Materials Chemistry and Physics

Effect of gold nanoparticles prepared in two different ways on the structural, optical,
and electrical properties of (PVA/PVP/CMC) based nanocomposites: a comparative
study
--Manuscript Draft--

Manuscript Number: MATCHEMPHYS-D-21-02782

Article Type: Full Length Article

Keywords: (PVA/PVP/CMC) blend; gold nanoparticles; AC conductivity; Relaxation dynamics;

Laser ablation.

Abstract: Due to the fast development in electronic devices required for the human lifestyle, such
as laptop computers, mobile phones, and digital cameras, it is highly demanded to
prepare ecofriendly dielectric nanocomposites that could participate in developing
polymer-based batteries, actuators and supercapacitors. So, as a constructive attempt
to pave the way for developing such electronic devices, (PVA/PVP/CMC) blend (TB)
filled gold nanoparticles (AuNPs) that were synthesized in two different ways, have
been prepared using solution casting technique. The XRD, UV/VIS and TEM analyses
provided the conclusive evidence for the success of preparation of AuNPs through
plant extract and by laser ablation technique. Optical, dielectric, morphological and
microstructural properties of the SPEs were prudently studied, where their
semicrystalline nature was confirmed. The electrical conduction mechanism inside the
samples was interpreted using the Jonscher’s power law. TEM study concluded that
AuNPs are more uniformly distributed in the TB/AuNPs-biosynthesized (TBAu-B)
matrix than in the TB/AuNPs prepared by laser ablation (TBAu-L) matrix. The electric
modulus formalism not only verified the non-Debye behavior of charge carriers inside
the TB-based nanocomposite samples, but also demonstrated that the nanocomposite
films are of a remarkable capacitive feature. Mixing the biosynthesized AuNPs with the
TB host matrix had a fruitful effect on amelioration in the structural, optical and
dielectric properties of the prepared nanocomposite sample. This beneficial
enhancement recommends the TBAu-B nanocomposite to be used in fabricating
polymer-based batteries, biosensors as well as electrode support materials for organic
solar cells with high performance.

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Title Page

Effect of gold nanoparticles prepared in two different ways on the structural,

optical, and electrical properties of (PVA/PVP/CMC) based nanocomposites:
a comparative study.
A.Y. Yassin1,*

1
Department of Basic Sciences, Delta University for Science & Technology, Gamassa, Egypt

Keywords: (PVA/PVP/CMC) blend; gold nanoparticles; AC conductivity; Relaxation dynamics;

Laser ablation.

* Corresponding author,

Ahmed Y. Yassin (A.Y. Yassin)

E-mail: a_yassin2200@yahoo.com,

Tel.: +201008708413
Manuscript Click here to view linked References

Effect of gold nanoparticles prepared in two different ways on the structural,

1
2 optical, and electrical properties of (PVA/PVP/CMC) based nanocomposites:
3
4 a comparative study.
5
6 A.Y. Yassin1,*
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8
9 1
Department of Basic Sciences, Delta University for Science & Technology, Gamassa, Egypt
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* Corresponding author: A.Y. Yassin (E-mail: a_yassin2200@yahoo.com, Tel.: +201008708413)
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16
Abstract
17
18 Due to the fast development in electronic devices required for the human lifestyle, such as
19
20 laptop computers, mobile phones, and digital cameras, it is highly demanded to prepare
21
22 ecofriendly dielectric nanocomposites that could participate in developing polymer-based
23
24 batteries, actuators and supercapacitors. So, as a constructive attempt to pave the way for
25
26 developing such electronic devices, (PVA/PVP/CMC) blend (TB) filled gold nanoparticles
27 (AuNPs) that were synthesized in two different ways, have been prepared using solution casting
28
29 technique. The XRD, UV/VIS and TEM analyses provided the conclusive evidence for the
30
31 success of preparation of AuNPs through plant extract and by laser ablation technique. Optical,
32
33 dielectric, morphological and microstructural properties of the SPEs were prudently studied,
34
35 where their semicrystalline nature was confirmed. The electrical conduction mechanism inside
36
37
the samples was interpreted using the Jonscher’s power law. TEM study concluded that AuNPs
38 are more uniformly distributed in the TB/AuNPs-biosynthesized (TBAu-B) matrix than in the
39
40 TB/AuNPs prepared by laser ablation (TBAu-L) matrix. The electric modulus formalism not
41
42 only verified the non-Debye behavior of charge carriers inside the TB-based nanocomposite
43
44 samples, but also demonstrated that the nanocomposite films are of a remarkable capacitive
45
46 feature. Mixing the biosynthesized AuNPs with the TB host matrix had a fruitful effect on
47
48
amelioration in the structural, optical and dielectric properties of the prepared nanocomposite
49 sample. This beneficial enhancement recommends the TBAu-B nanocomposite to be used in
50
51 fabricating polymer-based batteries, biosensors as well as electrode support materials for
52
53 organic solar cells with high performance.
54
55
56
57
58 Keywords: (PVA/PVP/CMC) blend; gold nanoparticles; AC conductivity; Relaxation
59 dynamics; Laser ablation.
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61 1
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 1. Introduction
1
2 From the beginning of the 21st century to the present, interest in noble metal nanoparticles
3
4 (MNPs) has increased among researchers, as it is an active area at the academic and industrial
5
6 research levels, especially in industrially applicable researches. The frequent use of NPs has
7
8 been increased as a filler over the traditional fillers because of their highly demanded features.
9
10 For example, gold nanoparticles are characterized by their high and superior electrical, optical,
11
12
and biological properties. Researchers have paid special attention to gold nanoparticles because
13 of their remarkable advantages, such as non-toxicity, high surface area, stability for a long time,
14
15 and their ability to interact with light where they are characterized by the phenomenon of
16
17 surface plasmon resonance (SPR) and their size-dependent optical properties. These multiple
18
19 properties pave the way to use and exploit them in potential technological applications and in
20
21 the field of energy storage and solar cells [1, 2]. Their uses also extend to the drug delivery,
22
imaging and for detecting biomolecules, encompassing DNA and proteins [3, 4].
23
24
25 Various methodologies are used to synthesize gold nanoparticles (AuNPs), including pulsed
26
27 laser ablation, chemical routes, irradiation, and using plant extracts.
28
29
30 Blending polymers technique using two different polymers or more is characterized by its ability
31
32
to produce new materials with remarkable physicochemical properties that could not be
33 achieved by using these polymers separately.
34
35
36 The two hydrophilic polymers, poly (vinyl alcohol) and poly (vinyl pyrrolidone), symbolized by
37
38 PVA and PVP, respectively, are distinctive polar eco-friendly polymers due to their peculiar
39
40 advantages such as; flexibility, biocompatibility, outstanding film formation capability, easy
41
42 processability, satisfactory thermal, optical, and electrical properties [5-7]. Further, they have
43 characteristic functional groups [(-OH of PVA) in addition to (carbonyl and rigid pyrrolidone
44
45 groups of PVP)], which are beneficial in establishing solid interactions between their main
46
47 chains and in forming hydrogen bonds, enhancing the performance of their complexes.
48
49
50 Their blend is fundamentally used as a host matrix for tailoring advanced functional materials
51
52 which can be valuable in preparing solid polymer electrolytes (SPEs) required to design novel
53 advanced energy storage devices e.g.; solar cells, supercapacitors, fuel cells, and nickel-
54
55 cadmium polymer batteries [8-11]. Furthermore, its interesting features have recommended it to
56
57 be used in numerous applications not only in electronics and electrical appliances but also in
58
59 biological, biomedical, technological, and engineering fields. So, they have garnered the
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61 2
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 attention of researchers in both industrial and academic communities over the past twenty years
1
2
[12-14].
3
4 Carboxymethyl cellulose (CMC) polymer is a cellulose derivative that is widely used, because it
5
6 has some beneficial merits such as non-toxicity, recyclability, plentiful accessibility,
7
8 biocompatibility, and eco-friendly behavior [15-16]. The films formed using sodium
9
10 carboxymethyl cellulose are characterized by transparency and high mechanical strength.
11
12
Further, CMC is frequently utilized in various commercial applications, such as; textiles,
13 varnish, paints, medicines, food, and makeups.
14
15
16 During the last fifteen years, the benefits of polymer-based nanocomposites containing MNPs
17
18 have been highlighted [8,17-18], where they merge the features of polymers and nanofillers,
19
20 which have a high surface area.
21
22 Although many published articles have concerned with studying the importance of surface
23
24 plasmons for AuNPs and how to benefit from this important feature in some applications, few of
25
26 them have paid attention to studying the dielectric properties of AuNPs after adding them to a
27
28 polymer. Therefore, this work came to cover this research point and find the best preparatory
29
30 methods characterized by simplicity and low cost and achieving a high dielectric constant of the
31
32
prepared compound. Further, this work aimed to find the correct scientific explanation to link
33 the structural and morphological properties of the materials understudy to the improvement in
34
35 their dielectric properties. The main aim extends to reducing the use of chemicals harmful to the
36
37 environment, negatively affecting human health.
38
39
40 I believe that the synthesized AuNPs/polymer nanocomposites will provide a new avenue
41
42 towards enhancing polymer-based energy storage devices, where controlled materials' physical
43 and chemical properties are key in their functionalities.
44
45
46 The high demands for high-performance rechargeable polymer-based batteries and
47
48 supercapacitors, have resulted from the fast development in electronic devices required for the
49
50 human lifestyle such as laptop computers, mobile phones, digital cameras, portable vacuum
51
52 cleaners, and electric toothbrushes, etc. Therefore, researchers in the last three decades spare no
53 effort to obtain novel polymer nanocomposites with high mechanical strength besides their high
54
55 electrical conductivity and work with high efficiency. Further, they concerned with fabrication
56
57 of SPEs due to their comparative merits over liquid electrolytes.
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 Some recent works [19-22] have been concerned with studying physicochemical properties of
1
2
PVA/PVP based composites. Still, only a few considerations have been given to preparing
3 ecofriendly dielectric nanocomposites that could participate in developing polymer-based
4
5 batteries, actuators and supercapacitors. Furthermore, the ability of nanoparticles to increase
6
7 dielectric permittivity is hampered by their tendency to aggregate. So, this work was carried out
8
9 as an attempt to cover this topic by adding AuNPs to the (PVA/PVP/CMC) polymer blend,
10
11 where the blend forms coating layers on the nanoparticles to overcome the AuNPs aggregations.
12
13 In the present work, structural, morphological, and optical properties of the AuNPs-filled TB
14
15 samples were examined using FT-IR, XRD, UV/VIS, SEM, and TEM. In addition, the AC
16
17 electrical conductivity, dielectric properties, and relaxation behavior of the charge carriers have
18
19 been systematically studied. These studies provided a deep insight into effect of AuNPs
20
21 synthesized in two different ways in improving the various properties of the present
22
nanocomposite samples for utilizing the final product which has the best features in designing
23
24 polymer-based batteries, sensors as well as electrode support materials for organic solar cells.
25
26
27 2. Experimental work
28
29 2.1. Materials
30
31
32 PVA bought from E-Merck (Germany) with molecular weight (M.W.) ≈ 14,000 g. mol-1 is
33 characterized by its highly analytical grade. PVP was purchased from SISCO Research
34
35 Laboratory Ltd. (located at Mumbai, India), and has M.W. ≈ 40,000 g. mol-1. CMC (M.W. ≈
36
37 90,000 g. mol-1) and chloroauric acid (HAuCl4) purchased from Sigma-Aldrich were prudently
38
39 used as received without any additional purification.
40
41
42 2.2. Preparation of leaves’ extract
43
44 Leaves of Hamelia patens were carefully rinsed many times with double distilled (DD) water
45
46 and left for four days to be dry. 25 grams of the collected powder were boiled in mixed solvents
47
48
for 50 min. The final extract was filtered and stored in a refrigerator at 4 °C for later use.
49
50 2.3. Bio-synthesis of AuNPs
51
52
53
2 ml of leaves extract was added to 150 ml of HAuCl4 solution (1 mM/ml) with stirring the
54 mixture for 20 min. As exhibited in Fig. 1a, the addition of faint yellowish-colored HAuCl4 to
55
56 the leaf extract (which has a pale brown color) resulted in a pink color, indicating the successful
57
58 synthesis of gold nanoparticles.
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61 4
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 2.4. Synthesis of AuNPs using laser ablation technique
1
2 The detailed preparation steps for Au nanoparticles are presented in Fig. 1b. In brief, a bulk of
3
4 gold previously cleaned using DD water and chlorobenzene with suitable dimensions 0.4 × 0.4 ×
5
6 0.1 (cm) has been used as a target for preparing AuNPs. A laser beam with 1064 nm basic
7 wavelength has produced from Nd: YAG nanosecond pulsed laser and perpendicularly incident
8
9 on the gold target, which was placed in 30 ml DD water. The gold has been smashed into very
10
11 small nanometer-sized pieces.
12
13
14
15 (a) (b)
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36 Fig. 1: Preparation steps of gold nanoparticles by: a) leaves extract, and b) laser ablation
37 technique.
38
39
40 2.5. Preparation of (PVA/PVP/CMC)/AuNPs samples
41
42 Three grams of PVA was completely dissolved in 200 ml. of DD water, and similar procedures
43
44 were done with three grams of PVP and CMC. The three solutions were strenuously stirred at
45
46 temperature 60 °C for 2.5 hours. PVA/PVP and PVA/PVP/CMC blends were formed by mixing
47
48 their previously prepared solutions with equal weight percentage ratios. AuNPs nanofillers
49
50 prepared in two different ways were added to the PVA/PVP/CMC blend. The homogeneous
51
52
mixtures were wisely dropped onto cleaned Petri dishes made from polypropylene and vacuum-
53 dried at 55 °C for three days in an oven.
54
55
56 The PVA/PVP binary blend and PVA/PVP/CMC ternary blend for simplicity were represented
57
58 as BB and TB blends, respectively. The PVA/PVP/CMC/Au-laser nanocomposite was
59
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61 5
62
63
64
65
 symbolized by TBAu-L, whereas the PVA/PVP/CMC/Au-biosynthesized nanocomposite was
1
2
given the symbol TBAu-B.
3
4 2.6. Characterization techniques
5
6
7 Several techniques have been used to study the various properties of the present composite such
8
9 as;
10
11 X-ray diffraction (XRD) examination was carried out at 293 K via high-resolution X-ray
12 Diffractometer (defined as PANalytical X'Pert PRO MRD) with Cu Kα radiation (run at voltage
13
14 30 kV and wavelength = 1.5406 Å). The best range for Bragg's angle (2θ) was from 3° to 70°.
15
16 Utilizing a double beam spectrophotometer, UV/VIS spectroscopic study of the previously
17
18 produced samples was performed in the wavelength ranged from 190 to 1100 nm. The
19
20 spectrophotometer is of JASCO model V/670 ~ UV/VIS./NIR. Fourier transforms infrared (FT-
21
22
IR) spectrometer (Nicolet iS10 single beam) was carefully utilized to study the structural
23 properties of all samples in the spectral range from 4000 cm-1 to 500 cm-1. Further, scanning
24
25 electron microscope (SEM) was used to provide a deep insight into the morphological changes
26
27 after AuNPs were incorporated into the TB blend. The model details of the SEM device are
28
29 JEOL JSM 6510 LV, USA; and it was operated at 20 kV. In transmission electron microscopic
30
31 analysis, the samples were loaded on carbon-coated Cu grids (200 mesh) and examined by
32
33
HRTEM operated at 200 kV. Its model is JEM-2100, JEOL (Tokyo, Japan). The broadband
34 dielectric spectrometer was used to examine dielectric properties of the described system in
35
36 addition to its AC electrical conductivity. This spectrometer contains high accuracy Novocontrol
37
38 system (concept 40 analyzer) that guarantee recording reliable results with changing frequency
39
40 from 0.1 Hz to 20M Hz.
41
42
43
3. Results and discussion
44 3.1. XRD analysis
45
46
47 XRD measurements are usually carried out due to their influential role in elucidating the
48
microstructural changes of polymer composites. So, it was employed to confirm the
49
50 amorphous/crystalline nature of the (PVA/PVP/CMC)/Au nanocomposite films understudy, and
51
52 investigate AuNPs effects on structural properties of these nanocomposites.
53
54
55 XRD representative patterns of the BB, TB, and the TB blend filled with AuNPs are displayed
56
57 in Fig. 2. The main broad peak at 2 ≈ 19.41° was attributed to the BB with (1 1 0) reflective
58
59 plane [7], and this peak has shifted to ≈ 19.71° because of incorporating CMC into the BB
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61 6
62
63
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65
 matrix. Further, its broadness proves the semicrystalline nature of the TB blend and its
1
2
nanocomposites.
3
4 After adding AuNPs, the intensity of this broad peak has increased, indicating the increase of
5
6 crystalline regions inside the host polymeric matrix. It is worth mentioning that the
7
8 nanocomposite sample containing biosynthesized AuNPs attained a slight increase in intensity
9
10 compared to the nanocomposite with AuNPs prepared by Laser ablation, promoting the previous
11
12
for use in designing energy storage devices.
13
14 New sharp diffraction peaks observed at 2θ = 37.91° (111), 42.12° (200) and 64.29° (220) have
15
16 been ascribed to AuNPs and they are in agreement with values recorded in the standard card
17
18 (JCPDS file No. 4-0784), signifying the successful synthesis of AuNPs. This change in intensity
19
20 of the main peak and the presence of such new peaks affirm the compatibility and efficacious
21
22
incorporation of the AuNPs into the TB host matrix.
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45 Fig. 2: XRD representative patterns of the BB, TB and the TB blend filled with AuNPs.
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47
48 3.2. FT-IR spectroscopy
49
50 Spectroscopic analysis based on FT-IR measurements was implemented at room temperature to
51
52 investigate the complexation, and intermolecular interaction of the TB blend with the AuNPs.
53
54 The FT-IR spectra ranged from 4000 cm-1 to 400 cm-1 in Fig. 3 were recorded for BB, TB,
55
56 TBAu-L and TBAu-B prepared films. The spectra are characterized by the presence of some
57
58
bands such as; 3366 cm-1 (O-H stretching of CMC and PVA), 2936 cm-1 (-CH2 asymmetrical
59 stretching), 1641 cm-1 (C=O stretching), 1442 cm-1 (-CH2 scissoring), and 848 cm-1 (C–H
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61 7
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65
 rocking of PVA). Some peaks that belong to PVP such as that one appeared at 1291 cm-1 was
1
2
ascribed to C–N stretching, while peaks centered at 1496 cm-1 and 933 cm-1 appeared because of
3 the presence of C=N (pyridine ring) and out-of-plane rings C–H bending vibrations, respectively
4
5 [9]. Two shoulder peaks observed at 2868 cm-1 and 1024 cm−1 were imputed to vibrational
6
7 groups of CH2 symmetrical stretching as well as C-O stretching of PVA, respectively.
8
9
10 Some of those peaks in the TBAu-L and TBAu-B spectra showed small shifts as a result of the
11
12
incorporation of AuNPs into the TB matrix. For example, the 3366 cm−1 band has shifted
13 towards lower wavenumber to 3333 cm−1 due to the addition of biosynthesized AuNPs. Further,
14
15 the spectra have exhibited noticeable changes in some bands’ intensities due to the
16
17 physicochemical interactions [23] where the TB matrices act as electron donors and the electron
18
19 acceptors were the AuNPs [24].
20
21
22
Oxygen in the ether linkage provides a great opportunity for originating inter-molecular
23 hydrogen bonds with different molecules in the PVP and CMC polymers and the result was the
24
25 formation of a high intensity peak at 1094 cm−1 [25]. This peak is known as amorphous peak
26
27 [26], confirming the semicrystalline structure of the current nanocomposite samples.
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48
49
50
51
52
53 Fig. 3: FT-IR spectra of the pure blends and the ternary blend doped with AuNPs prepared in
54
55 two different ways.
56
57
58 The two vibrational bands centered at 1559 cm−1 and 1319 cm−1 have ascribed to intramolecular
59
60 interaction of the asymmetric carboxylate (-COO−) stretching functional group and the hydroxyl
61 8
62
63
64
65
 (O–H) bending group because these two groups increase the opportunity for complexation
1
2
between the nanofiller and the polymeric materials [27]. This enhances the microstructural
3 properties of the TB-based nanocomposites and support the above findings.
4
5
6 3.3. Morphological properties
7
8 In order to study the effect of adding AuNPs on the morphological and microstructural
9
10 characteristics of the present nanocomposites, SEM analysis was carried out as demonstrated in
11
12 Fig. 4. The representative micrographs of the prepared nanocomposite samples were recorded at
13
14 magnification 2500 times. It is clear from this figure that the TB polymer blend is compatible
15
16 with AuNPs, as no phase separations were detected. In comparison with the pure blend
17
micrograph shown in Fig. 4a and characterized by its smooth surface, the other micrographs had
18
19 rough morphology. The SEM images appeared in Fig. 4c-d have bright protruded microparticles
20
21 which regularly dispersed on their surfaces. Fig. 4d of the TBAu-L nanocomposite has a much
22
23 rougher surface than Fig. 4c of the TBAu-B nanocomposite, promoting the sample containing
24
25 Au prepared using plant extraction over the sample containing Au prepared using laser ablation.
26
27 These protruded microparticles were attributed to AuNPs agglomerates, confirming the physical
28 interaction of the nanofiller with the TB polymer blend.
29
30
31 3.4. Ultraviolet and visible analysis
32
33 UV/VIS spectroscopy was exploited to elucidate the influence of interaction of AuNPs
34
35 synthesized in two different ways with the TB blend on optical behavior of the resulted films.
36
37 Figure 5 demonstrates the UV/VIS absorption spectra of BB, TB, and AuNPs-based
38
39 nanocomposites in the wavelength region from 190 to 1100 nm at room temperature. Absorption
40
41 sharp edge that characterizes the UV spectra appeared at about 238 for BB and 246 nm for the
42
43
TB blend. The obvious change in the height of this edge for the TBAu-B and TBAu-L samples
44 is ascribed to the disorder in the host matrices due to filling with AuNPs. In another expression,
45
46 this change is due to the wide spread of amorphous areas within the TB matrix beside the
47
48 presence of some crystalline regions, confirming XRD results, i.e., semicrystalline nature of the
49
50 samples [28-29]. Also, the bathochromic (red) shift in this edge from 246 nm to 260 nm leaves
51
52 no doubt about the successful occurrence of a considerable complexation between components
53
54
of the abovementioned nanocomposites.
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61 9
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 1 (a) (b)
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18 (c) (d)
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34
35 Fig. 4: The representative micrographs of a) BB blend, b) TB blend, c) TBAu-B, and d) TBAu-
36
37
L samples at magnification 2500 times.
38
39 Electronic transitions from HOMO to LUMO is considered the main reason of arising charge
40
41 transfer absorption bands. Thus, the band localized at ≈ 225 nm is assigned to n →* transition
42
43 [30], which was blue-shifted toward 220 nm. This shift in turn asserts the strong conjugation
44
45 among the nanofiller and TB polymer blend [31] where the TB host matrix acts as
46
47 reducing/capping agents on the surface of AuNPs.
48
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22
23 Fig. 5: The UV/VIS absorption spectra of BB, TB, and AuNPs-based nanocomposites in the
24
25 wavelength region from 190 to 1100 nm at room temperature.
26
27
28 Spectrum of the green synthesized gold nanoparticles in Fig. 6 exhibits a broad peak at 539 nm,
29
30
while the broad peak observed at about 531 nm is attributed to the AuNPs prepared by laser
31 ablation. The spectra have shown absorption peaks at about 525 nm for TBAu-B and 517 nm for
32
33 TBAu-L which were attributed to the surface plasmon resonance peak (SPR) of AuNPs [32].
34
35 Thus, this peak proves the successful synthesis of AuNPs by extraction from the Hamelia patens
36
37 and using the laser ablation technique.
38
39
40
Basically, the SPR is sensitive to light radiation, where free electrons of AuNPs oscillate due to
41 their interaction with incident photons. Thus, the presence of such peak suggests the appropriacy
42
43 of these prepared films characterized by flexibility to be used in biomedical devices and in
44
45 optoelectronic applications such as photosensors. The blue shift of SPR peaks, from 539 nm to
46
47 525 nm for biosynthesized AuNPs and from 531 nm to 517 nm for AuNPs prepared by laser
48
49 ablation, was stemmed from the quantum confinement effect which implies the decrease in the
50
51
AuNPs size, supporting the TEM results.
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61 11
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19 Fig. 6: The UV/VIS absorption spectra of synthesized AuNPs by: a) leaves extract, and b) laser
20
21 ablation technique.
22
23 3.4.1. Optical constants
24
25 3.4.1.a. Optical energy gap (Eg)
26
27
28
Additional studies on the optical absorption in UV/VIS regions were carried out in an attempt to
29 get more information about the electronic band structure of the nanocomposite samples.
30
31 Commonly, transitions that could occur at the absorption edge of polymeric composites have
32
33 two different kinds; indirect and direct transitions. Tauc’s plot is based on equations (1) and (2)
34
35 [33, 34], where (h)2 and (h)1/2 were plotted as functions of energy (h) in Fig. 7 to
36
37 determine the direct (Egd) and indirect (Egi) optical energy gaps, respectively.
38
39
(𝑛𝛼ℎ𝜐)2 = 𝐹1 (ℎ𝜐 − 𝐸𝑔𝑑 ) (1)
40
41 1
42 (𝑛𝛼ℎ𝜐)2 = 𝐹2 (ℎ𝜐 − 𝐸𝑔𝑖 ) (2)
43
44 where, h represents energy of incident photons,  is the absorption coefficient, F1 , F2 ,
45
46 constants, and n is an integer. The absorption coefficient was calculated by knowing the
47
48 absorbance (Abs) and the thickness (d) of the sample under study as represented in the following
49
50
formula [28, 35]:
51 𝐴𝑏𝑠
52 𝛼(𝜐) = 2.303 × (3)
𝑑
53
54 The calculated direct and indirect optical band gaps of the above-described samples have been
55
56 summarized in Table (2). From the obtained values, it is clear that incorporation of AuNPs led
57
58 to a significant decrease in the Eg values, where the TBAu-B nanocomposite is promoted over
59
60 the TBAu-L nanocomposite by attaining the lowest Eg value. This decrease has originated from
61 12
62
63
64
65
 the numerous polaronic contribution and imperfections arose within the TB-based
1
2
nanocomposites.
3
4
5 (a) (b)
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 Fig. 7: The (h)2 and (h)1/2 as functions of energy (h) for the current samples.
26
27 The exponential decay tail detected in all the curves of Fig. 7 at lower energies suggests that the
28
29 localized levels formed in the band gap was attributable to structural disorder in the host matrix
30
31 [36]. As well as, it confirms the domination of amorphous regions inside the synthesized films,
32
33 corroborating the results concluded from the previous measurements.
34
35
36
3.4.2.b. Refractive index (n)
37
38 Refractive index plays a very effective role in designing integrated optical devices, where it
39
40 largely relies on the electronic polarization of ions [37]. The n values were determined by
41 substituting by the previously calculated optical energy gap in the following equation [38] and
42
43 the obtained results were summarized in Table (2):
44
45
46 𝑛2 −1 𝐸𝑔
47 =1−√ (4)
𝑛2 +2 20
48
49
50 The increase in nanocomposite density due to embedding the AuNPs inside the TB host matrix
51
52 affected the speed of light penetrating it, increasing the refractive indices of the current samples.
53
54 In another expression, the decrease in interatomic distances caused by the higher density inside
55
56
the nanocomposites led to a rise in the coordination number. Thus, the more non-bridging
57 oxygen bonds there are, the higher the calculated refractive index [39], suggesting that the
58
59 TBAu-B and TBAu-L nanocomposites are viable candidates for use in some industrial
60
61 13
62
63
64
65
 applications in optoelectronic sector as well as for developing optical devices e.g.; filters, and
1
2
high refractive index lenses.
3
4 Table 2: Direct and indirect optical energy gap (Eg), refractive index, and the relaxation time (τ)
5
6 of the described composite films.
7
8
9 Eg (eV)
10 W (wt %) Refractive index (n) Relaxation time (s)
direct indirect
11
12 BB blend 5.13 4.91 2.01 -
13 TB blend 4.72 3.7 2.23 7.44 × 10-3
14
15 TBAu-B 4.32 2.49 2.55 5.52 × 10-4
16 TBAu-L 4.5 3 2.38 2.4 × 10-4
17
18
19
20 3.5. TEM analysis
21
22 The transmission electron microscope (TEM) technique is usually used to determine the size,
23
24 shape and distribution of the synthesized nanoparticles. Figure 8 exhibits the TEM micrographs
25
26 of the AuNPs prepared in two different ways and their corresponding histograms that
27 demonstrate the nanoparticles size distribution and their areas. This figure exhibits that the
28
29 AuNPs are more uniformly distributed in the TBAu-B matrix than in the TBAu-L matrix.
30
31 Further, the AuNPs shapes vary from triangular to hexagonal, irregular and spherical shapes.
32
33 The size of biosynthesized AuNPs has ranged from 3 to 24 nm, while the size of AuNPs
34
35 prepared by using Laser ablation has ranged from 2 to 30 nm, confirming the UV/VIS
36
37
spectroscopic results.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61 14
62
63
64
65
 1 (a) (b)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Fig. 8: The TEM micrographs of the AuNPs prepared in two different ways and their
58 corresponding histograms related to the nanoparticles size distribution and their areas.
59
60
61 15
62
63
64
65
 3.6. Dielectric spectra studies
1
2 3.6.1 Dielectric permittivity analysis
3
4 Dielectric performance of the BB, TB, TBAu-L and TBAu-B prepared films was studied in the
5
6 frequency range of 1 × 10-1 – 2 × 107 Hz. The real (') and imaginary (") parts of dielectric
7
8 permittivity are expressed by the following formula [40];
9
10 𝐶𝑒𝑥𝑝 𝑑
11 𝜀′ = (5)
𝜀𝑜 𝐴𝑒
12
13
𝜎
14 𝜀 ′′ = (6)
15 2𝜋𝑓𝜀𝑜
16
17
18 where, Cexp is the experimental value of capacitance recorded for a sample under study, while Ae
19
20
symbolizes cross-sectional area of the electrode and o is the well-known permittivity of free
21 space.
22
23
24 Figure 9a shows the ' values against frequency over the aforementioned range, whereas Fig. 9b
25
26 displays the change in " values with frequency over the same ranges for all the prepared
27
28 samples. The two parameters have similar behavior, where they had their highest values at low
29
30 frequency and decreased with the continuous increase in frequency. It is evident that ' and "
31
32 depend on the nanocomposites’ constituents, because their values have improved after
33
34 incorporating the AuNPs into the TB matrix. It is worth mentioning that the nanocomposite that
35
36
contains biosynthesized AuNPs has attained the best ' value.
37
38 On the one hand, the high ' values recorded for frequencies lower than 150 Hz were attributable
39
40 to the success of induced dipoles in following the periodic variation of the employed field
41
42 direction. This change is slow, so it grants the present dipoles a suitable time to bring
43
44 themselves into line with/against the applied field direction. This response led to a considerable
45
46 enhancement in interfacial polarization (known as the Maxwell-Wagner-Sillars polarization)
47
48
and this resulted in good dielectric properties of the present nanocomposite films.
49
50 On the other hand, the remarkable decrease in the ' values for frequencies higher than 150 Hz
51
52 was assigned to the ineptitude of charge carriers to change their directions with the applied field,
53
54 giving rise to the gradual gathering of ions at the interfacial regions between the TB polymer
55
56 blend and AuNPs which reduces the interfacial polarization [40].
57
58
59
60
61 16
62
63
64
65
 1 (a)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 (b)
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 Fig. 9: The variation of frequency with a) ' and b) " for the BB, TB, TBAu-B and TBAu-L
43
samples recorded at room temperature.
44
45
46 For the frequency region (f ≥102 Hz), the trivial variations in the ' and " values with
47
48 frequency, displayed in Fig. 9a and Fig. 9b, are due to the small effective influence of ionic
49
50 polarization in addition to the low participation of electronic polarization. Moreover, this
51
52 insignificant change is ascribed to the dielectric relaxation processes inside the TB host
53
54 polymeric matrix [41].
55
56 Therefore, incorporating AuNPs nanofiller into the PVA/PVP/CMC host matrix had a fruitful
57
58 effect on amelioration in the dielectric properties of all samples, especially the sample
59
60 containing biosynthesized AuNPs, confirming the XRD and UV/VIS findings.
61 17
62
63
64
65
 It is worth mentioning that the recorded dielectric loss has resulted from the leakage of current
1
2
resulting from the direct contact of AuNPs. Coating the gold nanoparticles with small layers of
3 the TB blend prevents such leakage, where the existence of these layers indicates that the TB is
4
5 respectably compatible with the AuNPs. The presence of AuNPs between two TB layers which
6
7 is characterized by their dielectric nature, is good evidence about the formation of micro-
8
9 capacitors inside the PVA/PVP/CMC host matrix [40].
10
11
12
3.6.2 Dielectric relaxation analysis
13
14 The variation of loss tangent (tan ) of the pure blends and their nanocomposite films with
15
16 frequency at 293 K is presented in Fig. 10. The carful study of this dependence provides a
17
18 deeper insight into the dielectric relaxation processes inside the current system. Tan  is
19
20 governed by the ratio between dissipated energy (") and energy stored (') by the sample under
21
investigation.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45 Fig. 10: The variation of loss tangent (tan ) of the pure blends and their nanocomposite films
46
47
with frequency at 293 K.
48
49 This figure is characterized by intense relaxation peaks, which are ascribed to dipolar relaxation
50
51 process of the polymeric segments as a result of ion-dipole complexation. These peaks have
52
53 asymmetrical behavior, confirming the semicrystalline nature of the (PVA/PVP/CMC)-based
54
55 composite. Further, the presence of such single relaxation peak indicates the dominance of ionic
56
57 conduction inside the host polymeric matrix. Furthermore, the appearance of this peak in the
58 low-frequency region (f ≤ 10-3 Hz) is due to α-relaxation process associated with a rotational
59
60
61 18
62
63
64
65
 motion of lateral functional groups distributed around the central chain axis inside the polymeric
1
2
matrix [11].
3
4 The first part of this peak which represents an increase in tan  with frequency at lower-
5
6 frequency is due to domination of ohmic elements over the capacitive nature of the samples.
7
8 With increasing frequency, tan  reached its maximum, and then it gradually decreased (the
9
10 second part) due to the increment in the capacitive components (micro-capacitors) inside the
11
12 prepared samples [42]. The highest value of tan  is found to be 11.7 for the TBAu-B
13
14 nanocomposite, while its value for the TBAu-L is 17.5.
15
16 The distinct shift in the peak’s position towards the high-frequency region indicates that the
17
18 relaxation times (τ) value decreased. In other words, the incorporation of AuNPs having a
19
20 conductive nature into the TB with a dielectric nature produced an interfacial polarization,
21
22 where new interfacial areas were formed between the PVA/PVP/CMC prepared blend and the
23
24 nanofiller. Moreover, the accumulation of AuNPs in these interfacial regions led to the observed
25
26
shift in the peak’s position towards the high-frequency region, and consequently the reduction in
27 the τ values. This reduction can be assigned to the decrease of free areas within the host matrix
28
29 due to the uniform distribution of the AuNPs, especially in the TBAu-B nanocomposite as
30
31 discussed in the TEM results. This sample has achieved the highest enhancement and
32
33 comparative features over the other samples, and this recommends it for use in manufacturing
34
35 energy storage devices that are characterized by high performance.
36
37 3.6.3. Electric modulus formalism and relaxation
38
39
40 The electric modulus formalism is characterized by its ability in tackling the dominant
41
42 conduction mechanism in the polymer electrolyte and in the successful suppression of the
43
44 contribution of electrode polarization. The dielectric real and imaginary moduli symbolized by
45
46 M' and M", respectively were calculated via the well-known formulas:
47
48 𝜀′
49 𝑀′ = 2 2 (7)
𝜀 ′ +𝜀 ′′
50
51
𝜀 ′′
52 𝑀′′ = 2 2 (8)
53 𝜀 ′ +𝜀 ′′
54
55 The variation of M' values versus frequency recorded at room temperature for the above-
56
57 described electrolyte samples are presented in Fig. 11a. The spectra in this figure are composed
58
59
60
61 19
62
63
64
65
 of two parts: the first one (a tail) lies at lower frequencies, while the other part has a sigmoid
1
2
shape and located at medium and at high frequency regions.
3
4 The presence of such tail is a clear indication about the complete elimination of the electrode
5
6 polarization contribution. The increase in the width of this tail after filling with AuNPs implies
7
8 that the TB-based nanocomposite films are of a remarkable capacitive feature [40], supporting
9
10 the above findings. Also, the observed decrease in M' values due to incorporating the nanofiller
11
12
into the TB matrix implies that induced ions move from one location to another location by
13 hopping, demonstrating the dominance conduction mechanism in the present nanocomposite
14
15 samples [43].
16
17
18 The dependence of M'' values on frequency recorded at room temperature for the present
19
20 complex films are exhibited in Fig. 11b. The M'' curves have a well-defined loss peak which has
21
22
stemmed from the migration of induced charge carriers and indicates that the main chain of the
23 host matrix has been relaxed. It is also known as the conductivity relaxation peak. The existence
24
25 of such peak in M″ spectrum refers to the alternation in charge carriers’ transition from long-
26
27 range inside the host polymeric matrix to short-range [44].
28
29
30 The observed decrease in the peak intensity due to mixing the AuNPs with TB is a good
31
32
evidence about the non-Debye behavior of the nanocomposite samples [21]. This reduction
33 behavior is largely congruent with the dielectric relaxation resulted from Maxwell-Wagner-
34
35 Sillars (MWS) polarization effect [40]. This dramatic decrease in the M'' values has followed by
36
37 a gradual increase with the further increase of the frequency which implies that another
38
39 dielectric relaxation process has arisen inside these nanocomposites at high frequency region.
40
41 The latter relaxation process at high frequency is attributed to the dipolar reorientation of some
42
43
functional groups such as; N–O and -OH. The shift appeared in the characteristic relaxation
44 peak in the direction of the high frequency side implies the decrease in relaxation times as
45
46 exhibited in Table (2) due to the introduction of new interfacial regions with the addition of the
47
48 Au nanoparticles, where the induced charge carriers can move through them and confirms that
49
50 the predominant conduction mechanism is of a hopping-type, emphasizing the M' findings.
51
52
53
54
55
56
57
58
59
60
61 20
62
63
64
65
 1 (a)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 (b)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 Fig. 11: The variation of frequency with a) M' and b) M" for the BB, TB, TBAu-B and TBAu-L
45
46 samples recorded at room temperature.
47
48
49 3.6.4. Electric modulus scaling
50
51 Scaling of M" curves versus normalized frequency (f/fmax) of the TBAu-B and TBAu-L
52
53 nanocomposites compared to the TB curve were depicted in Fig. 12 at room temperature. From
54
55 this figure, the spectra of above-described films have clearly collapsed onto a single master
56
57 curve in the medium frequency region for TBAu-B, whereas they have superimposed at lower
58
59
frequencies for TBAu-L. This behavior indicates that the relaxation dynamics do not depend
60
61 21
62
63
64
65
 onto composition of the nanocomposites [45]. Nevertheless, the spectra deviated from the
1
2
typical master curve at high frequency region because of the confinement of charge carriers in
3 potential wells. The observed small deviation also implies that the relaxation process during the
4
5 electrical conduction is contingent on the presence of AuNPs inside the films under study.
6
7 Moreover, the asymmetric peak characterized these curves confirms the non-Debye response of
8
9 the nanocomposite samples [11].
10
11
12 (a) (b)
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Fig. 12: The Scaling of M" curves versus normalized frequency (f/fmax) of a) TBAu-B, and b)
29
30 TBAu-L nanocomposites compared to the TB curve.
31
32
33 The variation of M" versus M' (Cole-Cole plot that represents Argan diagrams) were plotted for
34
35 the synthesized samples as exhibited in Fig. 13. The cole-cole plot is generally divided into three
36
37
frequency-dependent regions; low, middle and high frequency regions. The three regions are
38 ascribed to the grain boundary effect, the participation of grains, and the bulk conduction
39
40 relaxation process, respectively. The present spectra are characterized by a single semicircular
41
42 arc which is attributed to the grain boundary effect and surface polarization, while the spike
43
44 observed is assigned to the bulk conduction response. The asymmetrical behavior of this
45
46 relaxation peak confirms the non-Debye dielectric relaxation response. The dielectric relaxation
47
processes in the current system can be represented by a parallel combination of a resistor (R)
48
49 and geometrical capacitor (C) [46-47]. The relaxation peak frequencies are governed by the
50
51 following equation:
52
53
1
54 𝑓𝑚𝑎𝑥 ≈ (9)
2𝜋𝑅𝐶
55
56
57 According this equation, the peak frequency is inversely proportional to the capacitance of the
58
59 geometrical capacitor. Compared to the observed shift in the fmax toward the lower frequency
60
61 22
62
63
64
65
 region, the TBAu-B sample has achieved the highest capacitance, recommending it to be used in
1
2
designing electrical double-layer capacitors (EDLCs) and other electrochemical devices.
3 Further, this shift is a clear indication about the small contribution of the grain boundary to the
4
5 electrical conduction mechanism inside the TB host matrix. This behavior is attributed to the
6
7 dominance of the current composite film's capacitive component over the resistive one due to
8
9 the induced dipoles' random orientations in the chains laterally linked to the main chain of the
10
11 TB blend.
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Fig. 13: The variation of M" versus M' (Cole-Cole plot that represents Argan diagrams) for the
35
36 synthesized samples.
37
38 3.7. Electrical conduction behavior
39
40
41 Based on the above analyses and their findings, it is found that the TBAu-B sample have
42
43
achieved the best results. So, the real (') and imaginary (") parts of the electrical conductivity
44 have been carefully studied with varying frequency and temperature as displayed in Fig. 14.
45
46
47 The complex electrical conductivity (*) is expressed by the following relation [48]:
48
49
𝛿 𝐶
50 𝜎 ∗ = 𝜎 ′ − 𝑖𝜎 ′′ = − 𝑖2𝜋𝑓𝜀𝑜 (1 − ) (10)
51 𝜋𝑟 2 𝑅 𝐶𝑜
52
53 Where, Co symbolizes capacitance of the capacitor containing free space, while C is capacitance
54
55 of the capacitor containing the TBAu-B sample, r is radius of the used electrode, and  is the
56
57 distance between the two conducting electrodes.
58
59
60
61 23
62
63
64
65
 1
(a)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 (b)
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 Fig. 14: The variation of frequency and temperature with a) real ('), and b) imaginary (")
43
44 parts of the electrical conductivity for the TBAu-B nanocomposite sample.
45
46
47 The presence of the biosynthesized AuNPs gave rise to the dominance of amorphous regions
48
49
over crystalline regions, and thus facilitating the movement of induced ions with short-range
50 distances, resulting in the observed increase in the electrical conductivity.
51
52
53 With increasing frequency, the relaxation of charge carriers by jumping back and forth through
54
55 the localized sites resulted in the enhancement of electrical conductivity observed at the high
56
57 frequency region (dispersive region). This enhancement is ascribed to the change in hopping
58
59
behavior from long-range distances to short-range distances.
60
61 24
62
63
64
65
 The ' curves have distinguished by a plateau behavior (independent on frequency) that
1
2 represents the DC conductivity (dc) at lower frequencies, whereas the continuous increase in
3
4 frequency has resulted in the observed enhancement in ' and produced the dispersive region.
5
6 The dc values of the TBAu-B at different temperatures have been determined from the
7
8
frequency-independent region and listed in Table 3. Further, the ' has been improved with the
9 continuous increase in applied temperature, confirming the thermally activated behavior of the
10
11 induced charge carriers inside the TBAu-B nanocomposite matrix.
12
13
14 It is worth mentioning that the gained temperature has induced the charge carriers inside the
15
16 TBAu-B sample to hop for long-range distances from a localized site to another site. Further, the
17
18 rise in temperature facilitates the movement of small polarons with the aid of phonon-assisted
19 tunneling mechanism. These results demonstrate that the studied SPE filled with biosynthesized
20
21 AuNPs has advantageous features, indicating its suitability as a qualified base material for
22
23 designing and developing promising energy storage devices and flexible-type polymer-based
24
25 batteries.
26
27
28 It is observed from Fig. 14 that the frequency region corresponding to the electrode polarization
29 effect significantly increased with temperature, and that both the two conductivity parts follow
30
31 the universal power law at high frequency region. The power law is given by;
32
33
34 𝜎′𝑎𝑐 = 𝜎𝑑𝑐 + 𝛽𝜔 𝑆 (11)
35
36
37 where, β is a factor that depend on temperature, and S is a frequency exponent. S affects by
38
39 translational movement of the induced charge carriers that implies the presence of relaxation
40 response during the electrical conduction process inside the (PVA/PVP/CMC)/AuNPs
41
42 nanocomposite samples [29].
43
44
45 The S values for the TBAu-B sample were calculated in the temperature range 293K-353 K and
46
47 was listed in Table 3. The observed decrease in S values with the continuous increase in
48
49 temperature, indicating that the most appropriate model in elucidating and describing the
50 behavior of charge carriers during the conduction process inside the TBAu-B nanocomposite
51
52 sample is the correlated barrier hopping (CBH) model.
53
54
55 A suggested schematic diagram for preparing a battery using TBAu-B is exhibited in Scheme 1.
56
57 It is noteworthy that, the electrolyte in a solid-state polymer battery is the TBAu-B
58
59 nanocomposite film, while a metal foil represents the negative electrode. In the current battery
60
61 25
62
63
64
65
 structure, a cathode consists of three components: the present nanocomposite electrolyte which
1
2
acts as an ionic conductor, graphite blocks (carbon) which acts as electronic conductors, and
3 particles of Iodine as interaction material. The anode material consists of lithium ions.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Scheme 1: A suggested schematic diagram for preparing a battery.
30
31
32 Table 3: The DC conductivity values (dc) of the TBAu-B at different temperatures determined
33
34 from the frequency-independent region and the frequency exponent (S).
35
36
37 Temperature (K) σdc (S/cm) S
38
39 293 7.08 × 10-10 0.96 ± 0.09
40
41 313 1.78 × 10-8 0.78 ± 0.021
42
333 1.58 × 10-7 0.62 ± 0.029
43
44 353 7.94 × 10-7 0.45 ± 0.03
45
46
47 4. Conclusion
48
49
50
Plant extract and laser ablation techniques were used to synthesize AuNPs, whereas the simple
51 casting method was exploited to synthesis the TB/AuNPs nanocomposites. The microstructural,
52
53 morphological, dielectric, and optical properties of the described films were prudently studied.
54
55 FT-IR, UV/VIS, TEM, and SEM confirmed the successful complexation and compatibility
56
57 between the nanocomposites’ constituents. The asymmetrical single relaxation peak resulted
58
59 from the dipolar relaxation process of the polymeric segments in addition to the XRD results
60
61 26
62
63
64
65
 confirmed the semicrystalline nature of the TB-based samples and indicated the dominance of
1
2
ionic conduction inside the host polymeric matrix. The difference in nature between the TB
3 blend and AuNPs produced new interfacial regions, reducing the relaxation time from 10-3 S to
4
5 10-4 S. Further, this difference had an effective role in forming micro-capacitors inside the
6
7 matrix, enhancing the dielectric properties of the final product. The sample with biosynthesized
8
9 AuNPs has achieved DC electrical conductivity of 7.08 × 10-10 S/cm at room temperature, which
10
11 is enhanced to 7.94 × 10-7 S/cm with increasing temperature to 353 K. Utilizing the leaves’
12
extract led to producing well-uniformed distributed AuNPs, reducing the free areas within the
13
14 host matrix. This change resulted in the significant increase in AC conductivity values, where
15
16 the charge carriers hopping behavior changed from a long-range distance to short-range
17
18 distance. Also, the dependence of ' on temperature confirmed the thermally activated behavior
19
20 of the induced charge carriers inside the TBAu-B nanocomposite matrix. So, the TBAu-B
21
22 sample has achieved the highest enhancement and comparative features such as capacitance
23
24
over the other samples. Therefore, the overall findings obtained in this study propose that the
25 TBAu-B nanocomposite is an advantageous candidate for use as a qualified base material in the
26
27 design and development of promising energy storage devices and flexible polymer-based
28
29 batteries.
30
31
32 Conflicts of interest
33
34
The author declare that I have no known competing financial interests or personal relationships
35
36 that could have appeared to influence the work reported in this paper.
37
38
39
40 References
41
42 [1] Notarianni, M., Vernon, K., Chou, A., Aljada, M., Liu, J. and Motta, N., 2014. Plasmonic effect of gold
43
44 nanoparticles in organic solar cells. Solar Energy, 106, pp.23-37.
45 [2] Zhang, D., Wang, M., Brolo, A.G., Shen, J., Li, X. and Huang, S., 2012. Enhanced performance of dye-
46
47 sensitized solar cells using gold nanoparticles modified fluorine tin oxide electrodes. Journal of Physics D:
48 Applied Physics, 46(2), p.024005.
49
50 [3] S. Alex, A. Tiwari, Functionalized Gold Nanoparticles, Synthesis, properties and applications–a review, J.
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Captions - Figure(s)

Figure captions:

Fig. 1: Preparation steps of gold nanoparticles by: a) leaves extract, and b) laser ablation
technique.

Fig. 2: XRD representative patterns of the BB, TB and the TB blend filled with AuNPs.

Fig. 3: FT-IR spectra of the pure blends and the ternary blend doped with AuNPs prepared in
two different ways.

Fig. 4: The representative micrographs of a) BB blend, b) TB blend, c) TBAu-B, and d) TBAu-

L samples at magnification 2500 times.

Fig. 5: The UV/VIS absorption spectra of BB, TB, and AuNPs-based nanocomposites in the
wavelength region from 190 to 1100 nm at room temperature.

Fig. 6: The UV/VIS absorption spectra of synthesized AuNPs by: a) leaves extract, and b) laser
ablation technique.

Fig. 7: The (h)2 and (h)1/2 as functions of energy (h) for the current samples.

Fig. 8: The TEM micrographs of the AuNPs prepared in two different ways and their
corresponding histograms related to the nanoparticles size distribution and their areas.

Fig. 9: The variation of frequency with a) ' and b) " for the BB, TB, TBAu-B and TBAu-L
samples recorded at room temperature.

Fig. 10: The variation of loss tangent (tan ) of the pure blends and their nanocomposite films
with frequency at 293 K.

Fig. 11: The variation of frequency with a) M' and b) M" for the BB, TB, TBAu-B and TBAu-L
samples recorded at room temperature.

Fig. 12: The Scaling of M" curves versus normalized frequency (f/fmax) of a) TBAu-B, and b)
TBAu-L nanocomposites compared to the TB curve.

Fig. 13: The variation of M" versus M' (Cole-Cole plot that represents Argan diagrams) for the
synthesized samples.

Fig. 14: The variation of frequency and temperature with a) real ('), and b) imaginary (")
parts of the electrical conductivity for the TBAu-B nanocomposite sample.

Scheme 1: A suggested schematic diagram for preparing a battery.