Effects of Moisture on Structure and Electrophysical Properties of a Ferroelectric Composite from Nanoparticles of Cellulose and Triglycine Sulfate CONDENSED MATTER Effects of Moisture on Structure an[.]
Brazilian Journal of Physics (2019) 49:333–340 https://doi.org/10.1007/s13538-019-00658-5 CONDENSED MATTER Effects of Moisture on Structure and Electrophysical Properties of a Ferroelectric Composite from Nanoparticles of Cellulose and Triglycine Sulfate Bich Dung Mai & Hoai Thuong Nguyen 2,3 & Dinh Hien Ta Received: November 2018 / Published online: April 2019 # Sociedade Brasileira de Física 2019 Abstract In this study, a novel ferroelectric composite consisting of triglycine sulfate and cellulose nanoparticles at different weight composition ratios was successfully synthesized A comparative study on structure and electrophysical properties for dried and wet composite samples was carried out The measurements of electrophysical parameters were performed from 10 to 120 °C under a weak electric field with an amplitude of V cm−1 at low and infra-low frequencies (10−3–103 Hz) under different relative humidities of 0, 30, 60, 80, and 100% The characterization results showed a significant impact of moisture on crystallinity and features of functional groups in the composite Besides, phase transition temperature of the composite increased by to 63 °C higher than those for single crystal of triglycine sulfate (+ 49 °C) in dependence on cellulose content in the composite Along with a significant increase in dielectric constant, dielectric loss, and dielectric dispersion in the composite due to high conductivity caused by moisture, the water molecules on sample surface led to the appearance of addition peaks in temperature dependences of dielectric constant and dielectric loss tangent in the initial stage of heating All the anomalies can be explained by the strong interaction through hydrogen bonds between triglycine sulfate and cellulose components as well as between these components and water molecules in the composite Keywords Nanocomposites Ferroelectrics Humidity Phase transition Cellulose Introduction Recently, one of the most urgent global issues is related to the ever-growing amount of electronic waste (e-waste) discharged from out-of-order electronics devices with about 50 million tons forecasted to reach by 2018 [1, 2], causing serious problems for ecosystems and human health The reason is * Hoai Thuong Nguyen nguyenhoaithuong@tdtu.edu.vn Institute of Biotechnology and Food Technology, Industrial University of Ho Chi Minh City, Ho Chi Minh City, Vietnam Division of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam Faculty of Electrical & Electronics Engineering, Ton Duc Thang University, Ho Chi Minh City, Vietnam Faculty of Electrical and Electronics Engineering Technology, Ho Chi Minh City University of Food Industry, Ho Chi Minh City, Vietnam associated with the fact that most of materials used to manufacture electronics systems are originated from inorganic substances, which are toxic to environment after service life In the context, the inspiration from nature has encouraged researchers to create biodegradable forms called as Bgreen electronics^; for that, natural abundant materials are preferred to be used In this regard, cellulose with low cost, light weight, high electrical stability, and biodegradability is considered as a promising candidate [3, 4] With these advantages, cellulose can be a perfect substrate for preparing transistors [3, 5] and OLEDs [6], an ideal support material for photovoltaic cells [7] and the main material for processing of highly flexible, sustainable optoelectronic devices [2] However, to achieve the stable and optimal performance of cellulose in electronics devices, it is needed to overcome several shortcomings caused by its high adsorption capacity towards moisture In this regard, understanding of effects of humidity on electrophysical properties of materials is extremely important for preparation of cellulose-containing electrical and electronic equipment Among advanced electrical and electronics materials, ferroelectric nanocomposites are promising for manufacturing 334 Braz J Phys (2019) 49:333–340 modern electronics devices with several beneficial properties thanks to the size effects of ferroelectric fillers at nanoscale level [8, 9] In the role of nanosized ferroelectric fillers, t ri g l y c in e s u lf a te ( T G S ) w i t h c h e m i c a l f o r m u l a (NH2CH2COOH)3·(H2SO4) is one of the most popular materials and has been used to synthesize state-of-the-art ferroelectric nanocomposites [4, 10–12] because of its valuable ferroelectric properties and high wettability Because TGS is a hydrogen-containing ferroelectric, the presence of moisture may lead to the appearance of several effects such as the change of pyroelectric coefficients and coercive fields, the higher sensitivity of dielectric relaxation towards frequencies of measuring external fields, and the significant increase of dielectric permittivity and conductivity [13, 14] The influence of humidity on properties of nanocomposites from porous cellulose and triglycine sulfate was already investigated [15] However, a huge drawback of porous nanocomposite is related to difficulties in controlling the amount of inclusions embedded into nanopores Besides, in the study [15], the impact of moisture on structure of cellulose-containing composite was not reported yet In this regard, the present study is devoted to clarifying the effects of moisture on structure and electrophysical properties of a novel composite prepared from cellulose nanoparticles (CNP) and TGS The composite was prepared by precisely controlling the composition weight of CNP and TGS Then, various techniques as particle size analysis, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) were utilized to investigate the change of composite structure under different relative humidities The electrophysical properties of the composite were tested under a weak electric field in temperature range of 10–120 °C at low and infralow frequencies (10−3–103 Hz) mortar to get the mixture well mixed The obtained mixture was compressed into tablets of mm in diameter and mm thick under a pressure of 20 MPa For testing the influence of humidity on electrophysical properties of the composite, the synthesized samples were divided into groups and stored in different containers under different relative humidity (RH) of 0, 30, 60, 80, and 100% for 24 h at room temperature For dielectric measurements, silver leaf electrodes were applied on the prepared samples using a conductive glue The size of nanoparticles and their morphology were examined by a Zetasizer analyzer with a detection range of 0.3 nm–10 μm and a FE-SEM S4800 HITACHI scanning electron microscope with an accelerating voltage of 10.0 kV, respectively The structure of dried and wet samples was tested using a Rigaku Ultima IV X-ray diffractometer (Japan) using Cu Kα radiation (λ = 1.5406 Å) at a voltage of 40 kV and current of 30 mA in the scanning range 2θ of 5–70° with a step size of 0.02° The information of functional groups in the synthesized samples were analyzed by Fourier transform infrared spectroscopy on a Bruker Tensor 37 spectrophotometer (USA) at a scanning range over 400–4000 cm−1 with resolution of cm−1 The phase transition and dielectric relaxation of the composite were measured by a model GW Instek LCR821 meter at kHz and by Solartron 1260 impedance analyzer connected to an expanded model of Solartron 1296 dielectric interface at frequencies from mHz to kHz, respectively The study on electrophysical properties was conducted under a weak electric field with an amplitude of V cm−1 Samples and Experiments The characterization results for size distribution and morphology of cellulose particles are presented in Fig We can see that the size of cellulose particles was formed in near-spherical shape with size ranged in 40–80 nm The similar results were reported in several studies [17, 18] The XRD patterns and FTIR spectra for pure TGS, dried CNP, and composite samples of 0.5 CNP + 0.5 TGS stored at different RH of 0, 30, 60, 80, and 100% are shown in Figs and 4, respectively It is seen in Fig that the detected peaks for pure TGS were in good agreement with the ICPDS XRD data (00-015-0947), while for dried samples of CNP, three strong peaks of Iβ crystalline phase at 14.7° (101), 16.3° 101 , and 22.5° (002) were clearly revealed [19–21], indicating the formation of crystalline structure in cellulose Correspondingly, several characteristic adsorption peaks in FTIR spectra for dried CNP and pure TGS were also observed For examples, for TGS, a broad band detected in the range of 3300–2800 cm−1 corresponds to the asymmetric and Triglycine sulfate used to prepare composite samples was purchased from Merck supplier in the form of reagent-grade chemicals that can be utilized for preparation process without further purification Nanoparticles of cellulose were obtained from waste cotton using the method of enzymatic hydrolysis, sonification treatment, and free drying according to procedures described in [16] The scheme for preparation of the composite from CNP and TGS is shown in Fig Firstly, a determined amount taken from each of TGS powder and CNP was mixed using a magnetic stirrer in distilled water at 40 °C The weight of CNP and TGS was chosen at different composition weight ratios of xCNP + (1 − x)TGS with x changed from 0.2 to The stirring was kept for h at 40 °C in a sealed container and then in open air to obtain a solid mixture, which was separated, heated at 120 °C for h to remove residual water, cooled down at room temperature, and crushed in Experimental Results and Discussion 3.1 Materials Characterization and Influence of Water Braz J Phys (2019) 49:333–340 335 Fig Scheme for preparation of xCNP + (1 − x)TGS composite symmetric N–H (NH3), C–H (CH2), and O–H (COOH) stretching [22] Besides, the two small adsorption peaks at 1706 and 1621 cm−1 could 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−1 can be assigned for SO42− of sulfate groups In the case of dried CNP samples, a broad band centered at 3273 cm−1 is related to O–H stretching and the flexural vibration of intra- and intermolecular hydrogen bonds of cellulose [23] Besides, two peaks detected at 2900 and 2840 cm−1 are originated from CH2 asymmetric vibrations, while the peaks at 1433 and 1378 cm−1 are related to the OCH in-plane and CH deformation vibrations, respectively [16, 24] Additionally, the strong peaks observed at 1635 and 707 cm−1 correspond to OH stretching and OH out of plane bending [17, 25] Finally, the amorphous region which always exists in any cellulose structures was also detected at 899 cm−1, corresponding to the COC, CCO, and CCH deformation modes as well as stretching vibrations of the C5 and C6 atoms [16] The above obtained results indicated that the reagents for preparation of the composite are adequate Before analyzing the influence of moisture on structure of the synthesized composite, it is needed to characterize the obtained composite samples in dry form to confirm the successful synthesis For dried composite samples after heat treatment, their XRD pattern (Fig 3) and FTIR spectrum (Fig 4) contain almost all characteristic peaks for CNP and TGS components as described above However, several anomalies were detected For examples, the intensity of XRD peaks at 14.7° (101), 16.3° 101 , and 22.5° (002) characteristic for cellulose was lower than those for CNP without TGS, i.e., the crystallinity of cellulose decreased after becoming a component of the composite The similar phenomenon was also reported for the composite from porous nanocellulose and TGS [4] In Fig Particle size distribution (a) and SEM image (b) for cellulose suspension 336 Braz J Phys (2019) 49:333–340 Fig FTIR spectra for dried samples of TGS and cellulose nanoparticles and for composite 0.5 CNP + 0.5 TGS under different conditions of relative humidity Fig XRD patterns for dried samples of TGS and cellulose nanoparticles and for composite 0.5 CNP + 0.5 TGS under different conditions of relative humidity addition, in FTIR pattern, the broad band at wavelength higher than 2800 cm−1 is broadened as compared to those of TGS and CNP The reason for that might be related to the strong adsorption of functional groups characteristic for both TGS (the asymmetric and symmetric NH3, CH2, COOH stretching) and CNP (O–H stretching and hydrogen bonds) as mentioned above Moreover, the combination of TGS and CNP could lead to the formation of new hydrogen bonds in the composite due to the presence of OHˉ hydroxyl groups in cellulose and TGS As known [16, 24, 26] 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 that the expansion of this adsorption band is mainly due to the increase in number of hydrogen bonds in the composite Along with the expansion of the mentioned band, a slight deviation of peak position for the composite from that of its components and overlapping of peaks were also detected For instance, the peaks at 1433, 1164, and 707 cm−1 in FTIR spectrum of CNP were shifted to 1424, 1164, and 708 in the dried composite, or the strong peak at 1631 cm−1 is a result of overlapping the two peaks at 1621 and 1706 cm−1 of TGS and 1635 cm−1 of CNP Overall, the obtained results suggested that the mixed composite consisting of cellulose nanoparticles and triglycine sulfate was successfully synthesized The presence of moisture in the synthesized composite led to the appearance of several anomalies in XRD patterns (Fig 3) and FTIR spectra (Fig 4) Firstly, the intensity of charac teristic peaks for cellulose at 14.7° (101), 16.3° 101 , and 22.5° (002) for the composite increased with increasing RH, while the intensity of peaks for TGS component almost Braz J Phys (2019) 49:333–340 remained unchanged and the shift of position of XRD peaks for CNP as well as TGS was not detected (Fig 3) Secondly, the adsorption peaks at 1631 and 1151 cm−1 corresponding to OH stretching of cellulose and SO42− of sulfate groups of TGS were shifted to lower wavelengths with increasing RH At the same time, the adsorption intensity of these peaks increased In addition, the broad band of 2700–3800 cm−1 centered at 3340 cm−1 and small peaks at 1547 and 707 cm−1 became deeper under the influence of moisture All the obtained changes are obviously related to the interaction between functional groups of the composite and adsorbed water molecules 3.2 Electrophysical Properties and Influence of Moisture The results for investigation of phase transition in xCNP + (1 − x)TGS composite in dry form and at different composition weight ratios with x varied from 0.2 to are presented in Fig 5a, b Herein, the temperature dependences of dielectric constant ɛ′(T) and dielectric loss tangent tgδ(T) were measured at kHz According to the results for all composition weight ratios, the phase transition peaks were strongly Fig Temperature dependences of dielectric constant (a, c) and dielectric loss tangent (b, d) for dried (a, b) and wet (RH = 80%) (c, d) samples of the composite at different composition weight ratios at kHz 337 smeared as always found in most of ferroelectric composites [4, 10, 27–30], and the phase transition point was shifted to the region of higher temperatures as compared to those of single crystal TGS (+ 49 °C) Furthermore, the rise in the content of cellulose in the composite led to increasing of phase transition temperatures (Table 1), while reducing the maximum of dielectric constant In addition, for samples with ratios higher than 70% (x < 0.7) of TGS mass content (curves 1, in Fig 5a), there was an additional peak observed at higher temperatures as compared to those for the lower-temperature one This anomaly was probably associated with the structural changes of TGS nanocrystals in the composite [31] This was also observed for the mixed composite of SiO2 and TGS [10] It should be noted that in the case of matrix composite prepared from TGS embedded into nanochannels of porous cellulose [4], there was only one phase transition point detected under the same heating process and applied electric field In the case of CNP without TGS (x = 1), the values of dielectric constant are quite small (less than 10) in the entire temperature range (Fig 5a) The temperature dependences of tgδ(T) have a similar shape as for ɛ′(T) with the values of dielectric loss tangent not higher than 0.5 (Fig 5b) The inset shows the change of dielectric constant and dielectric loss tangent at the initial stage of heating 338 Braz J Phys (2019) 49:333–340 Table The increase in values of phase transition temperature in composite samples at different composition weight ratios as compared to those of TGS single crystals regions were observed in the plots and expanded with increasing RH, indicating the presence of static conductivity at infralow frequencies xCNP + (1 − x)TGS x 0.2 0.3 ΔT (°C) 0.5 34 0.7 53 0.9 63 – ΔT = To − Tc, To—phase transition temperature of composite, Tc = + 49 °C—the Curie point of TGS single crystals After storing the composite samples under RH = 80% for 24 h, both dielectric constant and dielectric loss tangent significantly increased and the transition peaks became more smeared as compared to that of dried ones (Fig 5c, d) Even so, the shift of phase transition in the composite at all composition weight ratios was not detected However, the second peaks of ɛ′(T) around 100–110 °C for samples containing TGS content higher than 70% as mentioned above disappeared Instead, there was only a rising tendency detected for dielectric constant with increasing temperature in this temperature range Besides, in the initial stage of heating process for wet composite samples, an addition peak in ɛ′(T) and tgδ(T) appeared in the range of 10–20 °C (insets in Fig 5c, d) It should be noticed that these peaks can be removed by heat treatment This anomaly has been reported in previous studies for various ferroelectric composites from TGS [14, 15] The similar character of ɛ′(T) and tgδ(T) for the composite was also observed under other RH To clarify the effects of humidity on dielectric relaxation for the synthesized composite, frequency dependences of the real ɛ′( f ) and imaginary ɛ″( f ) parts of the complex dielectric permittivity ɛ*( f ) = ɛ′( f ) + i ɛ″( f ) under different RHs of (dried samples), 30, 60, 80, and 100% at low and infralow frequencies of 10−3–103 Hz at room temperature were investigated The samples of 0.5 CNP + 0.5 TGS were chosen for these experiments The results are shown in Fig 6a, b It is seen in Fig 6a, b that the higher the moisture content is, the higher the values of ɛ′ and ɛ″ are Moreover, the dependences of ɛ′ and ɛ″ on frequency obey the universal power-law of dielectric relaxation (ɛ′, ɛ″ ~ f −n), where n varied between to [32, 33] In our case, the values of n tend to increase from 0.51 to 0.92 with increasing RH from to 100% It can be considered as an evidence of increased conductivity in the wet composite samples Indeed, the AC conductivity can be calculated by the following formula: AC ẳ 2f 1ị where felectric field frequency, ɛo—vacuum dielectric constant, and ɛ″—the imaginary part of complex dielectric permittivity The obtained results are shown in Fig 6c As seen, the values of conductivity increase drastically with increasing frequency at low RH of and 30% At higher RH, plateau 3.3 Discussion The anomalies of characterization results could be explained as follows Firstly, the increase in crystallinity level of cellulose component in the wet composite can be referred to the fact that the presence of moisture helps to recover partial collapse of cellulose structure in dry samples [34] It means that the dehydration process for cellulose can lead to partially decrystallizing cellulose structure and increasing strains as well as twist deformation [34] Besides, the water molecules introduced into the composite samples as analyzed above can interact with functional groups through hydrogen bonds, resulting in changes of adsorption intensity and the shift of adsorption peaks The shift of phase transition point in the synthesized composite towards higher temperatures as compared to those of single crystals TGS can be explained by the fixation of polarization in TGS inclusion due to the strong interaction between TGS and cellulose nanoparticles through hydrogen bonds The interaction could become more stronger with increasing the cellulose content in the composite because of more effective isolation of TGS particles surrounded by cellulose In addition to that when TGS particles were isolated by cellulose, they could interact with each other through dipole–dipole mechanism Based on the Landau–Ginzburg–Devonshire theory [34], the phase transition temperature To of a heterogeneous system from bounded particles can be determined by the following formula: T o ¼ T c− !* ! ∑ p E* αo i i i ð2Þ where To is Curie point of the bulk of ferroelectric particles, αo ! is a positive constant, p*i is intrinsic dipole moment of a fer! roelectric particle, E*i is an effective field acting on ith dipole !! from nearest neighbors, and the term of ∑ p*i E *i is the energy i of dipole–dipole interaction It is obviously seen in formula (2) that if the energy of dipole–dipole interaction is negative, i.e., the dipoles in TGS particles were oriented by the way so that their fields can be compensated by each other, the phase transition temperature increases Thus, it allows us to assume that the dipole–dipole interaction could be another reason and contribute to the above shift of phase transition point in the composite The presence of additional peaks in ɛ′(T) and tgδ(T) around 10–20 °C in the initial stage of heating process for the wet composite samples could be related to the evaporation of Braz J Phys (2019) 49:333–340 339 Fig Frequency dependences of real (a) and imaginary (b) parts of dielectric permittivity and of conductivity (c) for 0.5 CNP + 0.5 TGS composite under different conditions of relative humidity in the range of 10−3–103 Hz at room temperature water molecules from the sample surface, on which water molecules were loosely connected to the sample and therefore easily to be thrown out The similar behavior has been reported in previous studies for the composites based on triglycine sulfate [14, 15] The strong dielectric dispersion in the composite at 10−3– 10 Hz under influence of moisture was obviously associated with the presence of conductivity according to the Maxwell– Wagner–Sillars interfacial polarization mechanism This behavior was also observed in matrix composite from porous nanocellulose and TGS [33] Conclusion The obtained results confirmed the successful synthesis of the composite consisting of triglycine sulfate and nanocellulose particles with transition temperatures higher than those for single crystals TGS by to 63 °C depending on the cellulose content in the composite The increase in phase transition is explained by the fixation of polarization in TGS crystals due to strong interaction between TGS and cellulose nanoparticles through hydrogen bonds Besides, the phase transition temperature could be increased by increasing cellulose content due to effectively isolating TGS particles covered by cellulose In this case, the dipole–dipole interactions between TGS particles cannot be negligible The presence of moisture strongly affected the structure of composite as the change of crystallinity level of cellulose component and the change of intensity or adsorption position for several functional groups In addition to that, a significant increase in dielectric constant, dielectric loss, and dielectric dispersion in the composite was detected because of high conductivity Interestingly, the water molecules on sample surface led to the appearance of addition peaks in temperature dependences of dielectric constant and dielectric loss tangent The low and infra-low dispersion of dielectric permittivity was governed by Maxwell–Wagner– Sillars interfacial mechanism Overall, the obtained results could be useful in controlling dielectric properties of ferroelectric materials for practical applications 340 Braz J Phys (2019) 49:333–340 References 10 11 12 13 14 15 16 17 C.P Baldé, F Wang, R Kuehr, J Huisman, The Global E-Waste Monitor – 2014, (United Nations University, IAS – SCYCLE, Bonn, Germany, 2015) I.-V Mihai, E.D Glowacki, N.S Sariciftci, S Bauer, Green Materials for Electronics, (Wiley-VCH Verlag GmbH & Co KGaA, 2018) Print ISBN:9783527338658 |Online ISBN: 9783527692958 |https://doi.org/10.1002/9783527692958, https:// onlinelibrary.wiley.com/doi/book/10.1002/9783527692958 B Peng, P.K.L Chan, Flexible organic transistors on standard printing paper and memory properties induced by floated gate electrode Org Electron 15, 203–210 (2014) https://doi.org/10.1016/j.orgel 2013.11.006 N.H Thu’o’ng, A.S Sidorkin, S.D Milovidova, Dispersion of dielectric permittivity in a nanocrystalline cellulose–triglycine sulfate composite at low and ultralow frequencies Phys Solid State 60, 559–565 (2018) https://doi.org/10.1134/S1063783418030320 S Thiemann, S.J Sachnov, F Pettersson, R Bollstrưm, R Ưsterbacka, P Wasserscheid, J Zaumseil, Cellulose-based ionogels for paper electronics Adv Funct Mater 24, 625–634 (2014) https://doi.org/10.1002/adfm.201302026 E.F Gomez, A.J Steckl, Improved performance of OLEDs on cellulose/epoxy substrate using adenine as a hole injection layer ACS Photonics 2, 439–445 (2015) https://doi.org/10.1021/ ph500481c M.C Barr, J.A Rowehl, R.R Lunt, J Xu, A Wang, C.M Boyce, S.G Im, V Bulović, K.K Gleason, Paper Adv Mater 23, 3500– 3505 (2011) https://doi.org/10.1002/adma.201101263 S Li, J.A Eastman, Z Li, C.M Foster, R.E Newnham, Size effects in nanostructured ferroelectrics Phys Let A 212, 341–346 (1996) https://doi.org/10.1016/0375-9601(96)00077-1 M.F Vladimir, Phys.-Usp 49, 193 (2006) https://doi.org/10.1070/ PU2006v049n02ABEH005840 S.D Milovidova, A.S Sidorkin, O.V Rogazinskaya, E.V Vorotnikov, Dielectric properties of the mixed nanocomposites: triglycine sulfate - silica Ferroelectrics 497, 69–73 (2016) https://doi.org/10.1080/00150193.2016.1162620 Y Yang, H.L.W Chan, C.L Choy, Properties of triglycine sulfate/ poly(vinylidene fluoride-trifluoroethylene) 0–3 composites Frontiers of Ferroelectricity ((Springer, Boston, 2006) A Plyushch, J Macutkevic, V Samulionis, J Banys, D Bychanok, P Kuzhir, S Mathieu, V Fierro, A Celzard, Polym Compos (2018) https://doi.org/10.1002/pc.24932 V.E Khutorsky, S.B Lang, Very strong influence of moisture on pyroelectric and dielectric properties of triglycine sulfate-gelatin films J Appl Phys 82, 1288–1292 (1997) https://doi.org/10 1063/1.365900 O.M Golitsyna, S.N Drozhdin, A.E Gridnev, Influence of the humidity on dielectric characteristics of porous aluminum oxide with inclusions of triglycine sulfate Phys Solid State 54, 1961– 1965 (2012) https://doi.org/10.1134/S1063783412100149 H.T Nguyen, A.S Sidorkin, S.D Milovidova, O.V Rogazinskaya, Influence of humidity on dielectric properties of nanocrystalline cellulose – triglycine sulfate composites Ferroelectrics 501, 180– 186 (2016) https://doi.org/10.1080/00150193.2016.1204866 T Fattahi Meyabadi, F Dadashian, G Mir Mohamad Sadeghi, H Ebrahimi Zanjani Asl, Spherical cellulose nanoparticles preparation from waste cotton using a green method Powder Technol 261, 232–240 (2014) https://doi.org/10.1016/j.powtec.2014.04.039 P Lu, Y.-L Hsieh, Preparation and properties of cellulose nanocrystals: rods, spheres, and network Carbohydr Polym 82, 329–336 (2010) https://doi.org/10.1016/j.carbpol.2010.04.073 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 J Zhang, T.J Elder, Y Pu, A.J Ragauskas, Facile synthesis of spherical cellulose nanoparticles Carbohydr Polym 69, 607–611 (2007) https://doi.org/10.1016/j.carbpol.2007.01.019 P.B Filson, B.E Dawson-Andoh, D Schwegler-Berry, Enzymaticmediated production of cellulose nanocrystals from recycled pulp Green Chem 11, 1808 (2009) https://doi.org/10.1039/B915746H S.-S Wong, S Kasapis, Y.M Tan, Bacterial and plant cellulose modification using ultrasound irradiation Carbohydr Polym 77, 280–287 (2009) https://doi.org/10.1016/j.carbpol.2008.12.038 P Satyamurthy, P Jain, R.H Balasubramanya, N Vigneshwaran, Preparation and characterization of cellulose nanowhiskers from cotton fibres by controlled microbial hydrolysis Carbohydr Polym 83, 122–129 (2011) https://doi.org/10.1016/j.carbpol 2010.07.029 N Sinha, S Bhandari, H Yadav, G Ray, S Godara, N Tyagi, J Dalal, S Kumar, B Kumar, Performance of crystal violet doped triglycine sulfate single crystals for optical and communication applications Cryst Eng Comm 17, 5757–5767 (2015) https://doi org/10.1039/C5CE00703H Y Cao, H Tan, Structural characterization of cellulose with enzymatic treatment J Mol Struct 705, 189–193 (2004) https://doi org/10.1016/j.molstruc.2004.07.010 S.Y Oh, D.I Yoo, Y Shin, G Seo, FTIR analysis of cellulose treated with sodium hydroxide and carbon dioxide Carbohydr Res 340, 417–428 (2005) https://doi.org/10.1016/j.carres.2004 11.027 L Wang, Y Zhang, P Gao, D Shi, H Liu, H Gao, Changes in the structural properties and rate of hydrolysis of cotton fibers during extended enzymatic hydrolysis Biotechnol Bioeng 93, 443–456 (2006) https://doi.org/10.1002/bit.20730 H Zhao, J.H Kwak, Z.C Zhang, H.M Brown, B.W Arey, J.E Holladay, Studying cellulose fiber structure by SEM, XRD, NMR and acid hydrolysis Carbohydr Polym 68, 235–241 (2007) https://doi.org/10.1016/j.carbpol.2006.12.013 S.V Baryshnikov, A.Y Milinskiy, E.V Charnaya, A.S Bugaev, M.I Samoylovich, Dielectric studies of ferroelectric NH4HSO4 nanoparticles embedded into porous matrices Ferroelectrics 493, 85–92 (2016) https://doi.org/10.1080/00150193.2016.1134174 S.D Milovidova, O.V Rogazinskaya, A.S Sidorkin, H.T Nguyen, E.V Grohotova, N.G Popravko, Dielectric properties of composites based on nanocrystalline cellulose with triglycine sulfate Ferroelectcrics 469, 116–506 (2014) https://doi.org/10.1134/ S1063783415030178 A.Y Milinskii, S.V Baryshnikov, H.T Nguyen, Dielectric properties of nanocomposites based on potassium iodate with porous nanocrystalline cellulose Ferroelectrics 524, 181–188 (2018) https://doi.org/10.1080/00150193.2018.1432830 H.T Nguyen, A.S Sidorkin, S.D Milovidova, O.V Rogazinskaya, Investigation of dielectric relaxation in ferroelectric composite nanocrystalline cellulose – triglycine sulfate Ferroelectrics 498, 27–35 (2016) https://doi.org/10.1080/00150193.2016.1166835 T.R Volk, S.V Mednikov, L.A Shuvalov, Unipolarity of Tgscrystals induced in paraelectric phase Ferroelectrics 47, 15–23 (1983) https://doi.org/10.1080/00150198308227816 A.K Jonscher, The ‘universal’ dielectric response Nature 267, 673–679 (1977) https://doi.org/10.1038/267673a0 H.T Nguyen, A.S Sidorkin, S.D Milovidova, O.V Rogazinskaya, Electrophysical properties of matrix composites nanocrystalline cellulose – triglycine sulfate Ferroelectrics 512, 71–76 (2017) https://doi.org/10.1080/00150193.2017.1349900 V.L Ginzburg, Theory of ferroelectric phenomena Usp Fiziol Nauk 38, 390 (1949) Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations ... https://doi.org/10.1080/00150193.2016.1204866 T Fattahi Meyabadi, F Dadashian, G Mir Mohamad Sadeghi, H Ebrahimi Zanjani Asl, Spherical cellulose nanoparticles preparation from waste cotton using a green method Powder... to assume that the expansion of this adsorption band is mainly due to the increase in number of hydrogen bonds in the composite Along with the expansion of the mentioned band, a slight deviation... dried and wet samples was tested using a Rigaku Ultima IV X-ray diffractometer (Japan) using Cu Kα radiation (λ = 1.5406 Å) at a voltage of 40 kV and current of 30 mA in the scanning range 2θ of