Effects of composition ratio on structure and phase transition of ferroelectric nanocomposites from silicon dioxide nanoparticles and triglycine sulfate

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Phase Transitions

A Multinational Journal

ISSN: 0141-1594 (Print) 1029-0338 (Online) Journal homepage: https://www.tandfonline.com/loi/gpht20

Effects of composition ratio on structure and

phase transition of ferroelectric nanocomposites from silicon dioxide nanoparticles and triglycine sulfate

Bich Dung Mai, Hoai Thuong Nguyen, Thi Kim Anh Nguyen, Dinh Hien Ta & Thi Nhan Luu

To cite this article: Bich Dung Mai, Hoai Thuong Nguyen, Thi Kim Anh Nguyen, Dinh Hien Ta & Thi Nhan Luu (2019): Effects of composition ratio on structure and phase transition of ferroelectric nanocomposites from silicon dioxide nanoparticles and triglycine sulfate, Phase Transitions, DOI: 10.1080/01411594.2019.1607343

To link to this article: https://doi.org/10.1080/01411594.2019.1607343

Published online: 17 Apr 2019.

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E ffects of composition ratio on structure and phase transition of ferroelectric nanocomposites from silicon dioxide nanoparticles and triglycine sulfate

Bich Dung Maia, Hoai Thuong Nguyen b,c, Thi Kim Anh Nguyena, Dinh Hien Tadand Thi Nhan Luue

a

Institute of Biotechnology and Food Technology, Industrial University of Ho Chi Minh City, Ho Chi Minh City, Vietnam;bDivision of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam;cFaculty of Electrical & Electronics Engineering, Ton Duc Thang University, Ho Chi Minh City, Vietnam;dFaculty of Electrical and Electronics Engineering Technology, Ho Chi Minh City University of Food Industry,

Ho Chi Minh City, Vietnam;eFaculty of Basic Sciences, Hanoi University of Industry, Hanoi, Vietnam

ABSTRACT

The present work is devoted to study on in fluences of silicon dioxide

nanoparticles (SiO2) on structure and phase transition of a classical

ferroelectric of triglycine sulfate (TGS) by synthesizing a composite

containing SiO2and TGS at di fferent composition weight ratios Particle

size analysis, X-ray di ffraction (XRD) and Fourier-transform infrared

spectroscopy (FTIR) techniques were utilized to charaterize the

synthesized composite The experiments for investigation of phase

transition were conducted from 20 to 120°C under a weak electric field

(1 V.cm−1) at 1 kHz The results revealed an expansion of ferroelectric

phase of TGS by 15 –55°C with increasing the SiO 2 content Besides, an

additional phase transition point which is characteristic for the bulk

clusters of TGS was found at low content of SiO2 The detected

anomalies were discussed thoroughly based on the interaction between

components in the composite.

ARTICLE HISTORY

Received 26 January 2019 Accepted 10 April 2019

KEYWORDS

Silicon dioxide; triglycine sulfate; phase transition; ferroelectrics;

nanocomposites

1 Introduction

If silicon is known as a semiconductor at the heart of modern electronics, silicon dioxide (SiO2) takes part in electronics technology in the role of insulating material In the area of nanoelectronics, SiO2is commonly used in the form of nanoparticles, especially, as a reinforcing component for synthesizing advanced materials with several promising properties meeting the strict requirements in manufac-turing industry for more compact, thinner and lighter high-performance appliances Nanocompo-sites are such materials [1–5] In these nanocomposites, SiO2 nanoparticles play the role of not only a reinforcing material, but also an important factor for adjusting composite properties through the interaction of SiO2withfillers owing to its large specific area and hydrophilicity [5]

Triglycine sulfate (TGS) is a classical ferroelectric undergoing the second-order phase transition

at Tc= 49°C with diverse applications including infrared detectors, pyroelectric vidicon tubes and memories [6] However, TGS as well as other classical materials regarding to their primary properties have been becoming gradually less useful to modern demands Recently, the properties of TGS are strongly improved by its combination with other dielectric materials as cellulose [7–11], Al2O3

[12,13] and silicon [12,14] The influences of dielectric materials on TGS inclusion may lead to

CONTACT Hoai Thuong Nguyen nguyenhoaithuong@tdtu.edu.vn

the changes of its phase transition, domain structure, spontaneous polarization, dielectric suscepti-bility and conductivity As a result, the scope of TGS applications has also been expanded Although the composite based on SiO2 and TGS was synthesized already [15], there are some arguments needed to mention here Firstly, the composite was synthesized only at one composition ratio (50 wt%), and therefore the influence of different SiO2/TGS weight ratios– an important factor related to the contribution and isolation offillers – on structure and electrophysical properties of the composite were not reported Secondly, the surface of SiO2 nanoparticles is hydrophilic and may contain hydroxyl groups (−OH) [16] As a result, SiO2 could interact with hydrogen-containing materials as TGS through hydrogen bounds, leading to strongly affecting properties of TGS filler However, the synthesized composite as shown in [15] was not characterized and therefore its struc-tures and feastruc-tures of functional groups could not be clarified In this regard, the present work aims to clarify all these arguments The composite samples in this study were prepared at different compo-sition weight ratios and then carefully characterized by X-ray diffraction (XRD) and Fourier-trans-form infrared spectroscopy (FTIR) techniques The effects of SiO2/TGS weight ratios on XRD pattern, FTIR spectra and phase transition of the composite were investigated thoroughly

2 Sample preparation and experimental methods

The pure TGS powder was reagent-grade, purchased from Merck supplier and utilized in prep-aration process without any further purification Nanoparticles of SiO2was synthesized by sol–gel method in the form of silica hydrosol [17]

The procedure for preparation of the composite is presented inFigure 1 Firstly, SiO2and TGS were mixed together after taking a determined amount from each of saturated TGS solution at 40°C and SiO2at different SiO2to TGS weight ratios Stirring was kept for 3 h at 40°C in a closed bottle, then in open air until a solid mixture was obtained after partial evaporation of water The separated mixture was heated at 120°C for 2 h to removal residual water, cooled down at room temp-erature, crushed in motar to get the mixture well mixed and compressed into tablets of 6 mm in diameter and 1 mm in thickness

The information of crystalline structure and functional groups for SiO2, TGS and SiO2+ TGS composite were tested by using a Rigaku Ultima IV X-ray diffractometer and a Bruker Tensor 37 spectrophotometer (USA), respectively The particle size distribution was determined by a Zetasizer

Figure 1 Scheme for preparation of SiO + TGS composite.

analyzer The phase transition in the composite was measured on a model GW Instek LCR-821 meter at 1 kHz The temperature for all experiments was stabilized with an accuracy of 0.1 K The relative measurement error did not exceed 0.1%

3 Experimental results

Before preparation of the composite, the reagents of pure TGS and SiO2were carefully characterized The size of SiO2nanoparticles was ranged in 20–200 nm with an average size estimated as 60 nm (Figure 2) Besides, XRD patterns for SiO2 (2θ = 23.3°) and pure powder TGS (2θ = 12.3°, 14.1°, 16.14°, 17.3°, 17.6°, 20.2°, 21.2°, 22.38°, 23.42°, 24.68°, 25.56°, 26.7°, 28.34°, 30°, 32.74°, 36.26°, 37.06°) were in good agreement with the JCPDS XRD data (13-0026 and 00-015-0947), respectively (Figure 3) Meanwhile, FTIR spectra for these reagents have also typical shape with characteristic adsorption peaks and bands (Figure 4) For example, a broad band centered at 3478 and a deep peak detected at 1090 cm−1might be referred to -OH stretching vibrations and Si-O-Si asymmetric stretching vibration, respectively [18] In addition, a small peak around 801 cm−1is characteristic for Si-O bending vibration [19] In the case of pure powder of TGS (Figure 4), a broad band detected in the range of 3300–2800 cm−1 corresponds to the asymmetric and symmetric N-H (NH3), C–H (CH2) and O-H (COOH) stretching [20] Besides, the two small adsorption peaks at 1706 and

1621 cm−1could refer to the stretching of C=O bonds and symmetric stretching modes of COOˉ groups, respectively In addition, several peaks observed from 1128 to 909 cm−1can be assigned for SO24− of sulfate groups Based on the obtained characterization results, the staring materials of SiO2and TGS were ready for preparation of the composite

For SiO2+ TGS composite, XRD patterns (Figure 3) and FTIR (Figure 4) spectra at different SiO2: TGS weight ratios contained most of characteristic peaks and bands of composite components How-ever, several anomalies were detected In XRD patterns, the intensity of typical peaks for SiO2

decreased with decreasing its content in the composite while for TGS – increased, even though the position of peaks did not move In FTIR patterns, a main anomaly is related to the expansion

of the broad band 3800–2700 cm−1with increasing the SiO2content It is obviously caused by the presence of water molecules in the composite As reported in literature [21], there are four types

of water-related chemical groups includingα, β, γ1andγ2occurred SiO2 An annealing temperature

of 120°C could removeα-type from the composite and therefore water behavior was detected in the FTIR pattern As known [22–24] that the change in the number and strength of hydrogen bonds brings the change in intensity and the width of the related bands As a result, it is worth to assume

Figure 2 Size distribution of SiO nanoparticles used for preparation of SiO + TGS composite.

that the expansion of this adsorption band is mainly due to the increase in number of hydrogen bonds in the composite Along with this anomaly, overlapping and disappearance of peaks were also detected Indeed, the small peaks at 1740, 1706 and 1621 cm−1of TGS were transformed into one peak at 1713 cm−1in the composite In addition, the overlapping was also observed for peaks

at 615 and 573 cm−1 into 636 cm−1 Besides, the peak at 1128 cm−1 of TGS disappeared in the FTIR pattern of the composite, probably, due to the dominance of the peak at 1090 cm−1 character-istic for SiO2(Figure 4)

Temperature dependences of dielectric constantɛ′(T ) and dielectric loss tgδ(T ) for the SiO2+ TGS composite at different SiO2:TGS weight ratios and for pure SiO2 are shown inFigure 5 The results indicated the presence of two maxima inɛ′ (T ) for samples with SiO2:TGS weight ratios

of 0.2:1 and 0.5:1, i.e with TGS content higher than those of SiO2 in the composite (Figure 5(a)) The lower-temperature maxima were observed at 49°C coinciding with the Curie point of bulk TGS while the higher-temperature ones– at 64°C and 71°C corresponding to SiO2:TGS weight ratios

of 0.2:1 and 0.5:1, respectively (Table 1) In other words, the higher-temperature maxima ofɛ′(T ) were shifted towards higher temperatures as compared to those of Curie point in the bulk of TGS In addition, at other composition weight ratios with decreasing the TGS content, the lower-temperature

Figure 3 XRD patterns for TGS, SiO 2 and for SiO 2 + TGS composite at di fferent composition weight ratios.

peaks at 49°C disappeared (Figure 5(a)) At the same time, the higher the SiO2 content was, the stronger the shift of higher-temperature maxima (Table 1) and the lower the values of dielectric con-stant at maxima were observed (Figure 5(a)) As reported in previous studies [15,25] using SiO2

Figure 4 FTIR spectra for TGS, SiO 2 and for SiO 2 + TGS composite at di fferent composition weight ratios.

Figure 5 Temperature dependences of dielectric constant (a, c) and dielectric loss tangent (b, d) for SiO 2 + TGS composite at di ffer-ent composition weight ratios.

hydrosol to prepare SiO2-TGS composite, there was only one peak inɛ′(T ) observed during anneal-ing process without the peak characteristic for bulk TGS The reason was due to that the authors synthesized samples with 55 mol% SiO2only, and therefore the whole picture of composition weight influence on composite properties was not explored [15,25]

In order to confirm that the peaks detected above in ɛ′(T ) correspond to phase transition temp-eratures of TGS crystals in the composite, the behavior of temperature dependences of polarization P (T) was also investigated Based on the results shown inFigure 6, all curves of P(T) for the composite

at different composition weight ratios have similar shape that the polarization slowly decreases with increasing temperature until reaching minimum values, which remain unchanged with further increase in temperature Besides, the temperatures at these minimum values coincide with those

in higher temperature column listed inTable 1 In the term of ferroelectrics, their polarization should equal to zero at phase transition temperature as shown for pure TGS (inset inFigure 6) In our case, the values of polarization were different from zero, probably, due to the residual polarization of SiO2

in the composite (Figure 6) In this regard, the temperatures detected inɛ′(T ) are really character-istic for phase transition points of TGS crystals in the composite The nature of phase transition shift and the presence of lower temperature peaks ofɛ′(T ) will be discussed thoroughly in the present work

4 Discussion

The shift of phase transition point in TGS crystals mixed with SiO2nanoparticles as reported in sev-eral studies with other dielectric components as cellulose, Al2O3, glasses, etc [7–14] is related to a good maintenance of polarization of TGS inclusion This could take place if there was a strong inter-action between ferroelectric and dielectric component In our case, based on the characterization results, the water molecules remained in the composite structure and therefore TGS and SiO2

Table 1 Phase transition temperatures of SiO 2 + TGS composite at di fferent composition weight ratios.

Figure 6 Temperature dependences of polarization for SiO 2 + TGS composite at di fferent composition weight ratios The inset is for pure TGS.

particles might be connected to each other through hydrogen bonds With increasing SiO2content, the higher amount of water molecules could get stuck inside while TGS particles became more iso-lated, leading to stronger interaction between SiO2and TGS, resulting in the stronger shift of phase transition toward higher temperatures

Although the dielectric/ferroelectric interaction plays an important role, the influence of ferro-electric/ferroelectric interaction on phase transition in the composite through dipole–dipole mech-anism cannot be neglected Indeed, based on the Landau-Ginzburg-Devonshire theory [26], the phase transition temperature Toof a heterogeneous system from bounded particles can be deter-mined by the following formula:

To= Tc−a1

o

where Tois Curie point of the bulk of ferroelectric particles,αois a positive constant,piis intrinsic dipole moment of a ferroelectric particle,Eiis an effective field acting on ith dipole from nearest neighbors and the term ofp

iEi is the energy of dipole–dipole interaction It is obviously seen

in formula (1) that if the energy of dipole–dipole interaction is negative, i.e the dipoles in TGS par-ticles were oriented by the way so that theirfields can be compensated by each other, the phase tran-sition temperature increases In the case for SiO2+ TGS at high concentration of TGS, the dipole– dipole interaction can be neglected due to the formation of large-size TGS clusters However, at high content of TGS, TGS particles with smaller size could be formed and they were well isolated by SiO2

As a result, the dipole–dipole interaction became stronger, pulling the phase transition phase toward higher temperatures

Finally, the presence of lower-temperature peaks at 49 °C is obviously the bulk of TGS occurred in the composite at high content of TGS

5 Conclusions

The composite from silicon dioxide nanoparticles and triglycine sulfate was successfully synthesized

at different composition weight ratios The increase in SiO2content led to several anomalies detected

in the composite as the expansion of FTIR wavenumber of 3800–2700 cm−1, the shift of phase tran-sition point toward higher temperatures and the disappearance of additional phase trantran-sition characteristic for bulk TGS Thefirst anomaly is explained by presence of residual water in the com-posite, while the shift of phase transition was due to the interaction between SiO2and TGS through hydrogen bonds and between TGS particles through dipole–dipole mechanism Finally, the presence

of additional phase transition can be referred to the formation of bulk TGS in the composite Overall, the adjustment of SiO2 content can expand the ferroelectric phase of TGS and it is valuable to improve operating parameters of electronics devices

Disclosure statement

No potential con flict of interest was reported by the authors.

ORCID

Hoai Thuong Nguyen http://orcid.org/0000-0003-1290-5221

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