Next Article in Journal
Curcumin-Loaded Nanofibrous Matrix Accelerates Fibroblast Cell Proliferation and Enhances Wound Healing via GSK3-β Inhibition
Next Article in Special Issue
Boosting the Catalytic Performance of Au-Pd/Graphene Oxide Nanocomposites via the Controlled Oxidation of Graphene Sheets
Previous Article in Journal
Computational Investigation of the Mechanical Behavior of a Bone-Inspired Nanocomposite Material
Previous Article in Special Issue
Ion-Mediated Self-Assembly of Graphene Oxide and Functionalized Perylene Diimides into Hybrid Materials with Photocatalytic Properties
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
J. Compos. Sci.
Volume 7
Issue 8
10.3390/jcs7080342
jcs-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Composite Membrane Based on Graphene Oxide and Carboxymethylcellulose from Local Kazakh Raw Materials for Possible Applications in Electronic Devices

by
Tilek Kuanyshbekov
1,2,*,
Zhandos Sagdollin
1,2,
Elzhas Zhasasynov
1,
Kydyrmolla Akatan
1,
Bayan Kurbanova
3,
Nazim Guseinov
4,
Zhandos Tolepov
4,
Nurgamit Kantay
1,2 and
Madyar Beisebekov
2
1
National Scientific Laboratory of Collective Use, S. Amanzholov East Kazakhstan University, 55 Kazakhstan str., Ust-Kamenogorsk 070002, Kazakhstan
2
Scientific Center of Composite Materials, 79 Nurmakovstr., Almaty 050026, Kazakhstan
3
Department of Physics, School of Sciences and Humanities, Nazarbayev University, Astana 010000, Kazakhstan
4
Department of Physics and Technology, Al-Farabi Kazakh National University, Al-Farabi Avenue, 71, Almaty 050040, Kazakhstan
*
Author to whom correspondence should be addressed.
J. Compos. Sci. 2023, 7(8), 342; https://doi.org/10.3390/jcs7080342
Submission received: 3 August 2023 / Revised: 11 August 2023 / Accepted: 15 August 2023 / Published: 21 August 2023
(This article belongs to the Special Issue Graphene Oxide Composites)
Browse Figures
Review Reports Versions Notes

Abstract

:
The synthesis of new composite nanomaterials based on graphene oxide (GO)modified with cellulose and its derivatives, as well as nanocellulose, is currently an important direction and contributes toward solving many problems in various fields such as nanotechnology, information technology, medicine, high-dielectric materials, and nanoelectronics. In this work, for the first time, for the production of GO and its membrane with carboxymethylcellulose (CMC), local Kazakhstan “Ognevsky” graphite was used as the initial raw material. In this regard, the preparation of nanocomposites of GO modified with cellulose derivatives, including CMC, attracts great interest from scientists and expands its field of practical application due to the significant changes in its physicochemical properties. In this work, the GO obtained using the Hummers method was modified by CMC, and its physicochemical, structural, and electrical characteristics were studied. The GO/CMC membrane was synthesized by mixing 1% GO with crushed solid mass of CMC (0.03 g; 0.06 g; 0.15 g) and then processing using ultrasound. The surface morphology of the GO/CMC membrane was studied using scanning electron microscopy (SEM). It has been established that by increasing the mass of CMC (0.03 g; 0.06 g; 0.15 g), the polymerization of CMC occurs on the surface of GO nanosheets. Cross-sectional micrographs of GO/CMC show the formation of sandwich-like layered structures. The synthesis efficiency (yield) of GO from synthetic graphite is 10.8%, and GO from Ognevsky graphite is 11.9%, almost 1.1% more than GO from synthetic graphite. The mechanical tensile strength increases from 2.3 MPa to 14.3 MPa and the Young’s modulus from 2.3 MPa to 143 MPa. The electrical parameters of the humidity sensor based on GO and GO/CMC membranes (0.03 g; 0.06 g; 0.15 g) were studied as a function of humidity to determine the performance of the device.

1. Introduction

At present, continuous studies of nanocomposites, nanomaterials based on graphene oxide (GO) modified with cellulose and nanocellulose, including carboxymethylcellulose, make it possible to solve many problematic issues in the field of nanotechnology, information technology, medicine, and high-dielectric materials in nanoelectronics. GO can be obtained by the oxidation and exfoliation of graphite using the standard Hummers method, a result of which is the formation of hydroxyl, carboxyl and epoxy groups on the surface, increasing the hydrophilic character of GO and further expanding its possible functionalization, therefore expanding its scope of practical application as a sensing element in various sensors, biocomposite materials, and in drug delivery and other biomedical applications [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19].
In the chemical structure of carboxymethyl cellulose (CMC), like GO, there are functional oxygen-containing groups that polymerize well with graphene oxide, which contributes to a change in the physico-mechanical and physico-chemical properties and electrical and structural characteristics. In this regard, the preparation of nanocomposites of GO modified with CMC attracts the interest of scientists and expands its field of practical application due to the excellent physical and chemical properties. The CMC is a common semi-synthetic natural polymer derived from cellulose, which is an anionic linear biopolymer in which the hydroxyl groups of cellulose are partially replaced by carboxymethyl groups [20,21,22]. Along with other biopolymers, CMC has attractive properties such as water solubility, non-toxicity, hydrophilicity, film-forming ability, bioadhesiveness, pH sensitivity, non-toxicity, low immunogenicity, and gel-forming properties, which are used in areas like coating liquids, binders, textiles, paper, food, drug delivery systems, and cosmetics [1,23,24,25,26]. However, biocomposites based on CMC have poor mechanical properties and low thermal stability compared to common polymers, which makes them almost impossible for practical applications. Recently, scientists have been diligently engaged in the research and production of a composite material based on GO/CMC. For example [27], CMC/GO nanocomposite hydrogel beads have been investigated as a drug delivery system that is highly dependent on pH. Also, [1] researchers investigated the GO/CMC nanocomposite for dressing materials. In recent study [28], by combining GO with CMC, a three-dimensional composite aerogel was obtained to achieve additional advantages and synergistic effects. The reusable carboxymethyl cellulose/graphene oxide composite aerogel with a large surface area was made by a research team for methylene blue adsorption [29].
Due to the multifunctional properties of GO and its possible functionalization with various biopolymers, and also due to the presence of functional oxygen-containing groups, it provides a huge opportunity for surface modification. In this regard, the modification of GO with CMC contributes to the production of a biocomposite membrane of a certain thickness with uniform dispersibility and a relatively flat surface with improved mechanical properties [30,31,32,33,34,35,36,37]. Therefore, in this work, GO was modified with CMC using ultrasonic treatment and its physicochemical properties were studied.
The most important part in the production of GO and GO/CMC is the correct choice of the initial raw material, which, in turn, affects the quality of GO/CMC, as well as the cost of the obtained product. To obtain GO, synthetic graphite is mainly used, which is synthesized from graphitized carbon as a by-product of oil at a temperature of 3000 °C [12,13], which, in turn, is very expensive. The wide-scale application of commercial graphite in many industries, as well as in the battery industry, contributes to an increase in the price and demand for the product and other supply problems. Therefore, one of the best ways to solve the problem of using graphite as a raw material for GO and GO/CMC is to use natural graphite from local deposits of the Republic of Kazakhstan. Based on the above, the main goal and novelty of this work is the use of local Kazakh graphite “Ognevsky” as a raw material for the production of GO and GO/CMC and the study of their physicochemical properties and electro physical characteristics of the humidity sensor. The most basic reason for creating a GO/CMC-based humidity sensor is that the composite membrane has a smooth surface and compact lamellar structure compared to the original GO membrane, and the presence of a large number of oxygen-containing functional groups contributes to humidity sensitivity. In addition, the GO/CMC-based humidity sensor has improved mechanical properties, and the synthesis of graphene oxide from local Ognevsky graphite provides a higher yield than synthetic graphite, which contributes to an economically efficient, profitable, and high-quality composite membrane for the production of humidity sensors. The location of the raw graphite material is in the Ognevsk ore field (Ognevka mine), Kalbinsk ridge, Ulan district, East Kazakhstan region.

2. Experimental Section

2.1. Materials

In this study, the following materials were used: potassium permanganate (KMnO4, 99%), sodium nitrate (NaNO3, 99%), hydrochloric acid (HCl, 35%), graphite obtained from the Ognevsk ore field (Ognevka mine) located in the Ulan district, East Kazakhstan region, hydrogen peroxide (H2O2, 31%), glacial acetic acid (CH3COOH, ≥85%), ethanol (C2H5OH, 96%), sulfuric acid (H2SO4, 98%), sodium hydroxide NaOH, ≥99%), trichloroacetic acid (Cl3CHCOOH, 99%) obtained from Alita LLP (Kazakhstan), and deionized water. All other reagents were of analytical grade and were used without additional purification.

2.2. Methods

2.2.1. Synthesis of GO

GO was obtained using the Hummers method(Figure 1(1)–(8)), in which the synthesis was a two-stage oxidation of graphite and exfoliation of graphite oxide. Graphite oxidation included a three-phase procedure with low-, medium-, and high-temperature reactions, with each of them occurring separately in time. In the low-temperature reaction procedure, a beaker with 1 g of graphite was placed in a container filled with ice at a temperature of 0 °C (Figure 1(1)). Then, keeping the sequence, the following reagents were gradually added: 94% H2SO4; NaNO3(0.5g); KMnO4(3 g) (Figure 1(2)–(5)). After adding each reagent, the mixture was stirred for 15 min and left for 2 h for continuous stirring on a magnetic stirrer(Figure 1(6)). In order to carry out the medium-temperature reaction, the temperature was raised to 35 °C and held for 30 min. Then, after adding deionized water, the temperature was raised to 90 °C and stirring was continued for 30 min (Figure 1(7)). Finally, 30% hydrogen peroxide was added until the color of the mixture changed to bright yellow and gas evolution was detected (Figure 1(8)). The product was then filtered through filter paper and washed several times with 5% hydrochloric acid to remove residual metal ions, and finally was neutralized with deionized water in a centrifuge (Centrifugation 5427× R Eppendorf, Novosibirsk, Russia) to a pH of 7 (Figure 1).
At the stage of the delamination of the graphite oxide into few-layer graphene sheets, centrifugation and ultrasonic treatment were used, a result of which was that the graphite oxide with functional oxygen-containing groups was delaminated into multilayer sheets, and few-layer and single-layer sheets of GO were also present. The GO suspension was treated with a centrifuge at a rotation speed of 5000 rpm, and then processed using ultrasound at a frequency of 45 kHz (Ultrasound 0.15/22× UZTA-, Novosibirsk, Russia) at a temperature of 25 °C for 60 min (Figure 1).

2.2.2. Synthesis of CMC

For the synthesis of CMC, 5 g of cellulose, 100 mL of 95% ethanol, and 10 mL of 45% NaOH solution were poured into a flask and mixed with a magnetic stirrer at a speed of 750 rpm at room temperature for 60 min. After that, 5 mL of trichloroacetic acid was added to the mixture and stirred in a water bath at a temperature of 600 °C for 60 min. The solution was heated and cooled to room temperature before being neutralized with glacial acetic acid until the pH was 6–7.The prepared mixture was filtered with filter paper and washed with 500 mL of 80% ethyl alcohol in a Soxhlet for 3 h. The prepared CMC was dried at room temperature.

2.2.3. Synthesis of Composite Membrane Based on GO/CMC

In order to obtain the GO/CMC membranes, a 1% GO water solution was first prepared. To prepare 1% graphene oxide, first of all, a 1 g sample of synthesized graphene oxide was measured and dissolved in a 100 mL flask using an ultrasonic bath (Ultrasonic bath 11308× Sapfir, Moscow, Russia) at a frequency of 30 kHz for 30 min. Then, a 10 g sample of CMC was taken and ground in a ball mill at 500 rpm for 15 min.
After that, to obtain the GO/CMC membrane, 1% GO was continuously stirred for an hour with a crushed solid mass of CMC (0.03 g; 0.06 g; 0.15 g) on a magnetic stirrer (Figure 2). The GO/CMC suspensions were treated at 800 rpm using a magnetic stirrer (Magnetic stirrer 6120× ES- with heated, Ecroskhim, Saint Petersburg, Russia) at a temperature of 40 °C for 60 min. Further suspensions were processed using ultrasound at a frequency of 45 kHz (Ultrasound 0.15/22×- UZTA, Novosibirsk, Russia) at a temperature of 30 °C for 60 min.
The completely mixed mixture of GO and CMC was poured onto a flat plastic surface and dried in a drying chamber at a temperature of 50 °C for 48 h.

2.2.4. SEM Analysis

The surface morphology of the GO/CMC membranes was studied using a scanning electron microscope (Scanning electron microscope Jeol 6390× JSM-LV, Tokyo, Japan). Measurements were carried out in high-vacuum mode using a secondary electron detector at an accelerating voltage of 15 kV. The surfaces of theCMC and GO/CMC films were coated with gold to improve the transfer of electrons. The specimens were mounted on aluminum pins with carbon tape.

2.2.5. FTIR Analysis

FTIR analyses of the chemical structures of the GO and GO/CMC membranes were performed on a spectrometer (Spectrometer Simex,801× FT-, Moscow, Russia), with a resolution of 1 cm−1. The measurements were conducted in the region between 450 and 4700 cm−1 according to the standard method using a single-use universal full internal and mirror-diffuse reflection with the upper position of the model at a temperature of 25 °C.

2.2.6. X-ray Diffraction

The crystal structures of the GO and GO/CMC membranes were studied via X-ray diffraction on a X’PertPRO diffractometer (X’PertPRO diffractometer Malvern Panalytical Empyrean, Amsterdam, The Netherlands) using monochromatized copper (CuKα) at a scan speed of 0.05° for 10 s, with a K-Alpha1 wavelength of 1.54187 Å. The measurement in reflection mode, using an aluminum rectangular multi-purpose sample holder (PW1172/01), was performed at a diffraction angle 2θ between 10° and 40°, with the X-ray tube voltage at 45 kV, current intensity at 30 mA, and a measurement time of each step of 0.5 s.
The graphene periodicity was determined via the following Scherer formula:
D = kλ/βcosθ
where k is a shape factor that is often 0.94 [38]; λ is the wavelength of the diffractometer (0.1542nm); β is the FWHM (maximum half of the full width) of the diffraction peak in radians; and θ is the diffraction angle.

2.2.7. Mechanical Characterization

The mechanical characteristics of the GO and GO/CMC membranes were studied using a tensile testing machine (Tensile testing machine WDW5× kN, Time Group Inc., Beijing, China) with a measured load range of 0.01–5kN and a loading speed range of 0.0005–500 mm/min. Data registration was performed automatically using a computer with a special program. During the testing of the samples under a load of 0.01 kN, the movement speed was 2 mm/min. The samples were tested until the maximum tensile force was reached or before the sample became deformed.

2.2.8. Electrical Characterization

The electrical properties of the GO and GO/CMC membranes were investigated using the four-point probe method. Electrical measurements were made using the traditional four-probe method, with the current measured on a Keithley Picoammeter (Picoammeter 6485× Keithley, Cleveland, OH, USA) and the voltage applied with a Tektronix PWS2326.

2.2.9. Creation of a Humidity Sensor Based on GO and GO/CMC

The design of the humidity sensor is shown in Figure 3.The GO and GO/CMC (0.03 g; 0.06 g; 0.15 g) membranes were mounted on a dielectric substrate and connected with opposite ends of copper wire (0.15 mm in diameter) as electrodes to the samples. These electrodes were attached with stable fixtures to ensure good electrical contact. Four legs of the dielectric substrate were installed. As can be seen from Figure 3, the sensor substrate had the following dimensions: 10.5 × 5.7 cm; the thickness of the membranes was about 20 microns; the length was 3.5 cm; and the width was 1 cm. The surface of the GO and GO/CMC membranes was open on both sides, making it sensitive to the relative humidity of the environment. As can be seen from the diagram in Figure 3, a humidity sensor based on GO and GO/CMC (0.03 g; 0.06 g; 0.15 g) and an exemplary DHT 22 sensor on the Arduino platform were mounted together on a dielectric substrate and placed together in the test chamber (Figure 4) that was used to control the humidity. The DHT 22 sensor is designed to measure humidity levels in the range from 0 to 100% and the measurement accuracy is in the range of 2–5%.
A schematic representation of the installation for investigating the sensitivity of the sensor to humidity is shown in Figure 4. The humidity sensor test chamber has a main box and a humidity controller from 1% to 99% with a temperature sensor. A Keithley Picoammeter (Picoammeter 6485× Model, Keithley Instruments, Solon, OH, USA) was used to measure the electrophysical characteristics of the humidity sensor. The Keithley 6485 meter was attached to the copper electrodes with alligator clips. The error bars were limited by an instrument error of no more than 0.5%.

3. Results and Discussion

3.1. SEM Analysis

The obtained SEM results of the GO/CMC (0.03 g; 0.06 g; 0.15 g) demonstrated that the CMC particles are effectively dispersed in the GO matrix in almost all samples (Figure 5). In some images of the GO/CMC samples (0.03 g; 0.06 g; 0.15 g), individual CMC clusters can be seen depending on the mass of CMC particles added to the composite membranes. In general, in comparison with the initial GO, the surface morphology of all GO/CMC samples is smooth; only in single samples with an increase in the mass of added CMC can small particles of CMC and slight wrinkles on the surface be observed, which is associated with aggregation.
According to the obtained cross-section SEM images of the GO/CMC samples, depending on the mass of the added CMC particles, all composite membranes have compact lamellar structures compared to the original GO membrane, and only some samples have slightly coarse structures (Figure 5a–d). In addition, according to the literature data, the formation of a compact lamellar structure and a stable bond to impart a certain mechanical strength between GO and CMC is promoted by the presence of a large number of carboxymethyl groups in the CMC and various functional oxygen-containing groups in the GO, as well as hydrogen bonds between the composite membranes [16,39,40,41,42].

3.2. X-ray Diffraction

The X-ray phase analysis of the obtained membrane from a liquid suspension of GO with 1% concentration and GO/CMC membranes was carried out in order to assess their crystallinity (0.03 g; 0.06 g; 0.15 g) (Figure 6(0)–(4)). According to the obtained XRD spectrum of the GO and GO/CMC, the following peaks were found: 2θ = 7.06° (GO); 2θ = 11.97° (GO/CMC-0.03 g); 2θ = 11.22° (GO/CMC-0.06 g); and 2θ = 9.45° (GO/CMC-0.15 g).
The intense peak characteristic of GO was equal to 2θ = 7.06° (002) and an inter-layer distance d= 10.2 Å (Figure 6(0)) due to the presence of oxygen-containing functional groups attached to both sides of the graphene sheet. Atomic-scale roughness arising from structural defects (sp3 bond) formed on the initially atomically flat graphene sheet. In the diffractogram of the CMC, one peak characteristic of amorphous carbon was recorded at 2θ = 22.2°(Figure 6(1)) [43], which indicates that the hydrogen bonds in the cellulose molecule were completely broken during the synthesis of CMC, and the diffractogram of the obtained material corresponds to CMC [44,45].
According to the results of the XRD, compared with the initial GO, after the addition of CMC with a mass of 0.03 g, a shift of 2θ from 7.05° to 11.89° is observed; with an increase in the added mass of CMC (0.03 g; 0.06 g; 0.15 g), a shift in the peak positions is observed in the GO/CMC from 11.89° to lower values of 2θ = 11.35° and 9.70°, respectively. Moreover, the graphene periodicity was determined via the Scherer formula [38], which is shown in Table 1. The results obtained showed that with an increase in the added masses of CMC in GO, the crystallite sizes decreased from 27.93 to 0.30 nm (Table 1).
This is presumably explained by the fact that due to the hydrogen bond formed between GO and CMC, the space between the GO layers (sheet graphene) is saturated with the glucopyranose units of the cellulose polymer chains, disrupting the order of the arrangement of the graphene layers (sheet graphene) and resulting in a shift of the diffraction peak to the right and an increase in the peak area [46,47]. The existence of a hydrogen bond between GO and CMC is confirmed by the IR spectrum. Also, the reason for the shift in the 2θ value in the GO/CMC 0.06 g and 0.15 g samples to the initial GO value is explained by the fact that as the mass of CMC increases, the hydrogen bond between GO and CMC becomes more saturated and has a negative effect on the bond strength [48]. The obtained results are consistent with the results of the study [38,40,47,49,50,51,52].

3.3. FTIR Analysis

In Figure 7(2),(3), the synthetic graphite powder and the Ognevsky graphite exhibit peaks in the region of 1023–1043 cm−1, illustrating the vibration of the C-C aromatic compound. According to the spectra obtained, the synthesized samples of graphene oxide from the synthetic and Ognevsky graphite flakes consist of various oxygen functional groups (3600–3000 cm−1 O-H, aromatic ring 1585 cm−1 C=C, epoxy functional groups 1249 cm−1 C-O, alkoxy groups 1054 cm−1 C–O) (Figure 6(0),(1)) [10]. Based on this, the FTIR spectra data confirm that the Ognevsky graphite and the GO synthesized from it are of high quality and are similar to the GO obtained from synthetic graphite. The synthesis efficiency (yield) of the GO from synthetic graphite is 10.8%, and the GO from Ognevsky graphite is 11.9%, almost 1.1% greater than the GO from synthetic graphite. In this regard, on the basis of the above data, in comparison with synthetic graphite, Ognevsky graphite is the most efficient and economical material for the synthesis of GO.
According to the results of the FTIR spectroscopy of the GO, the following signals can be seen in the absorption region: 3600–3000 cm−1 O–H, aromatic ring 1585 cm−1 C=C, epoxy functional groups 1249 cm−1 C–O, alkoxy groups 1054 cm−1 C–O (Figure 8(0)) [10].
According to the FTIR spectrum, CMC is observed at the following wavelengths: hydroxyl group (stretching –OH) at 3200–3600 cm−1, C–H stretching vibration at 3000 cm−1, carbonyl group (stretching C=O) at 1680 cm−1, hydrocarbon groups (cleavage –CH2) at 1450 cm−1, and ester groups (stretch –O–) at 1000–1200 cm−1(Figure 8(1)) [40,42,43,44,45,46,47,48,49,50].
Figure 8(2)–(4) show the FTIR spectrum of the GO membrane with CMC [40,41,42,43,44,45,46,47,48,49,50,51]. The results of the FTIR spectroscopy of the GO membrane with CMC show the following signals in the wavelength range: 3600–3000 cm−1 O–H, aromatic ring 1585 cm−1 C=C, epoxy functional groups 1249 cm−1 C-O, alkoxy groups 1054 cm−1 C–O (Figure 7(2)–(4)). The decrease in the intensity at a wavelength of 1679 cm−1 denotes an ether bond (O=C–O) between the hydroxyl groups (–OH) from GO and carboxyl groups from CMC. In the FTIR spectra, new ether bonds, –C=O, were found at a wavelength of 1679 cm−1.

3.4. Mechanical Characterization

One important point of the study is the mechanical testing of the GO/CMC composites, which highlights the importance of the properties of the obtained composite membranes. Figure 9(0)–(3) show a graph of the applied force and relative elongation after stretching GO and GO with CMC (0.03 g, 0.06 g, and 0.15 g) at room temperature on WDW-5E. The obtained results regarding the mechanical properties of the GO and GO/CMC composites showed that with an increase in the added solid mass of CMC (0.03 g; 0.06 g; 0.15 g) in the GO, the mechanical tensile strength increases from 2.3 MPa to 14.3 MPa and the Young’s modulus from 2.3 MPa to 143 MPa (Figure 9(0)–(3)).
According to the obtained results, the tensile strength of the initial GO was 5.7 MPa and the Young’s modulus was 57 MPa. After adding 0.03 g of CMC to the GO, the strength limit was 2.3 MPa and the Young’s modulus was 9.2 MPa. Then, after adding 0.06 g of CMC to the GO, the ultimate strength was 9.9 MPa and the Young’s modulus was 66 MPa. Further, after adding 0.15 g of CMC to the GO, the strength limit was 14.3 MPa and the Young’s modulus was 143 MPa. Based on the results of this research, it can be seen that adding a small amount of CMC to the GO decreases the strength limit and Young’s modulus, and increasing the amount of CMC significantly increases the strength limit and Young’s modulus. In our opinion, presumably, the addition of CMC in a small amount can increase the porosity in the layer of graphene oxide film, and when the amount of CMC is further increased, it fills the pores between the GO lattices and forms a connection between the GO and CMC, leading to an increase in the Young’s modulus at the strength limit. Also, an increase in mechanical strength with an increase in the added mass of CMC particles in GO according to the Young modulus values of the GO/CMC composite membranes is explained by the presence of a large number of carboxymethyl groups in the CMC and various functional oxygen-containing groups in the GO, as well as the presence of hydrogen bonds between GO and CMC [16,39,40,41,42] and the ether bond –C=O, which is confirmed by the FTIR spectra. Therefore, the results regarding the mechanical testing of GO/CMC composite membranes are in good agreement with the data fromthe SEM, FTIR, XRD, and electrical characterization analyses.

3.5. Electrical Characterization

The electrical characterization of the GO and GO/CMC membrane was carried out using a Keithley Picoammeter (Model 6485) using the four-point probe method. The resistivity of the GO/CMC membrane increased from 1.51 × 106 to 1.26 × 107 Ohm × m compared to the initial GO with an increasing amount of CMC (0.03 g; 0.06 g; 0.15 g) (Figure 10(0)–(3)).
The value of the resistivity of the initial GO was equal to 1.51 × 106, and for the GO/CMC sample (0.03 g), it showed the following value: 6.46 × 106 (Figure 9(1)). On the following GO samples of added CMC solid masses (0.06 g; 0.15 g) there was an increase from 9.27 × 106 to 1.26 × 107(Figure 10(2),(3)).
In general, according to the obtained results of the specific resistance of the GO with added CMC particles (0.03 g; 0.06 g; 0.15 g), an increase in the resistivity was observed compared to the initial sample. According to the research, an increase in the permittivity of a composite with GO is associated with interfacial polarization that occurs at the CMC–GO interface [53,54]. Moreover, the increase in the dielectric constant was affected by the presence of polar functional groups of GO, such as –OH, –CHO, –CO, and –COOH, providing good adhesion and corresponding to local electrical contacts that can lead to strong interfacial polarization. In the case of a pure GO sample, this polarization can be due to the immiscible phase of the polymer matrix. Presumably, spatial polarization due to trap states leads to the accumulation of charge carriers and to an increase in the value of the permittivity [53,55].

3.6. Electrophysical Characteristics of the Humidity Sensor Based on GO and GO/CMC (0.03 g; 0.06 g; 0.15 g)

The electrical parameters of the humidity sensor based on the GO and GO/CMC membranes (0.03 g; 0.06 g; 0.15 g) were studied as a function of humidity to determine the performance of the device. The response and recovery of the humidity sensor were tested using a Keithley (Model 6485) meter attached to copper electrodes with alligator clips. The results of the sensor response and recovery tests as a function of time are shown in Figure 11. The response and recovery time of the humidity sensor was tested in a sealed chamber with a controlled humidity level in the range from 20% to 90% (RH) with an interval of 5% (RH) for 84 min (Figure 10). The results of the study showed that with an increase in the relative humidity, the electrical resistance of the humidity sensor decreased. According to the obtained results, it is obvious that in all samples with an increase in humidity from 20% to 90% (RH), a significant decrease in electrical resistance was observed of almost two to four orders of magnitude depending on the addition of CMC (0.03 g; 0.06 g; 0.15 g) to GO. In addition, a symmetrical change in the values of electrical resistance was observed when the humidity decreased from 90% to 20%. On the initial GO, with an increase in humidity from 20% to 90% (RH), the electrical resistance decreased by three orders of magnitude from 3.4 × 107 to 2.6 × 104 Log (R, Ohm). Then, after adding CMC (0.03 g; 0.06 g; 0.15 g) to the samples (1, 2, 3), the electrical resistance decreased as follows: (1)—from 1 × 108 to 7.8 × 104; (2)—from 2.9 × 108 to 4.1 × 104; (3)—from 6.4 × 109 to 6.2 × 104 Log (R, Ohm). In the dynamics of recovery, with a decrease in humidity from 90% to 20%, the electrical resistance of the GO and GO/CMC samples (0.03 g; 0.06 g; 0.15 g) increased in the following order: (0)—from 2.6 × 104 to 1, 7 × 107; (1)—from 7.8 × 104 to 5 × 107; (2)—from 4.1 × 104 to 1.2 × 108; (3)—from 6.2 × 104 to 1.1 × 109 Log (R, Ohm). In the results of the dynamics of sensor recovery at 20% humidity, the values of the electrical resistance of the samples were not significantly lower than the resistance at the response at the same level of 20% humidity, which is explained by the saturation of the membranes with water molecules, and indicates the successful recovery of the samples from moisture. In addition, with an increase in humidity compared to the initial GO after the addition of CMC (0.03 g; 0.06 g; 0.15 g), a significant increase in the electrical resistance was observed with an increase in the masses of the added CMC particles in the GO. This change is explained by the presence of hydrogen bonds between GO and CMC [16,38,39,40,41] and an ether bond, C=O, which is confirmed by the IR spectrum and electrical characteristics in Figure 11 as well as by the interfacial polarization that occurs at the CMC–GO boundary [52,53]. In general, during the response of the sensor, the process of reducing the electrical resistance with increasing humidity is due to the fact that a large number of water molecules are adsorbed on the surface of GO and CMC, which significantly increases its conductivity due to the proton–electron exchange between GO/CMC and adsorbed molecules [56,57,58,59]. Accordingly, during the dynamics of recovery, adsorbed water molecules are removed, which leads to an increase in resistance. Thus, according to the results of the dynamics of response and recovery of the humidity sensor, a decrease and increase in the electrical resistance values is observed in the entire range of relative humidity, which confirms the sensitivity of GO and GO/CMC (0.03 g; 0.06 g; 0.15 g) membranes to moisture.

4. Conclusions

Composite GO/CMC membranes were obtained by adding solid masses of CMC (0.03 g; 0.06 g; 0.15 g) to 1% GO suspension. For the production of GO and its membrane using carboxymethylcellulose (CMC), local Kazakhstan “Ognevsky” graphite was used as the initial raw material. The SEM images of the surface and side section of the GO/CMC sample showed that the obtained composite membranes have a smooth surface and a compact lamellar structure compared to the initial GO membrane, and small particles of CMC were only found on the surfaces of some membranes, as well as a slightly rough structure according to the side section images, which is associated with aggregation. The analysis of the XRD spectra showed that after the intercalation of solid masses of CMC (0.03 g; 0.06 g; 0.15 g) to the sheet layers of GO, peaks were detected at 2θ = 34.92° (GO/CMC), confirming crystal planes (041) of CMC, and the crystallite sizes decreased from 27.93 to 0.30 nm. Their mechanical tensile strength increased from 2.3 MPa to 14.3 MPa and the Young’s modulus from 2.3 MPa to 143 MPa. In the IR spectra after the modification of GO with CMC, new ether bonds of –C=O were found at a 1679 cm−1 wavelength. The resistivity of the GO/CMC composite membrane with increasing CMC mass (0.03 g; 0.06 g; 0.15 g), which were added to the GO, increased from 1.51 × 106 to 1.26 × 107 Ohm × m compared to the initial GO. These changes in resistivity values are presumably related to the interfacial polarization that occurs at the CMC–GO interface, indicating that the obtained membrane can be a composite material with dielectric properties. In all samples with an increase in humidity from 20% to 90% (RH), a significant decrease in electrical resistance was observed of almost two to four orders of magnitude depending on the addition of CMC (0.03 g; 0.06 g; 0.15 g) to GO. The synthesis efficiency (yield) of the GO from synthetic graphite was 10.8%, and the GO from Ognevsky graphite was 11.9%, almost 1.1% more than the GO from synthetic graphite.

Author Contributions

All authors contributed to the study conception and design. Material preparation, data collection, and analyses were performed by T.K., Z.S., E.Z., K.A., B.K., N.G., Z.T., N.K. and M.B. The first draft of the manuscript was written by T.K. and all authors commented on the previous versions of the manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan within the framework of Grant No. AP09058548 “Development of a sensitive humidity sensor based on a graphene oxide membrane obtained from activated carbon for military needs” (2021–2023).

Data Availability Statement

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Maria, L.S. Graphene Oxide Carboxymethylcellulose Nanocomposite for Dressing Materials. J. Mater. 2020, 13, 1980. [Google Scholar]
  2. Maio, D.; Giallombardo, R.; Scaaro, P.A.; Palumbo, I. Pibiri: Synthesis of a fluorinated grapheme oxide–silica nanohybrid: Im-proving oxygen a_nity. J. RSC Adv. 2016, 6, 46037–46047. [Google Scholar] [CrossRef]
  3. Mansurov, Z.; Jandosov, J.; Kerimkulova, A.; Azat, S.; Zhubanova, A.; Digel, I.; Savistkaya, I.; Akimbekov, N.; Kistaubaeva, A. Nanostructured Carbon Materials for Biomedical Use. J. Eurasian Chem. Tecnol. 2013, 15, 209–217. [Google Scholar] [CrossRef]
  4. Azat, S.; Rosa, B.; Pavlenko, V.V.; Kerimkulova, A.R.; Raymond, L.D.; Mansurov, Z.A. Applications of activated carbon sorbents based on greek walnut. J. Appl. Mech. Mater. 2014, 467, 49–51. [Google Scholar] [CrossRef]
  5. Azat, S.; Arkhangelsky, E.; Papathanasiou, T.; Zorpas, A.A.; Abirov, A.; Inglezakis, V.J. Synthesis of biosourced silica-Ag nano-composites and amalgamation reaction with mercury in aqueous solutions. J.ComptesRendusChim. 2020, 23, 77–92. [Google Scholar]
  6. Kuanyshbekov, T.K.; Ilyin, A.M.; Beall, G.W.; Guseinov, N.R. Creation of a Humidity Sensor Based on Functionalized Graphene Nanostructures. J. Sens. Transducers 2019, 229, 39–46. [Google Scholar]
  7. Ilyin, A.M.; Guseinov, N.R.; Kuanyshbekov, T.K.; Beall, G.W.; Tulegenova, M.A. Computer Simulation and First Principles Study of Ga-Doped Graphene Nanostructures. J. Comput. Theor. Nanosci. 2019, 16, 39–41. [Google Scholar] [CrossRef]
  8. Tulegenova, M.; Ilyin, A.; Guseinov, N.; Beall, G.; Kuanyshbekov, T. Computer Simulation of the Effect of Structural Defects on the Effectiveness of the Graphene’s Protective Properties. J. Comput. Theor. Nanosci. 2019, 16, 351–354. [Google Scholar] [CrossRef]
  9. Kuanyshbekov, T.K.; Ak, K.; Kabdrakhmanova, S.K.; Nemkaeva, R.; Aitzhanov, M.; Imasheva, A. Kairatuly Synthesis of Graphene Oxide from Graphite by the Hummers Method. J. Oxid. Commun. 2021, 44, 356–365. [Google Scholar]
  10. Akatan, K.; Kuanyshbekov, T.K.; Kabdrakhmanova, S.K.; Imasheva, A.A.; Battalova, A.K.; Abylkalykova, R.B.; Nasyrova, A.K.; Ibraeva, Z.E. Synthesis of nanocomposite material through modification of graphene oxide by nanocellulose. Chem. Bull. Kazakh. Natl. Univ. 2021, 102, 14–20. [Google Scholar] [CrossRef]
  11. Akatan, K.; Kabdrakhmanova, S.; Kuanyshbekov, T.; Ibraeva, Z.; Battalova, A.; Joshy, K.S.; Thomas, S. Highly-efficient isolation of mi-crocrystalline cellulose and nanocellulose from sunflower seed waste via environmentally benign method. J. Cellul. 2022, 29, 3787–3802. [Google Scholar] [CrossRef]
  12. Maio, R.; Scaffaro, R.; Lentini, L.; Piccionello, A.P. Perfluorocarbons–graphene oxide nanoplatforms as biocompatible oxygen reservoirs. J. Anal. Chim. Acta 2018, 1037, 1–380. [Google Scholar] [CrossRef]
  13. Scaaro, R.; Lopresti, F.; Maio, A.; Botta, L.; Rigogliuso, S.; Ghersi, G. Electrospun PCL/GO-g-PEG structures: Pro-cessing-morphology-properties relationships. J. Compos. Part S Appl. Sci. Manuf. 2017, 92, 97–107. [Google Scholar] [CrossRef]
  14. Scaaro, R.; Maio, A.; Presti, F.L.; Giallombardo, D.; Botta, L.; Bondì, M.L.; Agnello, S. Synthesis and self-assembly of a PEGylat-ed-graphene aerogel. J. Compos. Sci. Technol. 2016, 128, 193–200. [Google Scholar] [CrossRef]
  15. Wang, Y.; Li, Z.; Wang, J.; Li, J.; Lin, Y. Graphene and graphene oxide: Biofunctionalization and applications in biotechnology. TrendsBiotechnol. 2011, 29, 205–212. [Google Scholar] [CrossRef] [PubMed]
  16. Zhang, H.; Zhai, D.; He, Y. Graphene oxide/polyacrylamide/carboxymethylcellulose sodium nanocomposite hydrogel with enhanced mechanical strength: Preparation, characterization and the swelling behavior. J. RSC Adv. 2014, 4, 44600–44609. [Google Scholar] [CrossRef]
  17. Li, X.; Li, F.; Gao, Z.; Fang, L. Toxicology of graphene oxide nanosheets against paecilomyces catenlannulatus. J.Bull.Environ.Contam. Toxicol. 2015, 95, 25–30. [Google Scholar] [CrossRef] [PubMed]
  18. Liu, S.; Zeng, T.H.; Hofmann, M.; Burcombe, E.; Wei, J.; Jiang, R.; Kong, J.; Chen, Y. Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: Membrane and oxidative stress. J. ACS Nano 2011, 5, 6971–6980. [Google Scholar] [CrossRef]
  19. Song, Z.; Xu, Y.; Yang, W.; Cui, L.; Zhang, J.; Liu, J. Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation. Eur. Polym. J. 2015, 69, 559–572. [Google Scholar] [CrossRef]
  20. Jiao, Z. Carboxymethyl cellulose-grafted graphene oxide for efficient antitumor drug delivery. J. Nanotechnol. Rev. 2018, 7, 291–301. [Google Scholar] [CrossRef]
  21. Ampaiwong, J. Reduced Graphene Oxide/Carboxymethyl Cellulose Nanocomposites Novel Conductive Films. J. Nanosci. Nanotechnol. 2019, 19, 3544–3550. [Google Scholar] [CrossRef]
  22. Son, Y.-R.; Yop, R.K.; Park, S.-J. Influence of reduced graphene oxide on mechanical behaviors of sodium carboxymethyl cellulose. J. Compos. Part B Eng. 2015, 83, 36–42. [Google Scholar] [CrossRef]
  23. Potts, J.R.; Dreyer, D.R.; Bielawski, C.W.; Ruoff, R.S. Graphene-based polymer nanocomposites. Polymer 2011, 52, 5–25. [Google Scholar] [CrossRef]
  24. Li, G.H.; Liu, K.; Ma, Z.W. Flexible Solid-State Supercapacitors Based on Carbon Nanoparticles/MnO2Nanorods Hybrid Structure. J. ACS Nano 2012, 6, 656–661. [Google Scholar]
  25. Torres, F.G.; Commeaux, S.; Troncoso, O.P. Starch-based biomaterials for wound-dressing applications. J. Starch 2013, 65, 543–551. [Google Scholar] [CrossRef]
  26. Javanbakht, S.; Shaabani, A. Carboxymethyl cellulose-based oral delivery systems. Int. J. Biol. Macromol. 2019, 133, 21–29. [Google Scholar] [CrossRef]
  27. Rasoulzadeh, M.; Namazi, H. Carboxymethyl cellulose/graphene oxide bio-nanocomposite hydrogel beads as anticancer drug carrier agent. Carbohydr. Polym. 2017, 168, 320–326. [Google Scholar] [CrossRef]
  28. Ge, X.; Shan, Y.; Wu, L.; Mu, X.; Peng, H.; Jiang, Y. High-strength and morphology-controlled aerogel based on carboxymethyl cellulose and graphene oxide. Carbohydr. Polym. 2018, 197, 277–283. [Google Scholar] [CrossRef]
  29. Zhu, W.; Jiang, X.; Jiang, K.; Liu, F.; You, F.; Yao, C. Fabrication of Reusable Carboxymethyl Cellulose/Graphene Oxide Composite Aerogel with Large Surface Area for Adsorption of Methylene Blue. Nanomaterials 2021, 11, 1609. [Google Scholar] [CrossRef]
  30. Seidi, F.; Salimi, H.; Shamsabadi, A.A.; Shabanian, M. Synthesis of hybrid materials using graft copolymerization on non-cellulosic polysaccharides via homogenous ATRP. Prog. Polym. Sci. 2018, 76, 1–39. [Google Scholar] [CrossRef]
  31. Chivrac, F.; Pollet, E.; Avérous, L. Progress in nano-biocomposites based on polysaccharides and nanoclays. Mater. Sci. Eng. R Rep. 2009, 67, 1–17. [Google Scholar] [CrossRef]
  32. Imre, B.; García, L.; Puglia, D.; Vilaplana, F. Reactive compatibilization of plant polysaccharides and biobased polymers: Review on current strategies, expectations and reality. Carbohydr. Polym. 2019, 209, 20–37. [Google Scholar] [CrossRef]
  33. El-Shafai, N.M.; Ibrahim, M.M.; Abdelfatah, M.; Ramadan, M.S.; El-Mehasseb, I.M. Synthesis, characterization, and cytotoxicity of selfassembly of hybrid nanocomposite modified membrane of carboxymethyl cellulose/graphene oxide for photocatalytic antifouling, energy storage, and supercapacitors ap-plication. Colloids Surf. A Physicochem. Eng. Asp. 2021, 626, 127035. [Google Scholar] [CrossRef]
  34. Shakeri, A.; Salehi, H.; Nakhjiri, M.T.; Shakeri, E.; Khankeshipour, N. Carboxymethylcellulose-quaternary graphene oxide nanocomposite polymer hydrogel as a biode-gradable draw agent for osmotic water treatment process. Cellulose 2019, 26, 1841–1853. [Google Scholar] [CrossRef]
  35. Maslennikov, A.; Peretz, R.; Vadivel, V.K.; Mamane, H. Recycled Paper Sludge (RPS)-Derived Nanocellulose: Production, Detection and Water Treatment Application. Appl. Sci. 2022, 12, 3077. [Google Scholar] [CrossRef]
  36. Omar, A.; Badry, R.; Hegazy, M.A.; Yahia, I.S.; Elhaes, H.; Zahran, H.Y.; Ibrahim, M.A.; Refaat, A. Enhancing the optical properties of chitosan, carboxymethyl cellulose, sodium alginate modified with nano metal oxide and graphene oxide. Opt. Quantum Electron. 2022, 54, 1–15. [Google Scholar] [CrossRef]
  37. Sirajudheen, P.; Nikitha, M.R.; Karthikeyan, P.; Meenakshi, S. Perceptive removal of toxic azo dyes from water using magnetic Fe3O4 reinforced graphene ox-ide–carboxymethyl cellulose recyclable composite: Adsorption investigation of parametric studies and their mechanisms. Surf. Interfaces 2020, 21, 100648. [Google Scholar] [CrossRef]
  38. Lim, D.J.; Marks, N.A.; Rowles, M.R. Universal Scherrer equation for graphene fragments. Carbon 2020, 162, 475–480. [Google Scholar] [CrossRef]
  39. Hen, J.; Li, H.; Zhang, L.; Du, C.; Fang, T.; Hu, J. Direct Reduction of Graphene Oxide/Nanofbrillated Cellulose Composite Film and its Electrical Conductivity Research. J. Sci. Rep. 2020, 10, 124. [Google Scholar]
  40. Zhao, M.; Zhang, S.; Fang, G.; Huang, C.; Wu, T. Directionally-Grown Carboxymethyl Cellulose/Reduced Graphene Oxide Aerogel with Excellent Structure Stability and Adsorption Capacity. J. Polym. 2020, 12, 2219. [Google Scholar] [CrossRef] [PubMed]
  41. Ciolacu, D.E.; Suflet, D.M. Cellulose-Based Hydrogels for Medical/Pharmaceutical Applications in Biomass as Renewable Raw Material to Obtain Bioproducts of High-Tech Value; Elsevier: Amsterdam, The Netherlands, 2018. [Google Scholar]
  42. Yu, H.; Hong, H.-J.; Kim, S.M.; Ko, H.C.; Jeong, H.S. Mechanically enhanced graphene oxide/carboxymethyl cellulose nanofibril composite fiber as a scalable adsorbent for heavy metal removal. Carbohydr. Polym. 2020, 240, 116348. [Google Scholar] [CrossRef]
  43. Stobinski, L.; Lesiak, B.; Malolepszy, A.; Mazurkiewicz, M.; Mierzwa, B.; Zemek, J.; Jiricek, P.; Bieloshapka, I. Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods. J. Electron Spectrosc. Relat. Phenom. 2014, 195, 145–154. [Google Scholar] [CrossRef]
  44. Abdulhameed, A.; Harun, M.M.; Changamu, E.O.; Maingi, F.M. Microwave synthesis of Carboxymethylcellulose (CMC) from Rice Husk. IOSR J. Appl. Chem. 2019, 12, 33–42. [Google Scholar]
  45. Kumar, B.; Deeba, F.; Priyadarshi, R.; Sauraj; Bano, S.; Kumar, A.; Negi, Y.S. Development of novel cross-linked carboxymethyl cellulose/poly(potassium 1-hydroxy acrylate): Synthesis, characterization and properties. Polym. Bull. 2019, 77, 4555–4570. [Google Scholar] [CrossRef]
  46. Mekkaoui, A.A.; Orfi, H.; Bejtka, K.; Laayati, M.; Labyad, S.A.; El Firdoussi, L.; Pirri, C.F.; Chiodoni, A.; El Houssame, S. Carboxymethyl cellulose nanocolloids anchored Pd(0) nanoparticles (CMC@Pd NPs): Synthesis, characterization, and catalytic application in transfer hydrogenation. Environ. Sci. Pollut. Res. 2022, 30, 81619–81634. [Google Scholar] [CrossRef] [PubMed]
  47. Miao, Y.; Wang, X.; Liu, Y.; Liu, Z.; Chen, W. Preparation of Graphene Oxide/Cellulose Composites with Microcrystalline Cellulose Acid Hydrolysis Using the Waste Acids Generated by the Hummers Method of Graphene Oxide Synthesis. Polymers 2021, 13, 4453. [Google Scholar] [CrossRef] [PubMed]
  48. Wang, X.; Wan, K.; Xie, P.; Miao, Y.; Liu, Z. Ultralight, High Capacitance, Mechanically Strong Graphene-Cellulose Aerogels. Molecules 2021, 26, 4891. [Google Scholar] [CrossRef]
  49. Miao, Y.Y.; Zhang, C.Y.; Huang, D.J.; Tian, L.; Zhao, T.J.; Zhai, X.Y.; Liu, Z.B. Preparation of graphene oxide /cellulose composite in mixed acid solution derived from Hummers method. J. For. Eng. 2018, 3, 97–102. [Google Scholar]
  50. Priya, V.N.; Rajkumar, M.; Mobika, J.; Sibi, S.L. Adsorption of As (V) ions from aqueous solution by carboxymethyl cellulose incorporated layered double hydroxide/reduced graphene oxide nanocomposites: Isotherm and kinetic studies. Environ. Technol. Innov. 2022, 26, 102268. [Google Scholar] [CrossRef]
  51. Nayak, J.; Vashishtha, A. Synthesis, Characterization and Preparation of Nanocellulose and different Cellu-lose/Nanocellulose/Graphene Composites from Cassava root and its Potential Application for Pesticide Adsorption from water. J. IJRAR 2018, 5, 513–524. [Google Scholar]
  52. Mariano, M.; El Kissi, N.; Dufresne, A. Cellulose nanocrystals and related nanocomposites: Review of some properties and challenges. J. Polym. Sci. Part B Polym. Phys. 2014, 52, 791–806. [Google Scholar] [CrossRef]
  53. He, S.; Wang, G.S.; Lu, C.; Luo, X.; Wen, B.; Guo, L.; Cao, M.S. Enhanced wave absorption of nanocomposites based on the synthesized complex symmetrical CuS nanostructure and poly (vinylidene fluoride). J. Mater Chem. A 2013, 1, 4685–4692. [Google Scholar] [CrossRef]
  54. Song, W.-L.; Cao, M.-S.; Lu, M.-M.; Liu, J.; Yuan, J.; Fan, L.-Z. Improved dielectric properties and highly efficient and broadened bandwidth electromagnetic attenuation of thickness-decreased carbon nanosheet/wax composites. J. Mater. Chem. C 2012, 1, 1846–1854. [Google Scholar] [CrossRef]
  55. Zhang, J.; Zhao, X. Conducting polymers directly coated on reduced grapheme oxide sheets as high-performance supercapacitor electrodes. J. Phys. Chem. C 2012, 116, 5420–5426. [Google Scholar] [CrossRef]
  56. Lim, W.H.; Yap, Y.K.; Chong, W.Y.; Ahmad, H. All-Optical Graphene Oxide Humidity Sensors. Sensors 2014, 14, 24329–24337. [Google Scholar] [CrossRef]
  57. Ghosh, S.; Ghosh, R.; Guha, P.K.; Bhattacharyya, T.K. Humidity Sensor Based on High Proton Conductivity of Graphene Oxide. IEEE Trans. Nanotechnol. 2015, 14, 931–937. [Google Scholar] [CrossRef]
  58. Hernández-Rivera, D.; Rodríguez-Roldán, G.; Mora-Martínez, R.; Suaste-Gómez, E. A Capacitive Humidity Sensor Based on an Electrospun PVDF/Graphene Membrane. Sensors 2017, 17, 1009. [Google Scholar] [CrossRef]
  59. Anderson, J.H.; Parks, G.A. Electrical conductivity of silica gel in the presence of adsorbed water. J. Phys. Chem. 1968, 72, 3662–3668. [Google Scholar] [CrossRef]
Jcs 07 00342 g001
Figure 1. Synthesis of GO from local Kazakh graphite “Ognevsky” using the Hummers method.
Figure 1. Synthesis of GO from local Kazakh graphite “Ognevsky” using the Hummers method.
Jcs 07 00342 g001
Jcs 07 00342 g002
Figure 2. Synthesis scheme of the GO, GO/CMC (0.03 g; 0.06 g; 0.15 g) membrane: (a) GO suspension; (b) CMC.
Figure 2. Synthesis scheme of the GO, GO/CMC (0.03 g; 0.06 g; 0.15 g) membrane: (a) GO suspension; (b) CMC.
Jcs 07 00342 g002
Jcs 07 00342 g003
Figure 3. Structure of the humidity sensor.
Figure 3. Structure of the humidity sensor.
Jcs 07 00342 g003
Jcs 07 00342 g004
Figure 4. Schematic view of the installation.
Figure 4. Schematic view of the installation.
Jcs 07 00342 g004
Jcs 07 00342 g005
Figure 5. SEM images of GO, GO/CMC membranes: (a) GO membrane; (b) GO—1%, CMC—0.03 g; (c) GO—1%, CMC—0.06 g; (d) GO—1%, CMC—0.15 g.
Figure 5. SEM images of GO, GO/CMC membranes: (a) GO membrane; (b) GO—1%, CMC—0.03 g; (c) GO—1%, CMC—0.06 g; (d) GO—1%, CMC—0.15 g.
Jcs 07 00342 g005
Jcs 07 00342 g006
Figure 6. XRD analysis of GO and GO/CMC samples. (0) Initial GO; (1) CMC; (2) GO/CMC 0.03 g; (3) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
Figure 6. XRD analysis of GO and GO/CMC samples. (0) Initial GO; (1) CMC; (2) GO/CMC 0.03 g; (3) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
Jcs 07 00342 g006
Jcs 07 00342 g007
Figure 7. FTIR spectra of synthetic and Ognevsky graphite and GO obtained from them. (0) Graphene oxide from synthetic graphite; (1) graphene oxide from Ognevsky graphite; (2) synthetic graphite; (3) Ognevsky graphite.
Figure 7. FTIR spectra of synthetic and Ognevsky graphite and GO obtained from them. (0) Graphene oxide from synthetic graphite; (1) graphene oxide from Ognevsky graphite; (2) synthetic graphite; (3) Ognevsky graphite.
Jcs 07 00342 g007
Jcs 07 00342 g008
Figure 8. FTIR spectra of GO and GO/CMC samples: (0) initial GO; (1) initial CMC; (2) GO/CMC 0.03 g; (3) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
Figure 8. FTIR spectra of GO and GO/CMC samples: (0) initial GO; (1) initial CMC; (2) GO/CMC 0.03 g; (3) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
Jcs 07 00342 g008
Jcs 07 00342 g009
Figure 9. Mechanical tensile strengthof GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Figure 9. Mechanical tensile strengthof GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Jcs 07 00342 g009
Jcs 07 00342 g010
Figure 10. Electrical characterization of GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Figure 10. Electrical characterization of GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Jcs 07 00342 g010
Jcs 07 00342 g011
Figure 11. Dynamics of response and recovery of GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Figure 11. Dynamics of response and recovery of GO and GO/CMC samples: (0) initial GO; (1) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (3) GO/CMC 0.15 g.
Jcs 07 00342 g011
Table 1. Crystallite sizes of GO and GO/CMC samples. (0) Initial GO; (2) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
Table 1. Crystallite sizes of GO and GO/CMC samples. (0) Initial GO; (2) GO/CMC 0.03 g; (2) GO/CMC 0.06 g; (4) GO/CMC 0.15 g.
SamplesParametersPeak Positionθ (°)
(2θ(°)/2)		βcos θ (°)Crystallite Size (Ǻ) DCrystallite Size (nm) D
K [38]Λ (Ǻ)2θ (°)FWHM
(In Degree)		FWHM
(In Radian)
00.941.54187.053.520.270.00480750.92279.3127.93
20.941.541811.895.941.770.0310410.9444.054.40
30.941.541811.355.672.490.04355570.8227.312.73
40.941.54189.704.853.780.06609830.133.050.30
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Kuanyshbekov, T.; Sagdollin, Z.; Zhasasynov, E.; Akatan, K.; Kurbanova, B.; Guseinov, N.; Tolepov, Z.; Kantay, N.; Beisebekov, M. Composite Membrane Based on Graphene Oxide and Carboxymethylcellulose from Local Kazakh Raw Materials for Possible Applications in Electronic Devices. J. Compos. Sci. 2023, 7, 342. https://doi.org/10.3390/jcs7080342

AMA Style

Kuanyshbekov T, Sagdollin Z, Zhasasynov E, Akatan K, Kurbanova B, Guseinov N, Tolepov Z, Kantay N, Beisebekov M. Composite Membrane Based on Graphene Oxide and Carboxymethylcellulose from Local Kazakh Raw Materials for Possible Applications in Electronic Devices. Journal of Composites Science. 2023; 7(8):342. https://doi.org/10.3390/jcs7080342

Chicago/Turabian Style

Kuanyshbekov, Tilek, Zhandos Sagdollin, Elzhas Zhasasynov, Kydyrmolla Akatan, Bayan Kurbanova, Nazim Guseinov, Zhandos Tolepov, Nurgamit Kantay, and Madyar Beisebekov. 2023. "Composite Membrane Based on Graphene Oxide and Carboxymethylcellulose from Local Kazakh Raw Materials for Possible Applications in Electronic Devices" Journal of Composites Science 7, no. 8: 342. https://doi.org/10.3390/jcs7080342

Article Metrics

Back to TopTop