IZMIR KATIP CELEBI UNIVERSITY

FACULTY OF ENGINEERING AND ARCHITECTURE

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING

INVESTIGATION OF FeO & ZnO NANOPARTICLE

EMBEDDED POLYMER MATRIX COMPOSITES

Gökçe DUNLU

13.12.2023

IZMIR
ARTICLE.1: Magnetic studies of 0.7(𝐅𝐞𝟐 𝐨𝟑 )/0.3(ZnO) Nanocomposites in Nanopowder
Form and Dispersed in Polymer Matrix [1]

The 0.7(Fe2O3) / 0.3(ZnO) nanocomposites were investigated in this study using transmission
electron microscopy (TEM) and X-ray diffraction (XRD) techniques. To further investigate the
magnetic properties, research on magnetic hysteresis and isothermal magnetization was done.
Studies on the interactions between the nanocomposites and their surroundings were also
carried out. The composition of these nanocomposites is 30% ZnO and 70% Fe2O3.
Furthermore, nanocomposites distributed inside the polymer matrix at a certain weight percent
(0.1%) are explicitly investigated in the section that looks at them.

In the experimental section of the study, the 0.7(Fe2O3)/0.3(ZnO) nano powder was
synthesized using the traditional wet chemistry method and subjected to calcination. A mixture
of iron and zinc hydroxides was obtained by adding ammonia solution to the solution of Zn
(NO3)4·6H2O and Fe (NO3)3·4H2O in water. The obtained hydroxides were filtered, dried,
and calcined at 573 K for 1 hour.

RESULTS;
Upon examining the characterization results, it was observed from the SEM image that the
particles were strongly agglomerated. The agglomerates were generally in the size range of up
to 100 nm, typically between 30 nm and 60 nm. Hexagonal crystals corresponded to ZnO,
while small spherical crystals represented the ZnFe2O4 spinel phase. The TEM image depicted
a collection of nanocrystals, roughly comparable in size to those determined by XRD. While
the average size of crystallites calculated from XRD diffraction covered the entire sample, the
TEM image represented only a very small portion of the sample, leading to the conclusion that
XRD was more reliable than TEM [1].

Figure.1. SEM (left) and TEM (right) images of 0.7(Fe2O3)/0.3(ZnO) nanopowder.

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 ARTICLE.2: Sol‑Gel/Gel Casting Nano-architectonics of Hybrid 𝐅𝐞𝟐 𝐨𝟑 –ZnO/PS‑PEG
Nanocomposites and Their Optomagnetic Properties [2]

The aim of this study is to investigate the effect of incorporating FeO and ZnO nanoparticles
into a polymer matrix on performance and physical properties. The controlled sol-gel method
combined with gel casting to achieve the nanocomposites preparation stage. This procedure
created (ZnO)x(1-x)Fe2O3 nanocomposites that were incorporated into a polystyrene-
polyethylene glycol matrix. A sol-gel method and casting approach were used to generate the
PS/PEG mix loaded by Fe2O3 doped with ZnO at varied concentrations (0, 1, 3, 5, and 7 wt%)
nanoparticles, which were then stirred for two hours at 40 °C. The characterization of the
nanocomposites involved the use of methods such as X-ray diffraction (XRD), scanning and
transmission electron microscopy (SEM/TEM), Fourier transform infrared spectroscopy
(FTIR), and magnetic measurements. Additionally, a spectrophotometer was used for optical
spectrum analysis.

RESULTS;
XRD spectra exhibited the characteristic peaks of pure and doped PS, PEG, Fe3+, and ZnO
within the PS-PEG-Fe2O3 matrix. The XRD pattern of the pure sample displayed two phases
marked by the main three peaks indicating the PS-PEG-based Fe3O4 phase. Upon the addition
of ZnO nanoparticles, all XRD peaks shifted to lower angles, indicating the transition to the
zinc ferrite phase. With higher ZnO ratios, the formation of zinc ferrite oxide within the PS-
PEG matrix became more prominent.

Figure.2 The XRD patterns of PS-PEG-Fe/(0-7)ZnO nanocomposites

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The nanocomposites in the seven Fe3+ samples had a flat, compact surface with some nano-
spherical forms visible on it, according to the results of SEM and TEM investigations. The Fe-
doped nanocomposite showed a homogenous distribution and a smooth surface. The
production of evenly scattered gray and dark-colored dots in nano-sized spherical formations
inside the PS-PEG matrix was shown by TEM micrograph inspections and particle distribution
studies. This finding indicates that the intended phase has successfully formed and dispersed.
It was determined that the average particle size was around 23 nm. Fe-ZnO nanoparticles were
found to be continuously developing into crystals within the PP matrix, which suggests that the
polystyrene network has stabilized.

Figure.3 SEM images for (a) PPFe, (b) PPFe-7ZnO, (c), (d) the TEM for PPFe-(3, 7) ZnO,

The results obtained from the infrared spectroscopy analysis can be listed as follows:

1) Chemical Structure and Absorption Groups: Characteristic absorption groups such as

OH, CH, OH, and CH3 vibrations were identified at larger wavelengths.

2) Organic Polymerization: In the mid-infrared region, an increase in the intensity of bands

related to PS-PEG linkages and higher Zn content provided evidence for organic
polymerization.

3) Zn/Fe Polymerization: The polymerization of Zn/Fe was represented within the range of
1023–533 cm⁻¹ in the FTIR spectrum. It was concluded that doping PPFe nanocomposites with
ZnO nanoparticles resulted in increased structural and chemical benefits.

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4) Fe-O Bonds and Reactions: Changes in absorption bands indicated the presence of Fe-O-
Fe, Fe-O-Zn, and Fe-O-CH3 bonds, supporting reactions between the PS-PEG matrix and
Fe2O3/Zn/Fe nanoparticles.
5) Sol-Gel/Gel Casting Process: Emphasis was placed on this process as an indication of
condensation reactions occurring between Fe2O3, ZnO, and –OH groups during the process,
showing their interaction before being mixed with the PS-PEG matrix.

Figure.4 FTIR spectra for (a) PPFe, (b) PPFe-3ZnO, and (c) PPFe7ZnO nanocomposites

The examination of magnetic properties revealed a decrease in magnetization in high magnetic

fields. It was observed that this decrease was attributed to the hindrance of interaction between
low concentration magnetic centers, such as Fe3+, by diamagnetic polymers. Additionally, an
increase in iron concentration resulted in the observation of a magnetic hysteresis loop,
indicating an enhanced interaction between magnetic centers.

Figure.5 The magnetic hysteresis loop (M vs. H) of PPFe-(0–7)ZnO nanocomposites at room

temperature
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 ARTICLE.3: Visibly Active FeO/ZnO@PANI Magnetic Nano‑photocatalyst for the
Degradation of 3‑Aminophenol [3]

In this work, a visible light-active photocatalyst based on an assembly of polyaniline (PANI)

and FeO/ZnO magnetic metal oxide (FZ MMO) nanocomposite is synthesized and
characterized. The purpose of the study was to assess FZP's photocatalytic activity in the
presence of light. Furthermore, an investigation was conducted on the role that adsorption plays
in the elimination of 3-aminophenol. The synthesis of FeO/ZnO magnetic metal oxides (FZ
MMO) involved a reduction procedure. For one hour, a round-bottom flask containing a 35
mM ferric chloride solution and a 19 mM zinc nitrate solution were well mixed. After mixing,
sodium borohydride was added gradually and swirled constantly for a further thirty minutes.
The in-situ deposition method was used to synthesize FZP. Using 15 minutes of ultrasonication,
0.500 g FZ MMO was first well distributed in 10 mL of double-distilled water. The FZ MMO
dispersion was then gradually mixed while a 10% aniline and 0.1 M ammonium persulfate
solution, made in 1.0 M HCl, were added dropwise.

RESULTS;

The FTIR study revealed that the effective incorporation of FZ MMO into the polyaniline
matrix was indicated by the typical peaks. Fe-O and Zn-O stretching vibrations showed
characteristic peaks at 665 and 538 cm^-1, respectively. The presence of required units within
FZP is confirmed by the occurrence of discrete peaks at 2θ values in the XRD spectrum. The
spectrum shows peaks connected to PANI's orthorhombic phase, confirming the semi-
crystalline structure of FZP. The hexagonal structure of zinc oxide is validated by peaks that
match to ZnO. Likewise, the detected peaks for FeO attest to its existence. Together, these
results demonstrate the precise synthesis of the composite.

Figure.6 (a) FTIR and (b) XRD spectrum of FZP temperature

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While PANI's scanning electron microscopy (SEM) picture shows a rod-like appearance, the
SEM photos of FZ MMO show a highly agglomerated structure. Both FZ MMO and PANI are
clearly evident in the FZP SEM pictures, suggesting that FZ MMO is a part of the PANI matrix.
TEM pictures show the clumped structure of FZ MMO, indicating that PANI is present and
encasing FZ MMO in the FZP matrix.

Figure.7 SEM image of (a), (b) FZ MMO; (c) PANI and (d)–(f) FZP

Figure.8 TEM images of (a), (b) FZ MMO; (c)–(e) FZP and (f) HRTEM of FZP

FZP has facilitated a high degree of photocatalytic degradation of 3-aminophenol under visible
light (%92, over 120 minutes). The addition of hydrogen peroxide significantly increased the
degradation rate. Optical studies revealed that FZP exhibited a broader visible range absorption
compared to FZ MMO, indicating a lower bandgap energy. Furthermore, the chemical oxygen
demand (COD) analysis indicated a reduction of 21% in the COD value, signifying the
breakdown of 3-aminophenol into simpler compounds.

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 ARTICLE.4: Piezoelectric Properties of Zinc Oxide/Iron Oxide Filled
Polyvinylidene Fluoride Nanocomposite Fibers [4]

The purpose of this article is to investigate the piezoelectric properties of zinc oxide/iron oxide-
filled polyvinylidene fluoride nanocomposite fibers.

ZnO was synthesized using 2 g of zinc acetate dihydrate (Zn(CH3COO)2·2H2O), and FeO was
synthesized using 2 g of iron chloride (FeCl2). During the ZnO synthesis, 0.2 g of FeO
(dissolved in distilled water) was added to create the ZnO/FeO hybrid nanomaterial.
Nanofillers including ZnO, FeO, and FeO/ZnO were added to PVDF at a weight percentage of
1% to generate the polymer nanocomposite. The hybrid FeO/ZnO nanoparticles were dispersed
at a filler concentration of 3% to achieve a higher concentration.

The quantity of PVDF polymer was used to calculate the nanomaterial concentration. In each
instance, bath sonication was used to disperse the nanomaterials in the same DMF/acetone
solvent combination, and overnight magnetic stirring was used to combine them with the
polymer.

RESULTS;

The morphologies of FeO, ZnO, and FeO/ZnO nanoparticles are displayed in SEM and TEM
photographs. It has been established that the hydrothermal reaction influences the structural
characteristics of the FeO/ZnO hybrid material and encourages the production of ZnO in the
floral form. SEM pictures demonstrated that the fiber diameter rose when various nanofillers
were added to the PVDF polymer. SEM pictures do not clearly show the nanoparticles since
they are incorporated inside the polymer chains. EDX spectra confirmed the presence of the
element Zn in the ZnO samples, the element Fe in the FeO samples, and both elements in the
hybrid samples.

Figure.9 EDX spectra of (g) ZnO, (h) FeO and (i) FeO/ZnO nanomaterials

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 Figure.9.1 SEM images of (a) ZnO, (b) FeO and (c) FeO/ZnO; TEM images of (d) ZnO, (e) FeO and (f) FeO/ZnO

PVDF nanocomposites crystalline phases were discovered via FTIR analysis. The inclusion of
metal oxide nanoparticles was shown to boost the b-phase and the crystallinity value.

The PVDF composite fibers semi-crystalline structure and several crystal planes were
identified by XRD analysis. It was found that the b-phase changed and the electroactive phase
grew with the addition of nanoparticles.

Figure.10 FTIR and XRD spectra of PVDF nanocomposite fibers

The thermal behavior of PVDF nanocomposite fibers was examined using TGA and DTG
studies, which showed that they are stable up to 430°C before beginning to degrade. It was
determined that excellent nanoparticle dispersion and polymer chain movement limitation are
responsible for the great heat stability.

The two semiconductor metal oxide nanoparticles formed linked networks because they were
equally aligned along the chains of PVDF polymer. With the addition of nanoparticles and the
increase in concentration, it was found that the mechanical characteristics, such as tensile
strength, Young's modulus, and stiffness, improved.

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 ARTICLE.5: Investigation on the Effect of Gamma-Irradiation on the Dielectric and
Piezoelectric Properties of Stretchable PVDF/Fe–ZnO Nanocomposites for Self-
Powering Devices [5]

The aim of this study is to investigate the properties of polyvinylidene fluoride (PVDF)-based
nanocomposite films. The study aims to prepare nanocomposite films containing nanoparticle
additives (Fe-ZnO) at different ratios and explore their physical, mechanical, thermal, and
electrical properties.

The solution casting method was utilized for the synthesis of polymer nanocomposites. Both
neat PVDF and nanocomposites containing ZnO and ZnO-Fe were produced. Nanomaterials
of 1 wt% undoped ZnO and 0.5 wt% to 2 wt% Fe-doped ZnO were incorporated into the
polymer matrix.

The surface morphology of the produced nanoparticle-incorporated composite materials was

examined using SEM and TEM. Additionally, detailed analyses were performed using XRD,
DSC, and FTIR techniques.

RESULTS;

ZnO nanoparticles doped with the element Fe showed a star-like form when analyzed using a
SEM and TEM. An intermediate complex that was created during the hydrothermal
development using monoethanolamine (MEA) was discovered to have an impact on these
structures, resulting in the production of star-like forms. The Fe–ZnO distribution in PVDF
nanocomposites was shown to be homogenous by SEM and TEM examination. The analysis
of composite morphologies at varying filler concentrations revealed a greater particle presence
at higher filler concentrations, and the surface texture of the composite films was seen to be
impacted by gamma (γ)-irradiation.

The crystalline structure of PVDF was found to be impacted by filler concentration, and the
crystalline phase density was found to be enhanced by the addition of Fe–ZnO, according to
XRD examination of PVDF nanocomposites. Moreover, EDX analysis demonstrated
compositional variations at different filler concentrations and validated the homogenous
distribution of Fe–ZnO inside the PVDF matrix.

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 Figure.11 (a) SEM, (b) TEM, (c) X-ray diffraction patterns of pure ZnO and Fe-doped ZnO and (d)
EDX spectrum of Fe-doped ZnO.

The mechanical resilience of the nanocomposites has been demonstrated to increase with filler
concentration. The homogeneous distribution of Fe–ZnO contributes to the enhancement of the
nanocomposites' mechanical properties. However, excessive filler concentration might reduce
the polymer chain mobility, leading to a decrease in elongation at break. Overall, it has been
concluded that the mechanical properties of nanocomposites are closely related to the amount
and distribution of the filler material, contributing to the improvement of the polymer matrix's
strength by enhancing mechanical durability.

Table.1 Mechanical properties of the nanocomposites

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REFERENCES

[1] J. Typek et al., “Magnetic studies of 0.7(Fe2O3)/0.3(ZnO) nanocomposites in

nanopowder form and dispersed in polymer matrix,” Materials Science- Poland, vol. 34,
no. 2, pp. 286–296, Jun. 2016, doi: 10.1515/msp-2016-0032.

[2] A. B. Abou Hammad, A. M. Mansour, T. M. Elhelali, and A. M. El Nahrawy, “Sol-

Gel/Gel Casting Nanoarchitectonics of Hybrid Fe2O3–ZnO/PS-PEG Nanocomposites
and Their Optomagnetic Properties,” J Inorg Organomet Polym Mater, vol. 33, no. 2,
pp. 544–554, Feb. 2023, doi: 10.1007/s10904-022-02519-2.

[3] S. Sharma et al., “Visibly Active FeO/ZnO@PANI Magnetic Nano-photocatalyst for

the Degradation of 3-Aminophenol,” Top Catal, vol. 63, no. 11–14, pp. 1302–1313, Oct.
2020, doi: 10.1007/s11244-020-01294-z.

[4] A. M. AlAhzm, M. O. Alejli, D. Ponnamma, Y. Elgawady, and M. A. A. Al-Maadeed,

“Piezoelectric properties of zinc oxide/iron oxide filled polyvinylidene fluoride
nanocomposite fibers,” Journal of Materials Science: Materials in Electronics, vol. 32,
no. 11, pp. 14610–14622, Jun. 2021, doi: 10.1007/s10854-021-06020-3.

[5] H. Parangusan, D. Ponnamma, and M. A. A. Almaadeed, “Investigation on the effect of

γ-irradiation on the dielectric and piezoelectric properties of stretchable PVDF/Fe-ZnO
nanocomposites for self-powering devices,” Soft Matter, vol. 14, no. 43, pp. 8803–8813,
2018, doi: 10.1039/c8sm01655k.

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APPENDIX-1: Table of Literature Review Summary

Table 2. Literature Review Summary

Characterization
Date Study Aim Materials Used Conclusion
Method Used
Magnetic studies of
Investigating
0.7(Fe2O3)/0.3(ZnO) FeO and ZnO metal
magnetic *Nanofiller in the polymer sample shifts to lower temperature
2016 nanocomposites in oxides, polymer SEM, TEM, XRD
properties of the first stage of its decomposition.
nanopowder form and matrix
nanocomposites
dispersed in polymer matrix
Sol‑Gel/Gel Casting Investigating
*This study of magnetic Fe2O3 and a wide band gap ZnO in
Nanoarchitectonics of Hybrid optomagnetic Fe2O3-ZnO/PS- XRD, SEM, TEM,
PS-PEG modifies the structural, optical, and magnetic
2022 ­Fe2O3–ZnO/PS‑PEG properties of PEG FTIR, Magnetic
properties of these nanocomposites and will be useful
Nanocomposites and Their hybrid nanocomposites Tests
candidates for various optoelectronic and storage applications.
Optomagnetic Properties nanocomposites
Visibly Active
Producing
FeO/ZnO@PANI Magnetic *Minimized loss in degradation activity was obtained during
visibly active FeO-ZnO/PANI, FTIR, XRD, SEM,
2020 Nano‑photocatalyst for the reusability studies. FZP can provide us deep insight into the
magnetic nano- 3-Aminophenol TEM
Degradation of designing of such materials for water treatment processes.
photocatalyst
3‑Aminophenol
Investigating
Piezoelectric properties of piezoelectric FeO-ZnO metal
SEM, TEM, XRD, *A good correlation between the electroactive phase formation
zinc oxide/iron oxide filled properties of oxides,
2021 EDX, FTIR, TGA, and piezoelectric output voltage generation is observed for the
polyvinylidene fluoride FeO-ZnO filled polyvinylidene
DTG PVDF composite fibers.
nanocomposite fibers polyvinylidene fluoride
fluoride
Effect of γ-
Investigation on the Effect of
irradiation on
γ- irradiation on the Dielectric
the Dielectric SEM, TEM, XRD, * Containing Fe–ZnO nanostars revealed b-crystalline phase
and Piezoelectric Properties of PVDF/ZnO-FeO
2018 and EDX, Mechanical formation and enhanced filler–polymer interfacial interaction,
Stretchable PVDF/Fe-ZnO nanocomposites
Piezoelectric Tests thereby improving the composite performance.
Nanocomposites for Self-
Properties of
Powering Devices
Nanocomposites

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