakiac and Dipak Khastgir*a
Flexible polyurethane (PU)titania nanocomposites of different compositions are prepared by a meltmixing technique. Two different sequences of mixing method are adapted to prepare two different sets of composites. All these composites show composition-dependent dielectric properties, and composites with tunable dielectric properties can be obtained through judicial adjustment of composition. The morphology of these composites has been investigated by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and scanning probe microscopy (SPM). Dielectric properties at low frequency regions are found to depend on morphology. These composites show
Received 24th August 2012, Accepted 13th December 2012 DOI: 10.1039/c2ra22929c www.rsc.org/advances

excellent piezoelectric behaviour, where the dielectric constant and conductivity of these flexible composites change appreciably with changes in applied stress. The dielectric breakdown strength of these composite is also measured. To understand the thermal stability of these composites, thermogravimetric analysis has been applied and it was found that a composite containing 12.49 vol% titania shows higher thermal stability, beyond which, stability decreases due to the photocatalytic effect of titania.

1 Introduction
Polymer nanocomposites have attracted great attention due to their unique set of properties.1,2 These composites have either nano-clay,26 carbon fillers,710 carbon nanotubes,1,1113 or different types of inorganic fillers14,15 dispersed in an appropriate polymer matrix. Polymer composites filled with ceramic particles have received considerable attention in the past decade. Favourable features include a high dielectric constant, low dielectric loss, and good compatibility with printed-circuit-boards (PCB), making them promising candidates for embedded capacitors used in passive technology.16 In the present investigation, we have utilized titania nanoparticles in order to study their effect on the thermal, electrical, and piezoelectric properties of PUtitania composites. Composites derived from inorganic fillers dispersed in a polymer matrix have received significant attention because of their improved mechanical properties coupled with their tailor-made dielectric properties, and in order to prepare suitable dielectric materials.17 Dielectric materials are capable of storing large amounts of electrical energy which are desirable for many electronic and power devices. Polyurethane elastomer is a unique material that offers the
Rubber Technology Centre, Indian Institute of Technology, Kharagpur, W.B. 721302, India. E-mail: khasdi@rtc.iitkgp.ernet.in; Fax: +91-3222282292; Tel: +91-3222283192 b Department of Chemistry, Indian Institute of Technology, Kharagpur, W.B. 721302, India c Polymer-Nano Science and Technology, Chonbuk National University, Jeonju 561 756, Republic of Korea
a

elasticity of rubber combined with good mechanical properties, toughness and durability, and has become an important material for many applications.17,18 However, these materials are seldom used as pure polymers and are usually combined with mineral fillers.17 These fillers are used with a polymer in order to improve the mechanical, thermal, and electrical properties, and the dimensional stability of the final composites. Filled polyurethanes (PUs) are used for moderate strain applications whereas unfilled PUs are used where strain rates are low.19 PU composites are used in various applications such as artificial muscles, sensors, adhesives, electrostatic imaging, cables, and EMI shielding gasket materials.18,20,21 Titanium dioxide is an inorganic filler having large permittivity and is thus used for insulating material in electronics and as a dielectric for capacitors.22 Other applications of titania include use as a de-pollutant, self-cleaning agent, photocatalyst, photovoltaic cell, semi conductor, etc.23 Composites prepared from titania show increased tensile modulus,24 tensile strength, tear strength, hardness,25 and in some cases, mechanical properties such as the mechanical modulus value are found to decrease with an increase of filler concentration in the polymer matrix.26 Polyurethane is a polar polymer having relatively high permittivity compared to a non-polar polymer like polyethylene. Such a polymer can be used as a capacitor for electronic applications. A tailor-made capacitor with controlled dielectric properties can also be obtained using PU as a matrix filled with electro-ceramics, such as titania (TiO2), BaTiO3, PZT etc., having a high dielectric constant.2729 In fact, the dielectric constant of such composites depends on the composition. Upon selection of an

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Paper appropriate type of polyurethane, one can obtain suitable piezoelectric composites. To have piezoelectric characteristics, a flexible PU matrix is preferred. The present investigation deals with the development of a dielectric material using PU as the base matrix with varying concentrations of titania as a filler. The polyurethane chain here is elastomeric in nature so that some piezoelectric characteristics can also be brought into the system. Detailed electrical and dielectric properties of these composites over a wide range of frequency and applied pressure have been investigated. To understand the thermal stability of these composites, thermogravimetric analysis has been studied. The effect of processing conditions on the electrical properties of these composites has also been investigated.

RSC Advances These two methods differ in the sequence of addition of filler. Incorporation of all compounds was done according to two different sequences, for example: Method-1: PU was added in an internal mixer at a specified condition and softened for 2 min. Then, titania was added and mixed for 6 min followed by the addition of curative systems (DCP + TAC) and mixing was further continued for 2 min, thus, the whole process took 10 min. The mixed mass was then released from the internal mixer and sheeted out in a two role mill while it was hot. Thus, the sequence of mixing was as follows: [PU A TiO2 A curatives (DCP + TAC)]. Method-2: PU was added in an internal mixer at the specified condition and softened for 2 min followed by the addition of curatives for 2 min. After that the whole mass was released from the internal mixer to cool down to room temperature (y35 uC). Again the cold mass at 35 uC was reheated to 80 uC and titania was added and mixed for 6 min. After the completion of mixing, the hot mass was taken out from the internal mixer and sheeted out in a two roll mill. Thus, the sequence of mixing was as follows: [PU A curatives (DCP + TAC) A TiO2]. The optimum cure times of different compounds were evaluated by a rubber process analyzer (RPA) operating at 150 uC. Different test specimens from all the composites were prepared using a compression moulding press at 150 uC and cured upto the optimum curing time. Different composites were designated using alpha numerical number; for example, P100Tx, which means the composition of PU elastomer and TiO2 containing x parts of TiO2 by weight per hundred parts of polymer (php), where P represents PU and T represents titanium dioxide. Note: The concentration of curatives (dicumyl peroxide DCP and triallyl cyanurate TAC) remains constant in all the composites, so these terms are not included in the alpha numerical designation. 2.3 Measurements and characterization The DC resistivity of pristine PU and PUtitania composites were measured using a high resistivity meter (Agilent 4339B) attached with a resistivity cell (Agilent 16008B). Dielectric properties of these composites were measured using a precision LCR meter (Model. Quad Tech 7600) attached with a homemade sample holder having parallel plate circular electrodes. All measurements were carried out over the frequency range 10106 Hz. The effect of pressure on the dielectric properties and conductivity of all the composites was analyzed using a LCR meter (GW-Instek LCR-819). The dielectric breakdown strength (break down voltage) of the composites was measured using a Multiplex 11kV BDV tester (M/s Agro Scientific Industries, Pune, India). Thermogravimetric analysis (TGA) was carried out using TA

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2 Experimental
2.1 Raw materials Polyester-based commercial grade polyurethane elastomer was used as the base matrix for this work, which was supplied by Rheinchemie, Germany, having density = 1.2 g cm21 and ML5+4@100 uC = 3050. Dicumyl peroxide (DCP, m.p. = 80 uC, purity = 98%, Sigma Aldrich, USA) was used as the curing agent. Co-curing agent triallyl cyanurate (TAC, M.P. = 26 uC) was procured from Rheinchemie, Germany. Anatase grade titanium dioxide was procured from Merck chemical Ltd., India. 2.2 Preparation of PUtitania nanocomposites PUtitania nanocomposites of various formulations were prepared via a melt-mixing technique, where titania and other compounds were mixed with the PU matrix in an internal mixer (Brabender plasticorder, model PLE 330) operating at 80 uC with a shear rate of 45 rpm for a mixing time of 10 min. Different compositions by parts of filler per hundred parts of polymer by weight (php) were prepared and the concentration of filler in the composites varied from 30 to 90 php. However, for ease of understanding, php concentration of filler has been converted to volume percentage of filler and can accordingly be written as 30 php = 7.98 vol%, 50 php = 12.49 vol%, 70 php = 16.67 vol%, and 90 php = 20.45 vol%. Anatase grade titania obtained as such was subjected to ball milling in ethanol medium for 15 min to get nanosized particles. The mixing of titania and other compounds into the pristine PU matrix was done as per formulations given in Table 1 and two methods of preparation have been used to prepare these composites.

Table 1 Formulations of PUTiO2 nanocomposites

Composition by weight per hundred parts of polymer (titania amount in vol%) Compound PU TiO2 DCP TAC P100T0 100 0 2 0.5 P100T30 100 30 (7.89 vol%) 2 0.5 P100T50 100 50 (12.49 vol%) 2 0.5 P100T70 100 70 (16.67 vol%) 2 0.5 P100T90 100 90 (20.45 vol%) 2 0.5

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RSC Advances instruments (Q 50), at a heating rate of 10 uC min21 under nitrogen atmosphere from 30 to 650 uC. The wide angle X-ray diffraction (WAXD) analysis was carried out using a high resolution X-ray diffractometer (XPert PRO, Philips PAN analytical B.V., Almelo, Netherlands) with a Cu-Ka (l = 0.154 nm) radiation source. The phase and crystallographic state of the samples were scanned in the 2h range from 10 to 90u at a scan rate of 0.13u s21 using an Xcelerator mode. The morphology and distribution of titania filler in the composites were characterized by field emission scanning electron microscopy (FESEM, Supra 40, Carl Zeiss SMT AG, Germany), high resolution transmission electron microscopy (HRTEM, JEM-2100), and scanning probe microscopy (SPM, Multiview1000TM).

Paper 3.1.2 Dielectric properties. Log-log plots of dielectric constant and loss factor vs. frequency for different PUtitania composites are presented in Fig. 2a and 2b, respectively. There is a large change in both dielectric constant and loss factor with a change in frequency and filler loading. Moreover, at any particular frequency, the dielectric constant is increased with an increase in titania content. This is mainly because of the higher dielectric constant of filler compared to the matrix polymer; for example, the dielectric constant of neat PU is 7 (present system) at 1 MHz and that of titania is 85 at 1 MHz.30 The dielectric constant of all the composites is increased significantly with a decrease in frequency. This is mainly because of the increased contributions of interfacial as well as dipolar polarization at a lower frequency range. Over the frequency range 10103 Hz, it can be noticed that the dielectric constant increases dramatically as the frequency is lowered. This indicates the existence of strong interfacial polarization over this frequency region. Similar to the dielectric constant at any particular frequency, dielectric loss is also increased with an increase in titania content, as shown in the log-log plot of dielectric loss vs. frequency for different composites (Fig. 2 b). The variation of dielectric constant with filler (titania) loading at three particular frequencies (10 Hz, 1 kHz, and 1 MHz) is presented in Fig. 3. It is found that the dielectric constant increases with the filler loading at all frequencies. The change in dielectric constant with filler loading is more pronounced when the measurement frequency is decreased. The increase in dielectric constant with a decrease in

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3 Results and discussion

3.1 Effect of composition on electrical properties 3.1.1 DC resistivity. The DC resistivity of the PUtitania composites is found to be composition-dependent, as shown in Fig. 1. The neat PU matrix exhibits resistivity at the order of 1010 V cm. However, when particulate titania is incorporated in the PU matrix, the resistivity decreases progressively with the addition of titania. This is mainly because all particulate inorganic fillers contain some moisture. These small amounts of moisture with inorganic filler give rise to some ionic and polar impurities in the system. Ionic impurities dissociated into ions depending on the polarity of the matrix and under an electric field these ions migrate towards oppositely charged electrodes giving rise to some flow of current in the system. Thus, an increase in the concentration of titania in the PU matrix reduces the resistivity of the system. The presence of moisture associated with particulate filler assists the ionization of any ionic species present in the system and causes a reduction in the electrical resistivity of composites.

Fig. 1 Effect of filler (titania) concentration on DC resistivity.

Fig. 2 Log-log plots of dielectric constant and dielectric loss vs. frequency for PU-TiO2 composites at various filler loading.

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RSC Advances composites is found to depend on the mixing method. In fact, the method of mixing has a more pronounced effect on the dielectric constant at a lower frequency range. This is due to the fact that at lower frequencies, the contribution of interfacial polarization becomes more and more pronounced. In fact, two different mixing methods are adopted to generate different types of polymerfiller morphology and interface. Consequently, the effect of the mixing method is more pronounced at lower frequency ranges. The details of the morphology of these composites are discussed later in the text. The variation of mixing temperature has a relatively lower effect on the dielectric constant as shown in Fig. 5. In general, it is found that the effect of the processing condition affects the dielectric properties of titania-rich composites having more polymerfiller interface, which is more than the composites where titania concentration is less. In fact, any increase in titania concentration increases the interface of titaniaPU composites. 3.1.4 Piezoelectric behaviour with respect to conductivity and dielectric constant. The effect of applied stress/pressure on the dielectric constants for all composites prepared by method-2 has been studied and presented in Fig. 6(ae). It can be observed from Fig. 6 (ac) that the dielectric constants of all the composites are increased with an increase in pressure at all frequencies. In addition, the magnitude of the dielectric constant was also increased with an increase in titania concentration. Fig. 6d and 6e represent the effect of frequency on the dielectric constant (e) and the change in dielectric constant (De) against pressure for the composite prepared by method-2 containing 16.67 vol% titania. From this figure, it is apparent that the net change in the dielectric constant decreased with an increase in frequency. The higher change in the dielectric constant (De) values at low frequency regions is due to the contribution of interfacial and dipolar polarization. In fact, with the application of pressure there is a change in the geometry of the interface, and as a result, there is also a change in the overall dielectric constant of the system. The

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Fig. 3 Dielectric constant vs. filler loading at three different frequencies (10 Hz, 1 kHz, and 1 MHZ) for nanocomposites.

frequency is due to the increased contribution of interfacial polarization to net polarization present in the system.31 That is why the rate of change of dielectric constant with filler loading increased sharply as the frequency is reduced from 1 MHz to 10 Hz. At higher frequencies (1 kHz and 1 MHz), the variation of dielectric constant with the filler loading is almost linear, as seen from Fig. 3. 3.1.3 Effect of processing conditions on dielectric properties. The preparation method of these composites affects their dielectric properties. Two methods of composite preparation are described in the experimental section and they differ in the sequence of titania addition to the PU matrix. The effect of the sequence of titania addition to the PU matrix on the dielectric constants of composites containing 7.89 vol% and 20.45 vol% filler can be seen from Fig. 4. The dielectric constant of these

Fig. 4 Effect of sequence of titania addition to the PU matrix on the dielectric constant.

Fig. 5 Effect of mixing temperature on the dielectric constant.

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Fig. 6 (ac) The effect of pressure on the dielectric constant at different frequencies (10, 102, and 103 Hz); (d and e) the effect of pressure on the dielectric constant (e) and change in the dielectric constant (De) of the composite filled with 16.67 vol% of TiO2 at different frequencies; and (f) effect of pressure on DC conductivity of composites prepared by method-2.

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Paper effect of pressure on DC conductivity is also studied and it is found that conductivity is increased continuously with an increase in pressure for both the composites prepared by method-1 and method-2 (Fig. 6f and Fig. 7b). On comparison between Fig. 6f and Fig. 7b, it can be seen that composites prepared by method-1 show a slightly higher conductivity than composites prepared by method-2; this may be due to the better wetting of filler by the matrix polymer. Fig. 7a represents the effect of frequency on the dielectric constant (e) against pressure for the composites containing 16.67 vol% titania prepared via both methods. There is only marginal change in high frequency dielectric constant for any particular composition when preparation method of composites is changed. However, there is some difference for low frequency dielectric constant for different composites due to changes in the preparation method, as apparent from Fig. 4. Generally, composites prepared by method-2 show a higher dielectric constant at low frequency regions. The schematic representa-

RSC Advances tion of signals (C = capacitance/conductivity) developed before and after the application of pressure to piezoelectric polymer ceramic composites is shown in Fig. 8a. PUtitania composite dielectrics have different types of bound charges (+ve and 2ve charged particles present randomly) and under an electric field these bound charges undergo polarization, i.e., organized orientation and restricted displacement of these charges occur in the system. Due to the application of pressure, there is a change in the dimensions of the system and, consequently, there is a change in the charge density of the system (Fig. 8b). This change in charge density leads to a change in capacitance of the system. Progressive compression of the sample causes an increase in charge density; as a result, there is an increase in capacitance and hence, the dielectric constant. These restricted movements of charge also cause a flow of current in the system. As a result, the conductivity of the system increases (Fig. 6f and Fig. 7b). 3.1.5 Effect of filler concentration in composites on dielectric breakdown strength. Dielectric breakdown is the failure of an insulating material under an external electric field resulting in mechanical damage and electrical conduction, depending upon the defect density of the solid material.32 The dielectric breakdown strength of nanocomposites prepared through two mixing methods is compared with the base polyurethane elastomer which is presented in Fig. 9. In both cases, it is found that dielectric strength decreased continuously with the increase of filler concentration in PU matrix. As titania is an inorganic insulating filler, it always associated with some moisture which causes both polarization and ionization leading to formation of charged species in the system. Under high voltage, a heavy rush of bound charges occurs in the system and the system fails with the increase in filler loading. More and more charge species are generated in the system with the increase in filler concentration and increased filler concentration also increases the interface between matrix polymer and filler, leading to the generation of

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Fig. 7 (a) Effect of pressure on dielectric constant (e) of composite filled with 16.67 vol% of TiO2 at different frequencies (both method/sequence 1 and 2); (b) effect of pressure on DC conductivity of composites (16.67 vol% of TiO2) prepared by method-1.

Fig. 8 Schematic representation of (a) signals (C = capacitance/conductivity) before and after the application of stress/pressure to piezoelectric polymer ceramic composite; (b) positions of charged particles inside the composites before and after the application of electric field/pressure.

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Fig. 9 Effect of filler loading on dielectric breakdown strength (kV mm21).

interfacial charge causing breakdown of the system. Another reason for the decrease in dielectric breakdown strength may be due to the aggregation of filler particles, which introduce defect centers that distort and enhance the local electric field. This field distortion is primarily due to the difference in permittivities of the polymer matrix and filler particles under AC conditions.33 Thus, an increase in titania concentration in the PU matrix decreases the dielectric breakdown strength. From Fig. 9, it is apparent that there is only a marginal change in the dielectric strength for composites prepared by method-1 and method-2. Thus, it can be concluded that the mixing sequence has a marginal effect on the dielectric strength of the composites. 3.2 Thermal stability Thermogravimetric analysis (TGA) in an inert atmosphere (N2) was conducted at a heating rate of 20 uC min21 for pristine PU and its nanocomposites. Thermal degradation behaviour of pristine PU and composites prepared by method-1 addition are given in Fig. 10a and 10b and the quantitative values are given in Table 2. Similarly, the thermal degradation behaviour of pristine PU and composites prepared by method-2 addition are given in Fig. 11a and 11b and the quantitative values are presented in Table 3. The data given in Tables 2 and 3 includes: Tmax (T2D), the temperature at which maximum degradation of sample occurs, and R600wt%, the non-volatile fraction remains left as residual mass through decomposition process at 600 uC. Finally, T1D and T2D correspond to the first and second derivative peak temperatures, respectively, and are availed from the derivative thermogravimetric curves. The first DTG curves of PU and their composites are also important because they more clearly show the difference in thermal stability of all the components present in the PU matrix. PU shows a two step degradation process where the first degradation step is due the decomposition of soft segments and the second step is mainly due to the complete degradation of hard segments of the PU

Fig. 10 TGA and DTG thermograms of pristine PU and its nanocomposites (method-1).

matrix. From the results given in Tables 2 and 3, we found that there is an increase in the thermal stability with the incorporation of titania into the PU matrix but the increase is not linear. It is also observed that in the case of the maximum degradation temperature (T2D), the thermal stability has increased upto a titania loading of 16.67 vol%, beyond which, thermal stability has been found to decrease in the case of method-1 addition (in the case of method-2, 12.49 vol%, beyond which thermal stability decreases). The increase in the

Table 2 Data summarized from TGA and DTG thermograms of PU and PU-TiO2 nanocomposites (method-1 addition)

Composition Pristine PU PU + TiO2 (7.89 vol%) PU + TiO2 (12.49 vol%) PU + TiO2 (16.67 vol%) PU + TiO2 (20.45 vol%)

T1D (uC) 328.83 324.85 322.42 321.27 315.13

T2D (uC) 402.58 419.61 431.61 434.04 426.75

R600wt% 4.25 27.36 36.06 43.87 49.67

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Fig. 12 XRD patterns of the pristine PU, neat titania, and its composites prepared by method-1.

3.3 X-Ray diffraction analysis The matrix polymer PU has a small degree of crystallinity as depicted in Fig. 12 and Fig. 13. It is observed that two different crystal planes (corresponding to peak 1 and peak 2) for neat PU can be detected. The diffraction peaks are observed at 2h = 19.11 and 28.76 for two crystal planes. The X-ray diffraction analysis proved that addition of titania particles in the PU matrix causes a decrease in intensity of both peak 1 and peak 2 (Table 4) for composites prepared by method-1 and method-2. This means that the original crystallinity of the PU matrix decreased due to filler incorporation. This decrease in crystallinity of the matrix polymer due to addition of filler may be attributed to the fact that titania particles not only get into the

Fig. 11 TGA and DTG thermograms of pristine PU and its nanocomposites (method-2).

thermal stability of composites up to 16.67/12.49 vol% titania loading is due to the homogenous distribution of titania filler in the PU matrix and the higher thermal stability of TiO2 powder.34 However, the decreased thermal stability of composites containing filler beyond 16.67/12.49 vol% may be due to the photoactivity of TiO2 which surpasses the thermal stability of TiO2 powder.35 Upon comparison, it has been found that compounds prepared via method-2 show better thermal stability than compounds prepared by method-1.

Table 3 Data summarized from TGA and DTG thermograms of PU and PU-TiO2 nanocomposites (method-2 addition)

Composition Pristine PU PU + TiO2 (7.89 vol%) PU + TiO2 (12.49 vol%) PU + TiO2 (16.67 vol%) PU + TiO2 (20.45 vol%)

T1D (uC) 328.83 333.49 330.47 320.16 317.17

T2D (uC) 402.58 424.98 437.29 434.77 431.13

R600wt% 4.25 27.85 36.65 44.37 50.85

Fig. 13 XRD patterns of the pristine PU, neat titania, and its composites prepared by method-2.

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Table 4 The peak intensities of peak 1 and peak 2 for neat PU and its composites

Paper

Intensity (%) Titania Content (vol%) Method-1 0 7.89 12.49 16.67 20.45 0 7.89 12.49 16.67 I1 28.16 4.74 1.85 1.2 0.8 28.16 5.14 3.52 0 I2 100 17.43 6.85 3.42 2.41 100 12.48 5.47 4.13

Method-2

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amorphous region of the polymer but are also present in the interphase between the crystalline and amorphous regions. In fact, the presence of such particles in this region hampers the recrystallization of the PU matrix after melt-mixing (Fig. 14). 3.4 Field emission scanning electron microscopy (FESEM) study Cryo-fractured surfaces of different PUTiO2 nanocomposites with various filler loadings (e.g. 7.89 vol% (30 php), 12.49 vol% (50 php), 16.67 vol% (70 php), and 20.45 vol% (90 php) of titania) are analyzed by FESEM (Fig. 15 and Fig. 16). The white dots in these pictures indicate the presence of filler (titania) particles and the gray areas show the matrix polymer. Fig. 15 represents the FESEM images of composites prepared via method-1 addition whereas Fig. 16 represents the FESEM

Fig. 15 The microstructure of the cryo-fractured surfaces of the composites prepared via method-1 (a) 7.89 vol% titania, (b) 12.49 vol% titania, (c) 16.67 vol% titania, and (d) 20.45 vol% titania.

images of composites prepared via method-2 addition. It can be observed from both of these figures that the numbers of titania particles are increased for composites containing 16.67 vol% and 20.45 vol% of titania and the particles are firmly bound to the PU matrix. This can be attributed to the existence of interactions between titania particles and the PU matrix. From Fig. 16, a unique morphology (pitcher shape) is observed for all the composites. For all pitcher-like shapes, the internal part is the PU matrix and the outer white dots are for titania particles which are apparent from EDX analysis (Fig. 16f and

Fig. 14 Schematic representation of polymer chains before and after the addition of titania particles.

Fig. 16 The microstructure of the cryo-fractured surfaces of the composites prepared via method-2 (a) pristine PU, (b) 7.89 vol% titania, (c) 12.49 vol% titania, (d) 16.67 vol% titania, (e) 20.45 vol% titania, and (f) SEM-EDX image of composite containing 20.45 vol% titania.

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Paper Table 5). In the case of mixing method-2, the mixed mass of PU along with curatives is cooled down to room temperature and then mixed with titania. The mixing is accomplished at 80 uC. In fact, prior to mixing with titania, small spheres (pitcher shape) may be found for PU with curatives and these small PU spheres have some dimensional stability due to some curing having already taken place during the mixing of PU and curatives (DCP + TAC) at 80 uC (during 1st mixing). Thus, in the final mass of PUtitania composites, we can see small spheres in which titania particles are attached as titania has been added at the end of the mixing. From these images, it is observed that there is excellent wetting between the PU matrix and titania particles in all the composites. As we go from Fig. 16b to Fig. 16e, the area covered by titania particles is increased and it is also observed from these images that titania particles are uniformly distributed throughout the matrix. To understand the filler distribution in the PU matrix, various regions are targeted for analysis of elemental composition and it is observed that the different regions (spectrums 1 and 2 in Fig. 16f) contain more or less some amount of C and O from the PU matrix and Ti from titanium dioxide, as given in Table 5. The particle dispersion is also seen from area mapping of composite (containing at 12.49 vol% of titania) with respect to titanium Ti, C, and O concentration as presented in Fig. 17(ac). As seen from FESEM images, the distributions of particles are more or less uniform throughout the matrix when the concentration of particles is increased. 3.5 Scanning probe microscopy (SPM) Fig. 18 (ae) represents the tapping mode SPM images of pristine PU and its nanocomposite with 7.89 vol% titania loading, their corresponding 3D images, and height profiles. AFM is used to probe the morphology and the dispersion of titania particles in the PU matrix. From the 3D images of pristine PU and its composites, it is observed that the surface of the PUtitania composite is more rough than that of neat PU. This is due to the addition of titanium dioxide in the matrix polymer. From the AFM height profile, we can distinguish neat polymer (PU) from its composites containing titania. At selected parts of the SPM micrograph for the composite, some peaks can be identified. However, such peaks are absent in the SPM micrograph of the neat PU sample. The height profile of the PUtitania composite confirms the thorough distribution of titania particles (positions 1, 2, and 3) in the PU matrix. The height profile of the PUtitania composite along the three particular lines drawn on the image is given in Fig. 18c. The presence of

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Fig. 17 Distribution of Ti, C, and O in the 12.49 vol% titania filled composite.

Table 5 SEM-EDX values of the PU-TiO2 nanocompositea

Spectrum Spectrum-1 Spectrum-2

a

C 40.07 30.73

O 42.16 44.57

Ti 17.78 24.71

Total 100.00 100.00

titania in different locations can be detected, e.g. particle with height y135 nm (position 1), particle with height y 100 nm (position 2), and particles with height (y80 and y210 nm in position 3). All these particles have a diameter of about 300 nm with well-defined profiles that can be detected from the picture.

Processing option: All elements analyzed (normalized); all results in wt%.

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Fig. 18 AFM image of (a) pristine PU, (b) height profile of pristine PU, (c) AFM image of composite (PU + 7.89 vol% TiO2) with height profile (in inset), (d) 3D image of pristine PU, and (e) 3D image of composite (PU + 7.89 vol% TiO2).

3.6 High resolution transmission electron microscopy (HRTEM) The typical HRTEM images of nanocomposites containing 7.89 vol% and 20.45 vol% titania are presented in Fig. 19a and 19b, respectively. The dispersion and distribution of titania particles can be understood from these figures. It is found that filler particles are more or less well-dispersed in the matrix polymer. However, there is clear evidence of some particle agglomeration in the polymer matrix containing higher titania content. From these images, it is observed that the shapes of the particles are more or less spherical in nature and that particle size varies from ,100 to 300 nm. Particle distribution also depends on the concentration of titania in the matrix. With the increase in filler content, uniform distributions of filler are observed, where regions without filler are less. At very high filler loadings, a close network of filler particles is formed in the matrix polymer where the average gap between filler particles is much less. Moreover, the tendency of the distribution of particles to form particle clusters is more pronounced.

Fig. 19 Composites with (a) 7.89 vol% and (b) 20.45 vol% titania in PU matrix.

4 Conclusions
Preparation methods of PUtitania nanocomposites change the morphology of the composites, which in turn affects the dielectric properties. The frequency-dependent dielectric properties suggest that there is a strong effect of interfacial polarization in the net dielectric properties of these composites. These composites also exhibit excellent piezoelectric behaviour, which is composition dependent. Both the dielectric constants and the conductivities of different composites varied with the applied stress. The change in properties with respect to applied stress becomes more and more pronounced

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Paper at higher titania content and at low frequency. This is due to changes in the charge density with applied stress.

RSC Advances 15 I.-Y. Jeon and J.-B. Baek, Mater. Chem. Phys., 2010, 3, 36543674. 16 Y. Song, Y. Shen, H. Liu, Y. Lin, M. Li and C.-W. Nan, J. Mater. Chem., 2012, 22, 1649116498. 17 A. Akinci, Archives of Material Science and Engineering, 2009, 35, 2932. 18 J. Njuguna and K. Pielichowski, J. Mater. Sci., 2004, 39, 40814094. 19 M. A. Vallance, J. L. Castles and S. L. Cooper, Polymer, 1984, 25, 17341746. 20 L. Cuve, J.-P. Pascault and G. Boiteux, Polymer, 1992, 33(18), 39573967. 21 L. Petit, B. Guiffard, L. Seveyrat and D. Guyomar, Sens. Actuators, A, 2008, 148, 105110. 22 F. Carpi and D. D. Rossi, IEEE Trans. Dielectr. Electr. Insul., 2005, 12(4), 835843. 23 D. M. Blake, P.-C. Maness, Z. Huang, E. J. Wolfrum and J. Huang, Sep. Purif. Rev., 1999, 28(1), 150. 24 T. P. Selvin, J. Kuruvilla and T. Sabu, Mater. Lett., 2004, 58, 281289. 25 A. Saritha, K. Joseph, A. Boudenne and S. Thomas, Polym. Compos., 2011, 32(10), 16811687. 26 G. Polizos, E. Tuncer, I. Sauers, D. R. James, A. R. Ellis and K. L. More, AIP Conf. Proc., 2010, 1219, 4146. 27 G.-S. Wang, L.-Z. Nie and S.-H. Yu, RSC Adv., 2012, 2, 62166221. 28 D. Khastgir and K. Adachi, Polymer, 2000, 41, 64036413. 29 D. Khastgir and K. Adachi, J. Polym. Sci., Part B: Polym. Phys., 1999, 37, 30653070. 30 http://www.azom.com/article.aspx?ArticleID=1179,26.05.2012. 31 S. Nayak, M. Rahaman, A. K. Pandey, D. K. Setua, T. K. Chaki and D. Khastgir, J. Appl. Polym. Sci., 2013, 127(1), 784796. 32 P. Barber, S. Balasubramanian, Y. Anguchamy, S. Gong, A. Wibowo, H. Gao, H. J. Ploehn and H.-C. z. Loye, Mater. Chem. Phys., 2009, 2, 16971733. 33 G. Chen and A. E. Davies, IEEE Trans. Dielectr. Electr. Insul., 2000, 7, 401407. 34 D. S. Kim and S.-Y. Kwak, Appl. Catal., A, 2007, 323, 110118. 35 F. Lin, A thesis: Preparation and characterization of polymer TiO2 nanocomposites via in situ polymerization, Chemical Engineering, University of Waterloo, Ontario, Canada, 2006, 1145.

Acknowledgements
The authors would like to thank Defence Materials and Stores Research and Development, Kanpur, India for providing financial support to carry out this research. The authors are also thankful to Mr Gopal Chandra Dhara and Mrs Barnali Mandal, Sr. Manager (R&D), Nicco Corporation Ltd., Kolkata, India for providing the dielectric breakdown strength measurement facility.

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