Next Article in Journal
Synthesis and Thermo-Responsive Performance of Chitosan-Based UCST-Type Superplasticizers for Cement Composites
Next Article in Special Issue
Mechanical Pretreatment of Plant Biomass: Mechanisms, Energy Efficiency, Technologies, and Life Cycle Assessment
Previous Article in Journal
Upcycling Pineapple Waste Polysaccharides for Producing Reduced-Fat Sausage and Casings: A Circular Economy Approach
Previous Article in Special Issue
Comparative Assessment of Edible Oil Plant Lignocellulosic Biomass as Raw Material for a Fiber-Based Integrated Fractionation
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Polysaccharides
Volume 7
Issue 1
10.3390/polysaccharides7010016
polysaccharides-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
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers

by
Abdirakym Nakyp
1,2,*,
Elena Cherezova
1,
Yulia Karaseva
1,
Nurgali Akylbekov
3,
Rakhymzhan Turmanov
3,* and
Akbota Kuandykova
4
1
Institute of Polymers, Kazan National Research Technological University, 68 K. Marx Str., Kazan 420015, Russia
2
Center for Physical and Chemical Methods of Research and Analysis, Al-Farabi Kazakh National University, 71 Al-Farabi Ave., Almaty 050012, Kazakhstan
3
Laboratory of Engineering Profile “Physical and Chemical Methods of Analysis”, Korkyt Ata Kyzylorda University, 29 Aiteke Bi Str., Kyzylorda 120014, Kazakhstan
4
Department of Chemistry, Kazakh National Women’s Teacher Training University, 99 Aiteke Bi Str., Almaty 050012, Kazakhstan
*
Authors to whom correspondence should be addressed.
Polysaccharides 2026, 7(1), 16; https://doi.org/10.3390/polysaccharides7010016
Submission received: 18 November 2025 / Revised: 15 December 2025 / Accepted: 27 January 2026 / Published: 1 February 2026
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
Browse Figures
Versions Notes

Abstract

The present work investigates the effect of powdered lignocellulose from alfalfa straw obtained by a chemo-extrusion method, as well as its carboxymethylated derivative, on the physicomechanical properties and swelling behavior of vulcanizates based on nitrile butadiene rubber (NBR, BNKS-28 AMN grade). Carboxymethylation of lignocellulose was performed using microwave activation. The functional group composition of the modified lignocellulose was characterized by Fourier-transform infrared (FTIR) spectroscopy, which confirmed successful carboxymethylation and revealed a reduction in crystallinity. Thermogravimetric analysis (TGA) was used to determine the thermal stability of the swelling carboxymethylated fillers. The degree of crystallinity of the carboxymethylated swelling fillers was evaluated by X-ray diffraction (XRD). It was shown that the introduction of powdered lignocellulose and its carboxymethylated derivative into the rubber compounds lead to an increase in compound viscosity and prolong the optimum cure time, while having no effect on the scorch time, in a manner similar to that observed for the commercial product sodium carboxymethylcellulose (NaCMC). It has been shown that the introduction of powdered lignocellulose and its carboxymethylated derivative increases the tensile strength of the rubber and improves its resistance to the action of mineralized water compared with the samples containing NaCMC. It was also demonstrated that carboxymethylated lignocellulose exhibits enhanced sorption capacity comparable to that of NaCMC. Overall, carboxymethylation of lignocellulose derived from alfalfa straw significantly improves the stability and sorption characteristics of nitrile butadiene rubber composites. These findings indicate that carboxymethylated lignocellulose is a sustainable and effective alternative to industrial NaCMC for use as a functional filler in elastomeric materials.

Graphical Abstract

1. Introduction

Water-swelling rubbers represent a distinct class of elastomeric composites capable of increasing their volume upon contact with water or mineralized aqueous solutions due to liquid absorption by hydrophilic fillers within the polymer matrix. As a result, the material expands to fill gaps, cracks, and joints, forming a reliable seal without the application of external pressure. These characteristics make swelling rubbers highly in demand in engineering practice. They are widely used in the form of sealing profiles and cords for waterproofing construction and hydraulic structures, as well as sealing elements of swelling packers employed for zonal isolation of producing formations in the oil and gas industry, providing long-term protection against water or fluid ingress [1,2].
When selecting an elastomeric matrix for sealing and waterproofing systems, it is essential to consider the working media and operating conditions, as different rubbers exhibit markedly different resistance and durability profiles. Oil- and fuel-resistant nitrile butadiene rubber (NBR) is most commonly used as the elastomeric base for swelling rubbers due to its high thermal stability and chemical resistance [3]. Compared to natural rubber, chloroprene rubber, and ethylene–propylene–diene rubber (EPDM), NBR provides an optimal combination of mechanical strength, chemical stability, and compatibility with hydrophilic additives, making it the preferred material for water-swelling systems and sealing composites in the oil and gas industry [4]. Previous studies have shown that EPDM-based rubbers are prone to degradation under hydrocarbon exposure, limiting their applicability in such environments [5], whereas NBR-based materials retain mechanical integrity and dimensional stability even during prolonged contact with crude oil [6]. Moreover, studies on oil-swelling elastomers [7,8,9,10] emphasize that NBR-based rubbers offer the most favorable balance between swelling capacity and resistance to aggressive liquid media. The presence of polar nitrile groups in the NBR macromolecular structure enhances compatibility with polar fillers and aqueous environments compared to nonpolar rubbers, which is critical for the performance of water-swelling composites [11,12].
In recent decades, cellulose-based biofillers have attracted increasing attention from researchers and industry due to their environmental friendliness, affordability, and favorable thermomechanical properties [13,14]. The study [15] examined the potential of using cereal straw as an environmentally friendly reinforcing filler in composites based on natural rubber. The results showed that such composites exhibit high hardness, excellent barrier properties, and aging resistance comparable to or exceeding those of traditional fillers. The study [16] reported improvements in the mechanical, barrier, and damping properties of bioelastomer composites containing cereal straw. The study [17] demonstrated that treated rice straw fibers (20 parts per hundred rubber (phr)) can be used as a reinforcing filler for styrene–butadiene rubber (SBR). The authors of study [18] identified the potential interactions of biobased fillers derived from cellulose, chitosan, and starch with natural rubber. The research focused on the mechanical and thermal characteristics of the composites. The study [19] investigated the effect of bioadditives derived from alfalfa (biomass, bioash and lyophilizates) on natural rubber-based vulcanizates. The tensile strength values increased by 50% or more compared to the control sample.
In studies [20,21,22,23,24,25,26] the use of carboxylated cellulose derivatives obtained from wood raw materials as fillers capable of increasing the volume of rubber in aqueous environments has been described. The literature also provides examples of the use of modified cellulose fillers derived from various agricultural residues [15], including rice straw [17,27], as well as data emphasizing the importance of optimizing the structure and chemical composition of cellulose fillers [28].
In recent years, increasing attention has been paid to the potential use of powdered cellulose (PC) [7,29,30] and lignocellulosic products [31] derived from non-wood plant raw materials as swelling fillers. Powdered cellulose is characterized by a high specific surface area, hygroscopicity, and the ability to form time-stable gel-like dispersions. The properties of PC depend on the source of the cellulose material as well as on the method and conditions of its production [32,33]. Several methods for obtaining PC are distinguished: mechanical, chemical, and combined. The mechanical method involves grinding purified fibrous lignocellulose into a powder state through intensive mechanical action, such as in ball mills [34,35,36], rotor grinders, and other devices that provide mechanical disintegration of the initial fiber. Cellulosic materials subjected to such mechanical treatment generally exhibit a significant reduction in the degree of crystallinity (DC) of the original fibrous cellulose.
The production of powdered cellulose using chemical methods begins with the preparation of fibrous plant raw materials and includes the removal of lignin and hemicellulose to increase cellulose purity. This is achieved through acid or alkaline bleaching: acid hydrolysis breaks the bonds between hemicellulose and lignin, while alkaline treatment removes impurities from the fiber surface, facilitating its further processing [18]. The combined method for producing PC has become widespread; it involves the preliminary treatment of raw materials with alkaline solutions at elevated temperatures, followed by mechanical processing. Lignocellulosic fillers derived from agricultural waste represent a promising class of additives due to their low cost, rapid renewability, availability, and biodegradability [37,38,39]. At the same time, the use of alfalfa straw as a source of lignocellulose and its derivatives in water-swelling rubbers remains insufficiently studied.
The aim of this study is to evaluate the physicomechanical and sorption properties of water-swelling rubbers containing powdered lignocellulose obtained from alfalfa straw by a combined chemical–extrusion method and its carboxymethylated derivative as fillers.
The scientific novelty of this work lies in identifying the effect of lignocellulosic filler derived from alfalfa straw and its carboxymethylated derivative on the enhancement of tensile strength and the swelling capacity of the rubber.

2. Materials and Methods

2.1. Materials

Sodium carboxymethylcellulose (NaCMC) Polycell CMC 9 grade (Polycell CJSC, Vladimir, Russia) with a substitution degree of 0.8–0.9 was used as a swelling filler (SF), along with powdered lignocellulose derived from alfalfa straw and obtained using a combined technology [40,41], which included preliminary alkaline cooking (3% NaOH and 0.1% H2O2 for 60 min at 90–95 °C with a liquor ratio of 1:10) (lignin content—14.5%) (LC-Alf) [42]. Carboxymethylated lignocellulose (CMLC–Alf), obtained according to the procedure described [43], was used in this study. At the first stage, the reaction mixture comprising lignocellulose (5 g) and NaOH (pure for analysis, impurities not more than 1.0 wt.%, Bashkir Soda Company JSC, Sterlitamak, Russia) (4.2 g) in isopropyl alcohol (50 mL) was activated by microwave irradiation at a power of 350 W for 90 s. At this stage, sodium hydroxide reacts with cellulose, removing hydrogen from hydroxyl groups at specific positions [44]. The average bulk temperature did not exceed 75 °C. At the second stage, 6.9 g of monochloroacetic acid (MCAA) (chemically pure, impurities not more than 0.001 wt.%, Nouryon, Delfzijl, The Netherlands) was added to the activated reaction mixture, and the process was continued under the same conditions (350 W for 90 s). The precipitate was then separated using a Büchner funnel and washed with a 70% aqueous ethanol solution. To neutralize the alkali, several drops of acetic acid were added. The resulting product was filtered on a vacuum filter and subsequently air-dried. The lignin content was 7.0% [45], and the degree of carboxymethylation was 0.64 [46]. The swelling fillers were preliminarily fractionated using a sieve method. Based on previously obtained data [23] on the influence of the swelling filler particle size on the physical and mechanical properties of the rubber, the fraction with a particle size of 0.5–1 mm was used in this study.
Nitrile butadiene rubber BNKS-28 AMN grade (technical conditions TU 38.30313-2006, 2nd group, Krasnoyarsk Synthetic Rubber Plant JSC, Krasnoyarsk, Russia), which is one of the most commonly used elastomers in the formulations of water-swelling rubbers [25,47,48,49], was employed as the elastomeric matrix due to its good strength characteristics combined with satisfactory hardness. Sulfur-based curing was carried out using a vulcanization system containing a thiazole-type accelerator (2-mercaptobenzothiazole).
Technical sulfur (grade 9995, 1st class, SERA CJSC, Orenburg, Russia), vulcanization accelerator benzothiazole disulfide (MBTS, 2,2′-dithiobis(benzothiazole), State Standard GOST 7087-75 [50], BINA Group LLC, Moscow, Russia), the vulcanization activator zinc oxide (ZnO) (grade A, Empils-Zinc LLC, Rostov-on-Don, Russia), and stearic acid (grade T-32, Nefis Cosmetics JSC, Kazan, Russia) were used as the vulcanizing system components. Carbon black (CB) grade P 324 (Sterlitamak Petrochemical Plant JSC, Sterlitamak, Russia) was also incorporated into the formulation.
To improve the dispersion of the SF and other ingredients in the rubber compound, reduce the risk of premature vulcanization, and shorten the mixing and processing time, the plasticizer Oxal T-92—a by-product formed in the industrial production of isoprene monomer, which is a mixture of high-boiling dioxanes and alcohols—(Himavanguard LLC, Dzerzhinsk, Russia) was used. This plasticizer is well miscible with both the rubber matrix and the lignocellulosic filler [11]. The main composition of the high-boiling dioxane alcohols is described in [51].

2.2. Preparation of Rubber Compounds and Vulcanizates

The preparation of the rubber compounds was carried out in two stages. In the first stage, the ingredients (1, 3–6) of the base rubber compound (BRC) (Table 1) were mixed for 15 min on laboratory rollers LB 320 160/160 (Polimermash Group, Saint Petersburg, Russia) with a friction ratio of 1:1.25, at a roller surface temperature of 60 ± 5 °C. The gap between the rollers was initially set to 2.0 mm, which was gradually increased as the ingredients were added to ensure the uniform distribution of fillers. The mixture was then left for 24 h at room temperature to release internal stresses accumulated during the milling process and to allow structure relaxation. Following this, it was mixed with the curing agent (sulfur), the water-swelling filler and the plasticizer in a closed laboratory mixer—a Brabender “Plasti-Corder® Lab-Station” W50 E (Brabender, Duisburg, Germany)—for 6 min at a temperature of 60 °C and a rotor speed of 60 rpm, with a filling factor of 85%.
The vulcanization of the rubber compounds was carried out using a laboratory vulcanization press with induction-heated plates (model 100-400-2E, Krasin Plant JSC, Kirov, Russia) at a temperature of 160 °C in accordance with State Standard GOST 269-66 [52]. The thickness of the test sheets was 2.0 ± 0.2 mm. For the determination of elasticity and Shore hardness, disk-shaped specimens with a diameter of 50 mm and a thickness of 6 mm were prepared. The optimum cure time was determined based on the analysis of rheometric curves.

2.3. Methods

2.3.1. Fourier-Transform Infrared Spectroscopy

Functional group analysis of the powdered lignocellulose from alfalfa straw and its carboxymethylated derivative was performed using a Nicolet iS10 FTIR spectrometer (Thermo Fisher Scientific, Waltham, MA, USA). The spectra were recorded in the range of 600–4000 cm−1 with a resolution of 2 cm−1. IR spectra were recorded in ATR mode.

2.3.2. Thermogravimetric Analysis (TGA)

The thermal stability of the prepared rubber composites was evaluated in the temperature range of 25–500 °C under a nitrogen atmosphere using a thermal analyzer STA 6000 (PerkinElmer, Waltham, MA, USA) at a heating rate of 5 °C/min.

2.3.3. Particle Size Analysis of Cellulosic Fillers

Particle size distribution was determined by laser diffraction using a Bettersizer 2600 analyzer (Bettersize Instruments Ltd., Dandong, China). Ethyl alcohol was used as the dispersion medium to ensure effective particle separation and to minimize particle aggregation during the measurements.

2.3.4. Scanning Electron Microscope (SEM)

The distribution of water-swelling fillers and the morphology of the rubbers were investigated on a scanning electron microscope (SEM) JSM-7800F (Jeol, Akishima, Japan) in the secondary electron mode at an accelerating voltage of 1.0–1.5 kV. The samples for the study (brittle chips) were obtained by the brittle fracture method at liquid nitrogen temperature.

2.3.5. Rheometric Characteristics of the Rubber Compounds

The rheometric characteristics of the rubber compounds were determined using a Moving Die Rheometer (MDR) MD-3000A (Gotech, Taichung, Taiwan) in accordance with State Standard GOST 12535-84 [53] (ASTM D5289) at a temperature of 160 °C for 30 min.

2.3.6. Determination of the Swelling Degree of the Rubbers

The swelling degree of the rubbers in aqueous media was determined in accordance with State Standard GOST R ISO 1817-2009 [54] by measuring the change in sample mass using the following equation:
α = m − m 0 m 0 × 100 %
where m is the mass of the swollen sample and m0 is the initial mass of the sample. To determine the swelling capacity of the rubber, vulcanized specimens with D = 10 mm, h = 10 mm were used. Swelling tests were carried out in formation water, the composition of which is presented in Table 2.

2.3.7. Determination of the Physical and Mechanical Properties of the Rubbers

The elastic and strength properties of the rubbers—tensile strength (TS) and elongation at break (ε)—were determined in accordance with State Standard GOST 270-81 [55] using a TRM-P 50 C1 Tochline universal electromechanical testing machine (NPO Tochpribor, Russia) at a crosshead speed of 500 mm/min and a temperature of 23 ± 2 °C.
Rebound resilience was determined using a Shoba-type UMR-1 rebound resilience tester (Polymermash Group LLC, St. Petersburg, Russia) in accordance with State Standard GOST 27110-86 [56]. Shore A hardness of the rubber composites was measured with a TH-200 portable durometer (TIME Group, Beijing, China) according to State Standard GOST 263-75 [57].
The resistance of the rubbers to the effects of mineralized water was assessed based on the changes in their physical and mechanical properties after exposure to formation water for 72 h at room temperature.

3. Results and Discussion

The properties of cellulose obtained from different types of raw materials vary due to the molecular heterogeneity of its structure, which is determined by the nature and characteristics of inter- and intramolecular interactions. To study the structure and hydrogen bonding in cellulose, the highly sensitive method of FTIR spectroscopy is commonly used [58]. In this study, FTIR spectra were recorded for lignocellulose (LC-Alf), its carboxymethylated derivative (CMLC-Alf), and NaCMC in Attenuated Total Reflectance mode (FTIR-ATR) within the wavelength range of 600–4000 cm−1 (Figure 1).
The main absorption bands in the FTIR spectra (Figure 1) of the LC-Alf, CMLC-Alf, and commercial NaCMC samples are presented in Table 3.
The broad absorption band in the range of 3000–3700 cm−1 in the FTIR spectrum of LC-Alf corresponds to the stretching vibrations of hydroxyl groups involved in hydrogen bonding. The broadening of this peak is attributed to the presence of several types of hydrogen bonds in the cellulose structure—intramolecular (O2–H···O6, O3–H···O5) and intermolecular (O6–H···O3)—which give rise to absorption bands at 3430, 3350, and 3275 cm−1, respectively [59]. It should be noted that the hydroxyl groups of lignin also contribute to absorption in this spectral region. The stretching vibrations of the CH2 and CH groups of cellulose, as well as those associated with lignin, appear in the range of 2800–3000 cm−1. Due to the strong interaction of CH2 groups with neighboring structural elements, it is difficult to distinguish between the stretching vibration frequencies of CH2 and CH groups. The shape of the peak at 2926 cm−1, its splitting, and its intensity are determined by the presence of different conformers (rotations of the CH2OH groups around the C5–C6 bond), as well as by the presence of strong bonds between cellulose and lignin [60]. The broad band at 1580 cm−1 is attributed to the ν(C=C) vibrations of the aromatic rings of lignin [19]. The frequency range of 1400–1500 cm−1 in the spectrum of LC-Alf corresponds to the vibrations of oxymethyl groups present in different conformational states. The FTIR spectra of lignocellulose also contain a band of stretching vibrations at 900 cm−1. This band is referred to as the “amorphous band” since its intensity changes upon mechanical or chemical modification of cellulose and is associated with alterations in the pyranose ring and deformation of the C1–H bond in the amorphous regions of cellulose [61]. The absorption band at 1317 cm−1 corresponds to deformation vibrations of the C–H bond.
In the spectrum of CMLC-Alf, a broad band with a maximum at 3343 cm−1 is observed, corresponding to the stretching vibrations of O–H groups, along with peaks at 2920 cm−1 and 2871 cm−1 associated with CH2 and CH vibrations. The appearance of a band at 1715 cm−1 indicates the presence of carboxyl groups, while the enhancement of signals at 1061 cm−1 confirms modification of the glycosidic structure and the presence of C–O–C bridging bonds.
In the FTIR spectrum of the NaCMC sample, a broad and intense peak of O–H stretching vibrations with a maximum at 3415 cm−1 is observed. The bands in the range of 1605–1637 cm−1 are associated with the bending vibrations of bound water molecules (H–OH), while the signal at 1595 cm−1 corresponds to the presence of the carboxylate anion. The intense peaks in the region of 1157–1059 cm−1 are attributed to C–O–C vibrations of the pyranose ring, and the band at 840 cm−1 reflects β-glycosidic bond vibrations.
It is well known that the swelling ability of cellulose is associated with the presence of amorphous regions, into which liquids can penetrate most easily. Several studies [62,63,64,65] have proposed using FTIR spectra to calculate the crystallinity index of cellulose.
In the work of O’Connor [66], the lateral order index was used to determine the crystallinity degree—the ratio of the absorption band intensities D1430/D900. These bands are highly sensitive to the degree of crystallinity and amorphousness of cellulose. Nelson and co-authors [61] introduced the total crystallinity index, defined as the ratio of the absorption band intensities D1375/D2900. Table 4 presents the crystallinity values of the samples calculated from the FTIR spectra using both methods.
The presented data show that the values obtained by both methods are comparable. The LC-Alf sample exhibits the highest crystallinity index of 0.48 (0.42). Upon carboxymethylation of LC-Alf, the crystallinity decreases to 0.22 (0.18) for the CMLC-Alf sample, indicating that the chemical modification leads to the disruption of ordered regions in lignocellulose and an increase in the proportion of the amorphous phase.
Based on a review of the literature, the crystallinity index of alfalfa-derived lignocellulose (LC–Alf) has been reported to be approximately 77% [40]. Following carboxymethylation of cellulose, a decrease in the crystallinity index is commonly observed, which is attributed to disruption and distortion of the crystalline structure caused by swelling of the cellulose macromolecules. This structural transformation results in a further reduction in crystallinity; reported crystallinity index values for sodium carboxymethyl cellulose (NaCMC) typically decrease to approximately 32–45%, depending on the degree of substitution and the preparation method. Such behavior is well documented in the scientific literature and is supported by X-ray diffraction studies, which demonstrate the disappearance of sharp crystalline peaks and an increase in the amorphous fraction after carboxymethylation [67,68,69]. The reduction in crystallinity is generally attributed to the introduction of carboxymethyl groups, which disrupt the hydrogen-bonding network stabilizing the crystalline lattice of native cellulose. As a result, the amorphous phase content increases, enhancing accessibility for chemical modification and, consequently, improving the functional properties of the material.
An important criterion for the use of additives in composite formulations is their thermal stability, since rubber compounds are processed at a temperature of 160 °C. Thermograms were recorded in a nitrogen atmosphere over the temperature range of 25–500 °C at a heating rate of 5 °C/min (Figure 2).
On the thermogram of the LC-Alf sample, a mass loss of about 4% was observed up to 150 °C, associated with the desorption of residual moisture. A rapid mass-loss region in the temperature range of 250–350 °C corresponded to the thermochemical degradation of the sample. This was followed by a slow mass-loss stage, reaching a plateau at around 450 °C. The residual mass of the sample at 500 °C was approximately 28%. Carboxymethylation of LC-Alf shifted the temperature range of the rapid decomposition stage for CMLC-Alf toward lower temperatures (240–318 °C). At the same time, the residual mass of the CMLC-Alf sample at 500 °C was significantly higher (45%) compared to LC-Alf, indicating that pyrolysis of the carboxymethylated cellulose derivative results in the formation of a more thermally stable carbonaceous structure than that produced from LC-Alf. These results are consistent with literature data, which report a noticeably higher yield of carbonaceous residue for carboxymethylated cellulose (34.2% at 600 °C) compared to cellulose (19.6%) [70].
For comparison, a thermogram of the commercial NaCMC sample was recorded. On the TG curve, desorption of residual moisture was observed up to 150 °C, during which the sample lost about 10% of its mass. Rapid thermochemical decomposition with the formation of volatiles began at temperatures above 240 °C, which is comparable to CMLC-Alf, and was completed at 303 °C. This was followed by a region of slow mass loss. The inflection points observed in our study are close to those reported in [68]. The residual mass of the sample at 500 °C is approximately 55% of the initial mass ℃.
Analysis of the particle size distribution of the investigated cellulose-containing materials revealed pronounced differences in the granulometric composition of NaCMC, alfalfa-derived lignocellulose (LC-Alf), and carboxymethylated lignocellulose (CMLC-Alf) (Figure 3). The particle size characteristics exhibit broad ranges, reflecting different degrees of dispersibility and material heterogeneity. The largest particles were observed for the NaCMC sample, with a median particle size D50 of 560.8 µm and an upper percentile D90 approaching 1 mm (999.8 µm). The wide distribution range (from D10 = 244.3 µm to D90 = 999.8 µm) indicates pronounced polydispersity, which can be attributed to the specific features of the industrial production process of this type of carboxymethyl cellulose. The presence of large agglomerates may be associated with incomplete hydration and secondary particle aggregation in the aqueous medium. The LC-Alf sample exhibited a coarser particle size distribution with a median diameter D50 = 325.1 µm and a shift in the distribution curve toward larger particle sizes. The values of D10 = 130 µm and D90 = 598.6 µm indicate a more uniform structure compared with NaCMC, although with lower dispersibility than CMLC-Alf. The CMLC-Alf. sample was characterized by the smallest median particle size (D50 = 161 µm) and the narrowest distribution, with D10 and D90 23.25 and 503.3 µm, respectively. This indicates a high degree of dispersion and a predominance of fine fractions, which is also supported by the shape of the distribution curve. The presence of a substantial fraction of particles smaller than 100 µm suggests enhanced reactivity of the material due to an increased specific surface area.
The high content of swelling filler (SF) (150 parts per 100 rubber) in the vulcanizates significantly affects the formation of the composite’s microstructure. Increasing the filler concentration was typically accompanied by the formation of particle agglomerates and deterioration of their dispersion, which is confirmed by studies on the filling of rubber composites with cellulose-containing fillers and the observed morphology of compounds of a similar nature [71]. The micrographs (Figure 4) clearly show pronounced phase boundaries, localized filler accumulations, and a distinct surface microrelief of the vulcanizates, indicating non-uniform phase distribution and limited wetting of the filler by the rubber matrix.
Similar morphological features associated with structural heterogeneity have also been reported for composites with high cellulose fiber content, where impaired dispersion leads to the formation of noticeable agglomerates within the polymer matrix [72]. These microstructural characteristics suggest weak interfacial adhesion between the filler and the matrix, which may result in stress concentration in agglomerated regions and negatively affect the physicomechanical properties of the composites due to defect formation and uneven stress distribution [18].
Given the differences in the structure—and consequently in the properties—of the obtained swelling filler samples, differences in the properties of the swelling rubbers can also be expected. Table 5 presents (Figure 5) the results of rheometric analysis of rubber compounds based on nitrile–butadiene rubber BNKS-28 AMN grade filled with various swelling fillers. The main parameters include the scorch time (ts), the minimum (ML) and maximum (MH) torque values, and the time required to reach 90% of the vulcanization degree—optimum cure time (t90). The measurements were carried out at 160 °C with a test duration of 30 min. Samples WSR-1–WSR-3 contain 100 phr of the swelling filler, while samples WSR-4–WSR-6 contain 150 phr of the swelling filler (Table 1).
According to the obtained data, the scorch time of the samples filled with the swelling fillers remains at the level of the control sample that contains no filler. This indicates the chemical inertness of the introduced swelling fillers with respect to the vulcanization process. In general, the incorporation of the swelling filler (SF) into the rubber compound leads to an increase in the maximum torque [72]. This effect is due to the fact that cellulose is a rigid-chain polymer characterized by a Kuhn segment exceeding 140 Å [73], as it contains a cyclic repeating unit and highly polar OH-groups that participate in strong intermolecular interactions. Therefore, the incorporation of cellulose-containing swelling fillers into the rubber formulation leads to a significant restriction of deformation and chain mobility, thereby increasing the compound viscosity. The time required to reach the optimum degree of vulcanization for the samples filled with the swelling fillers increases compared to the base rubber compound, which may be associated with the high filler loading. Therefore, the incorporation of cellulose-containing swelling fillers into the rubber formulation significantly restricts chain deformation and mobility, thereby increasing the compound viscosity. The time required to reach the optimum degree of vulcanization for the samples filled with the swelling fillers increases compared to the base rubber compound, which may be attributed to the high filler loading.
The decrease in minimum torque (ML) observed for sample WSR-3 containing carboxymethylated lignocellulose (CMLC-Alf), compared with sample WSR-2 containing unmodified lignocellulose (LC-Alf), may indicate a reduction in the crystallinity of lignocellulose after carboxymethylation. According to reported literature data, carboxymethylation of cellulose leads to a significant decrease in its crystallinity, and at high degrees of substitution the crystalline phase may disappear completely [74,75]. This reduction in crystallinity is attributed to the disruption of hydrogen bonds that stabilize the crystalline lattice. In the context of rubber compounds, this implies that the swelling filler becomes less rigid and offers lower resistance to shear in the uncured matrix, which is reflected in a lower ML value for the compound containing carboxymethylated lignocellulose compared with the non-carboxymethylated counterpart.
The amount of the swelling filler also affects the rheometric properties of the samples. Increasing the filler content to 150 phr (WSR4–WSR6) leads to an increase in torque values compared with the samples containing 100 phr (WSR1–WSR3).
In Table 6, the results illustrating the influence of the type and amount of the swelling filler on the physical and mechanical properties of the rubbers are presented. The control sample (BRS) is characterized by the following physicomechanical properties. The tensile strength (TS) was 13.8 MPa, the elongation at break (ε) was 480%, the rebound resilience (R) was 34%, and the Shore A hardness (HSA) was 65 units. These values indicate a balanced combination of strength and elasticity, as well as a relatively high ability of the material to recover after tensile deformation.
According to the experimental data, the highest TS is observed for the swelling rubber filled with 100 phr of LC-Alf (WSR-2, 9.1 MPa). This result is apparently due to the fact that LC-Alf contains about 14% lignin. The obtained results are consistent with literature reports indicating the reinforcing properties of lignin. In particular, ref. [76] presents data on the reinforcing ability of lignin and the resulting improvement in the physical–mechanical properties of polymer materials. According to ref. [77], the incorporation of Klason lignin into natural-rubber-based composites leads to an increase in tensile strength compared with the composite without lignin. Ref. [72] further emphasizes that lignin, owing to its phenolic and aromatic structure as well as its relative hydrophobicity, can enhance interfacial adhesion and improve the mechanical properties of rubber biocomposites. The tensile strength of the rubber filled with CMLC-Alf (WSR-3, 6.4 MPa) decreases due to the reduced lignin content (7%) and the lower degree of crystallinity. The rubber containing NaCMC, which is characterized by the absence of lignin and a low crystallinity level, exhibits the lowest strength (WSR-1, 4.0 MPa). The presence of a rigid-chain structure in the swelling filler restricts the mobility of the polymer chains, which is reflected in the low elongation at break (ε) and the high Shore A hardness (HSA). The rubber filled with LC-Alf (WSR-2) exhibits an elongation at break of ε = 60% and a hardness of 95 Shore A units. Amorphization of the filler structure and the reduction in hydrogen-bond strength during carboxymethylation increase the segmental mobility of the polymer chains, which is reflected in the higher elongation at break and lower hardness of the rubber filled with CMLC-Alf (WSR-3, ε = 160%, HSA = 79). The highest elongation at break was observed for the sample containing NaCMC (WSR-1), which has a high degree of carboxymethylation. Its elongation reached 280% at a comparatively low hardness of 72 Shore A units.
When the amount of the rigid-chain swelling fillers is increased to 150 phr (WSR-4, WSR-5, WSR-6), a decrease in tensile strength and elongation at break is observed, along with an increase in Shore A hardness. This is due to the fact that adding larger amounts of a rigid-chain filler leads to an increase in compound viscosity. The higher viscosity, in turn, creates unfavorable conditions for the uniform distribution of the ingredients and the applied load, which results in reduced material strength and elasticity. In particular, the tensile strength of the sample containing 150 phr of LC-Alf (WSR-5) decreased from 9.1 to 7.9 MPa, while ε decreased from 60% to 50%, and the hardness increased from 95 to 102 Shore A units. When the amount of NaCMC was increased, the tensile strength and elongation at break of the rubber (WSR-4) decreased to 3.5 MPa and 220%, respectively, while the HSA value increased from 72 to 78 Shore A units. A similar trend was observed for the sample containing CMLC-Alf (WSR-6): the tensile strength decreased to 5.8 MPa, the elongation at break decreased to 130%, and the Shore A hardness increased to 84 units. The obtained trends are consistent with the results reported in the literature [78,79].
Next, the swelling behavior of the rubber samples in mineralized water was investigated. The swelling capacity of the polymer was evaluated based on the mass of liquid absorbed by the polymer relative to its initial mass. The swelling mechanism involves the penetration of water molecules into the near-surface layers of the polymer and the solvation of specific segments of the polymer chain. As a result, the macromolecules become “loosened,” which facilitates further ingress of water molecules and leads to an increase in the mass and volume of the polymer. In the samples containing swelling fillers, the filler particles interact with water molecules through hydrogen bonding—this serves as the primary driving force for water uptake by the polymer chains. Water is drawn into the elastomer network due to the activity of the filler; however, the dispersion of water is limited by the crosslinks in the elastomer chains, as well as by the intrinsic absorption capacity of the swelling filler. As a result, resistance to swelling is formed. An energetic imbalance arises, and the system tends to achieve equilibrium by establishing a diffusion gradient between the swelling polymer and the surrounding solution, which ultimately leads to a balanced state.
Each repeating unit of the cellulose molecule contains three hydroxyl groups—two secondary (at positions C-2 and C-3) and one primary (at position C-6), which differ in their electrolytic reactivity [80,81]. Since in carboxymethylated cellulose the primary hydroxyl group is substituted with a carboxyl group, differences in the swelling behavior of the filler can be expected.
Not only the type of swelling filler but also its amount influences the swelling capacity of the rubbers, as further examined in this work. Figure 6 shows the swelling kinetics of the rubber samples filled with different swelling fillers during exposure to formation water (pH 6.3). The highest initial swelling in the saline solution was observed for the sample filled with 150 phr of NaCMC (WSR-4). During the first 2–3 days, the swelling degree reached 78%, after which partial dissolution and leaching of the swelling filler occurred, and the value stabilized at about 65% for the remainder of the test period. For the sample containing 100 phr of NaCMC (WSR-1), the swelling during the first two days was 71%, followed by stabilization at around 61%. This behavior is attributed to the high degree of carboxymethylation (0.9). Carboxyl groups, being electrolytic in nature, enhance the swelling capacity of the polymer material.
The swelling capacity of the rubber filled with CMLC-Alf during the first 2–3 days is lower compared to that of NaCMC due to its lower degree of carboxymethylation (0.64). In addition, CMLC-Alf contains about 7% lignin. Since lignin is known to be hydrophobic, it can reduce the water absorption of lignocellulose-based materials [39,82]. At equilibrium, the swelling of sample WSR-3 (100 phr of CMLC-Alf) in formation water reached 58%, while for sample WSR-6 (150 phr of CMLC-Alf) it was 65%. In this case, however, no dissolution or leaching of the swelling filler was observed.
The samples filled with LC-Alf (WSR-2 and WSR-5) exhibit low swelling values. The relative mass increase of these samples was 17–20%. This behavior is attributed to their high degree of crystallinity, the absence of carboxyl groups—which enhance hydrophilicity by converting the filler into a polyelectrolyte—as well as the presence of lignin (14%) in the structure of the swelling filler. Lignin contributes to the formation of a denser, less water-permeable polymer network.
Thus, it can be concluded that the swelling degree of the rubber composites is determined not only by the nature and chemical composition of the filler (including the content of hydrophobic lignin and hydrophilic carboxyl groups). When carboxyl groups interact with an ionic medium, carboxylate forms (–COO−) are generated. The resulting carboxylates have increased polarity and are capable of binding significant amounts of water through ion–dipole interactions. As a result, the swelling degree increases (Figure 7).
The physical and mechanical properties of the rubbers were further examined after a 3-day exposure to formation water (Table 7). After exposure to formation water, the samples containing lignocellulosic fillers (LC-Alf and CMLC-Alf) retained their tensile strength to a greater extent. In contrast, the samples with NaCMC showed a significant reduction in strength (up to 50%), whereas the water-swelling rubbers filled with LC-Alf and CMLC-Alf lost only 8–19%. This effect is associated with the presence of lignin, which enhances interfacial adhesion and increases the hydrophobicity of the system [83]. Lignin present in the lignocellulosic fillers provides a pronounced reinforcing effect, thereby ensuring the preservation of the mechanical properties of the composite when exposed to an aqueous medium. Several review studies have demonstrated that, under appropriate processing conditions and with good dispersion, lignin can provide a noticeable reinforcement of the mechanical properties of rubber composites, acting as an environmentally friendly alternative to conventional fillers [84,85]. An increase in the amount of swelling filler from 100 to 150 phr slightly improves the stability of the tensile strength parameter; however, higher filler loadings lead to partial loss of structural integrity and a decrease in the absolute tensile strength values.
According to the results of the conducted studies, the optimal content of the swelling filler in water-swelling rubbers—providing the best balance between physical–mechanical properties and swelling capacity—is 100 phr of the filler. This dosage is more preferable compared with 150 phr. Such a ratio ensures uniform distribution of the filler particles within the polymer matrix, promotes the formation of strong interfacial bonds, and prevents agglomeration of solid particles, which is observed at higher filler concentrations and leads to a decrease in the elastic and strength properties of the composite.

4. Conclusions

The influence of fillers derived from alfalfa straw and its carboxymethylated derivative on the vulcanization, physical–mechanical, and sorption properties of limited-swelling rubbers based on nitrile–butadiene rubber BNKS-28 AMN grade was investigated. The content of the swelling filler in the rubber ranged from 100 to 150 parts per hundred rubber.
Carboxylation of powdered lignocellulose was carried out using microwave activation. The functional group composition of the obtained product was determined. IR spectroscopy confirmed that carboxymethylation is accompanied by a decrease in the degree of crystallinity. It was established that the incorporation of powdered lignocellulose produced by the chemo-extrusion method, as well as its carboxymethylated derivative, into rubber compounds leads to an increase in viscosity and a longer time to reach the optimum degree of vulcanization, without affecting the scorch time. A similar effect on the rheometric characteristics was observed when the commercial NaCMC product was introduced into the rubber compound.
Mechanical testing showed that the tensile strength of the rubber filled with the lignocellulosic filler and its carboxymethylated derivative is higher compared to the rubber containing the commercially used NaCMC filler. At the same time, carboxymethylation of lignocellulose led to a decrease in the tensile strength of the rubber and an increase in its elasticity due to the reduced degree of crystallinity. It was shown that the tensile strength of the rubber filled with lignocellulosic fillers derived from alfalfa straw changes to a lesser extent after 72 h of exposure to formation water compared with the rubber filled with NaCMC. After exposure to formation water, the samples filled with the lignocellulose obtained from alfalfa straw by the chemo-extrusion method exhibit the highest tensile strength.
Based on a comparative assessment of mechanical strength and sorption properties, it was determined that the sample containing alfalfa-derived lignocellulose (LC–Alf) at a loading of 100 phr (parts per hundred rubber) provides the most balanced performance. Compared with a filler content of 150 phr, the formulation with 100 phr exhibits an optimal balance between mechanical strength, resistance to water exposure, and controlled swelling behavior. The developed material shows strong potential for application in engineering fields requiring a combination of mechanical integrity and regulated swelling, particularly in sealing systems, drilling operations, and oilfield exploitation, including casing sealing elements, elastomeric gaskets, and swelling tapes.

Author Contributions

Conceptualization, E.C. and Y.K.; methodology, A.N., N.A., A.K. and Y.K.; validation, A.N., E.C. and Y.K.; formal analysis, A.N.; investigation, A.N.; resources, A.N., A.K. and R.T.; data curation, A.N.; writing—original draft preparation, A.N. and E.C.; writing—review and editing, A.N., E.C. and Y.K.; visualization, A.N., E.C. and Y.K.; supervision, E.C.; funding acquisition, N.A. and R.T.; project administration, E.C.; All authors have read and agreed to the published version of the manuscript.

Funding

The study was carried out with partial financial support from the Non-Commercial Joint-Stock Company “Korkyt Ata Kyzylorda University” (grant No. 79-05-24).

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding authors.

Conflicts of Interest

The author Rakhymzhan Turmanov has received to receive research grants from Non-Commercial Joint-Stock Company “Korkyt Ata Kyzylorda University”. The funding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Abbreviations

The following abbreviations are used in this manuscript:
BRCBasic rubber compound
CMLC-Alf.Carboxymethylated alfalfa lignocellulose
LC-Alf.Alfalfa lignocellulose
NaCMCSodium salt of carboxymethyl cellulose
PCPowdered cellulose
SFSwelling filler
WSRWater-swelling rubber
TSTensile strength

References

  1. Dehbari, N.; Tang, Y. Water Swellable Rubber Composites: An Update Review from Preparation to Properties. J. Appl. Polym. Sci. 2015, 132, 42786. [Google Scholar] [CrossRef]
  2. Karmanova, O.V.; Moskalev, A.S.; Shutilin, Y.F.; Vlasova, L.A. Unvulcanized Elastomeric Waterproofing Materials for Construction Application. Proc. Vor. State Univ. Eng. Technol. 2016, 228–232. [Google Scholar] [CrossRef][Green Version]
  3. Beknazarov, K.; Tokpayev, R.; Nakyp, A.; Karaseva, Y.; Cherezova, E.; El Fray, M.; Volfson, S.; Nauryzbayev, M. Influence of Kazakhstan’s Shungites on the Physical–Mechanical Properties of Nitrile Butadiene Rubber Composites. Polymers 2024, 16, 3370. [Google Scholar] [CrossRef]
  4. Polgar, L.M.; Fallani, F.; Cuijpers, J.; Raffa, P.; Broekhuis, A.A.; van Duin, M.; Picchioni, F. Water-Swellable Elastomers: Synthesis, Properties and Applications. Rev. Chem. Eng. 2018, 35, 45–72. [Google Scholar] [CrossRef]
  5. Zielińska, M.; Seyger, R.; Dierkes, W.K.; Bielinski, D.; Noordermee, J.W.M. Swelling of EPDM Rubbers for Oil-Well Applications as Influenced by Medium Composition and Temperature. Polimery 2016, 20, 6–17. [Google Scholar]
  6. Ren, W.; Peng, Z.; Zhang, Y.; Zhang, Y. Preparation and Properties of a Water-Swelling Rubber by in Situ Formed Lithium Acrylate in Nitrile Rubber. Polym. Polym. Compos. 2005, 13, 181–190. [Google Scholar] [CrossRef]
  7. Cherezova, E.N.; Karaseva, Y.S.; Momzyakova, K.S. Hydrophilic Rubber Based on Butadiene–Nitrile Rubber and Phytogenic Powdered Cellulose. Polym. Sci. Ser. D 2022, 15, 118–121. [Google Scholar] [CrossRef]
  8. Vaniev, M.A.; Lopatina, S.S.; Sychev, N.V.; Savchenko, Y.Y.; Bruk, A.D.; Novakov, I.A. Properties Of Water-Swellable Compounds Based On Nitrile Rubber With Varied Acrylonitrile Content. Rubber Chem. Technol. 2021, 94, 591–599. [Google Scholar] [CrossRef]
  9. Wei, D.; He, N.; Zhao, J.; Wang, Z. Mechanical, Water-Swelling, and Morphological Properties of Water-Swellable Thermoplastic Vulcanizates Based on High Density Polyethylene/Chlorinated Polyethylene/Nitrile Butadiene Rubber/Cross-Linked Sodium Polyacrylate Blends. Polym. Plast. Technol. Eng. 2015, 54, 616–624. [Google Scholar] [CrossRef]
  10. Lv, X.; Song, S.; Wang, H.; Wang, S. Effect of CO2 Gas on the Swelling and Tribological Behaviors of NBR Rubber in Water. J. Mater. Sci. Technol. 2015, 31, 1282–1288. [Google Scholar] [CrossRef]
  11. Cherezova, E.; Karaseva, Y.; Nakyp, A.; Nuriev, A.; Islambekuly, B.; Akylbekov, N. Influence of Partially Carboxylated Powdered Lignocellulose from Oat Straw on Technological and Strength Properties of Water-Swelling Rubber. Polymers 2024, 16, 282. [Google Scholar] [CrossRef]
  12. Zang, L.; Chen, D.; Cai, Z.; Peng, J.; Zhu, M. Preparation and Damping Properties of an Organic–Inorganic Hybrid Material Based on Nitrile Rubber. Compos. Part B Eng. 2018, 137, 217–224. [Google Scholar] [CrossRef]
  13. Mokhothu, T.H.; John, M.J.; John, M.J. Bio-Based Fillers for Environmentally Friendly Composites. In Handbook of Composites from Renewable Materials; Wiley: Hoboken, NJ, USA, 2017; pp. 243–270. [Google Scholar]
  14. Kuan, H.T.N.; Tan, M.Y.; Shen, Y.; Yahya, M.Y. Mechanical Properties of Particulate Organic Natural Filler-Reinforced Polymer Composite: A Review. Compos. Adv. Mater. 2021, 30. [Google Scholar] [CrossRef]
  15. Masłowski, M.; Miedzianowska, J.; Strzelec, K. Natural Rubber Composites Filled with Crop Residues as an Alternative to Vulcanizates with Common Fillers. Polymers 2019, 11, 972. [Google Scholar] [CrossRef]
  16. Masłowski, M.; Miedzianowska, J.; Strąkowska, A.; Strzelec, K.; Szynkowska, M.I. The Use of Rye, Oat and Triticale Straw as Fillers of Natural Rubber Composites. Polym. Bull. 2018, 75, 4607–4626. [Google Scholar] [CrossRef]
  17. Khalaf, E.S.A. Studying the Effect of Untreated and Treated Rice Straw on Different Properties of Carbon Black Filled Styrene-Butadiene Rubber Composites. J. Rubber Res. 2024, 27, 639–652. [Google Scholar] [CrossRef]
  18. Thomas, S.K.; Parameswaranpillai, J.; Krishnasamy, S.; Begum, P.M.S.; Nandi, D.; Siengchin, S.; George, J.J.; Hameed, N.; Salim, N.V.; Sienkiewicz, N. A Comprehensive Review on Cellulose, Chitin, and Starch as Fillers in Natural Rubber Biocomposites. Carbohydr. Polym. Technol. Appl. 2021, 2, 100095. [Google Scholar] [CrossRef]
  19. Miedzianowska-Masłowska, J.; Masłowski, M.; Strzelec, K. Alfalfa/Lucerne (Medicago sativa) as a Source of Functional Bioadditives for Elastomeric Natural Rubber Composites. Polymers 2024, 16, 3444. [Google Scholar] [CrossRef]
  20. Liu, C.; Ding, J.; Zhou, L.; Chen, S. Mechanical Properties, Water-swelling Behavior, and Morphology of Water-swellable Rubber Prepared Using Crosslinked Sodium Polyacrylate. J. Appl. Polym. Sci. 2006, 102, 1489–1496. [Google Scholar] [CrossRef]
  21. Zhang, S.T. Preparation, Water Absorbent and Mechanical Properties of Water Swellable Rubber. Plast. Rubber Compos. 2012, 41, 326–331. [Google Scholar] [CrossRef]
  22. Jiang, X.L.; Hu, K.; Yang, P.; Ren, J. Study on Preparation and Properties of Water Swellable Rubber Modified by Interpenetrating Polymer Networks. Plast. Rubber Compos. 2013, 42, 327–333. [Google Scholar] [CrossRef]
  23. Cherezova, E.N.; Karaseva, Y.S.; Galikhanov, M.F. Influence of Sodium Carboxymethyl Cellulose on the Properties of Highly Filled Vulcanizates Based on Nitrile-Butadiene Rubber (in Russian). Prom. Proizv. Ispol’z. Elastom. 2021, 3, 33–37. [Google Scholar] [CrossRef]
  24. Tang, Y.; Zhou, D.; Zhang, J. Novel Polyvinyl Alcohol/Styrene Butadiene Rubber Latex/Carboxymethyl Cellulose Nanocomposites Reinforced with Modified Halloysite Nanotubes. J. Nanomater. 2013, 2013. [Google Scholar] [CrossRef]
  25. Cherezova, E.N.; Karaseva, Y.S. Water-Swelling Rubbers Filled With Modified Cotton Powder. ChemChemTech 2022. [Google Scholar] [CrossRef]
  26. Cherezova, E.N.; Galikhanov, M.F.; Karaseva, Y.S.; Nakyp, A.M. Impact of the Composition of Rubbers Filled with Carboxymethyl Cellulose on Their Properties. Russ. J. Appl. Chem. 2023, 96, 462–467. [Google Scholar] [CrossRef]
  27. Fayzullin, I.; Gorbachev, A.; Volfson, S.; Zhakypova, G.; Uderbayev, S.; Nakyp, A.; Akylbekov, N. Influence of Different Dosages of Rice Husk Particles on Thermal, Physical, Mechanical and Rheological Properties of Polypropylene-Based Composites. J. Compos. Sci. 2025, 9, 443. [Google Scholar] [CrossRef]
  28. Kazemi, H.; Parot, M.; Stevanovic, T.; Mighri, F.; Rodrigue, D. Cellulose and Lignin as Carbon Black Replacement in Natural Rubber. J. Appl. Polym. Sci. 2022, 139. [Google Scholar] [CrossRef]
  29. Cherezova, E.N.; Nakyp, A.M.; Karaseva, Y.S. Use of Powdered Cellulose, Obtained from Cotton Fiber Waste, in the Composition of Hydro-Swelling Rubber. Butlerov Commun. 2021, 68, 47–53. [Google Scholar] [CrossRef]
  30. Cherezova, E.; Nakyp, A.; Karaseva, Y.; Zhapparbergenov, R.; Akylbekov, N. Application of Epoxidized Soybean Oil in Highly Filled Water-Swelling Rubbers. Eng. Sci. 2023, 25, 936. [Google Scholar] [CrossRef]
  31. Nakyp, A.M.; Cherezova, E.N.; Karaseva, Y.S.; Nuriev, A.I. Powder Carboxylated Lignocellulose from Oat Straw as a Filler for Limited Swelling Rubbers. Bull. Technol. Univ. 2023, 26, 58–63. [Google Scholar] [CrossRef]
  32. Azubuike, C.P.; Okhamafe, A.O. Physicochemical, Spectroscopic and Thermal Properties of Microcrystalline Cellulose Derived from Corn Cobs. Int. J. Recycl. Org. Waste Agric. 2012, 1, 9. [Google Scholar] [CrossRef]
  33. Toptunov, E.A.; Sevastyanova, Y.V. Powdered Cellulosic Materials: Overview, Classification, Characteristics And Fields Of Application. Chem. Plant Raw Mater. 2021, 31–45. [Google Scholar] [CrossRef]
  34. Pérez-Merchán, A.M.; Rodríguez-Carballo, G.; Torres-Olea, B.; García-Sancho, C.; Maireles-Torres, P.J.; Mérida-Robles, J.; Moreno-Tost, R. Recent Advances in Mechanochemical Pretreatment of Lignocellulosic Biomass. Energies 2022, 15, 5948. [Google Scholar] [CrossRef]
  35. Lee, H.; Mani, S. Mechanical Pretreatment of Cellulose Pulp to Produce Cellulose Nanofibrils Using a Dry Grinding Method. Ind. Crops Prod. 2017, 104, 179–187. [Google Scholar] [CrossRef]
  36. Taylor, M.; Alabdrabalameer, H.; Skoulou, V. Choosing Physical, Physicochemical and Chemical Methods of Pre-Treating Lignocellulosic Wastes to Repurpose into Solid Fuels. Sustainability 2019, 11, 3604. [Google Scholar] [CrossRef]
  37. Hejna, A.; Sulyman, M.; Przybysz, M.; Saeb, M.R.; Klein, M.; Formela, K. On the Correlation of Lignocellulosic Filler Composition with the Performance Properties of Poly(ε-Caprolactone) Based Biocomposites. Waste Biomass Valorization 2020, 11, 1467–1479. [Google Scholar] [CrossRef]
  38. Cruz Fabian, D.R.; Durpekova, S.; Dusankova, M.; Cisar, J.; Drohsler, P.; Elich, O.; Borkova, M.; Cechmankova, J.; Sedlarik, V. Renewable Poly(Lactic Acid)Lignocellulose Biocomposites for the Enhancement of the Water Retention Capacity of the Soil. Polymers 2023, 15, 2243. [Google Scholar] [CrossRef]
  39. Ridho, M.R.; Agustiany, E.A.; Rahmi Dn, M.; Madyaratri, E.W.; Ghozali, M.; Restu, W.K.; Falah, F.; Rahandi Lubis, M.A.; Syamani, F.A.; Nurhamiyah, Y.; et al. Lignin as Green Filler in Polymer Composites: Development Methods, Characteristics, and Potential Applications. Adv. Mater. Sci. Eng. 2022, 2022, 1–33. [Google Scholar] [CrossRef]
  40. Momzyakova, K.S.; Deberdeev, T.R.; Valishina, Z.T.; Deberdeev, R.Y.; Ibragimov, A.V.; Alexandrov, A.V. Research of Physical and Chemical Properties of Powder Cellulose from Various Type of Raw Materials. Mater. Sci. Forum 2020, 992, 791–795. [Google Scholar] [CrossRef]
  41. Momzyakova, K.S.; Pulyaeva, M.A.; Kazakov, Y.V.; Deberdeev, T.R.; Kanarskii, A.V.; Aleksandrov, A.A.; Deberdeev, R.Y. Evaluation of the Paper-Making Properties of Cellulose Extracted from Oat and Alfalfa Straw. Polym. Sci. Ser. D 2022, 15, 431–435. [Google Scholar] [CrossRef]
  42. Momziakova, K.S.; Shinkarev, A.A.; Deberdeev, T.R.; Valishina, Z.T.; Berlin, A.A.; Deberdeev, R.Y. X-Ray Structural Analysis Of Cottons And Herbaceous Cellulose. Chem. Plant Raw Mater. 2021, 61–71. [Google Scholar] [CrossRef]
  43. Nakyp, A.; Cherezova, E.; Karaseva, Y.; Shalmagambetov, K.; Aleksandrov, A.; Zhapparbergenov, R.; Akylbekov, N.; Turmanov, R. Extraction of Lignocellulose from Rice Straw and Its Carboxymethylation When Activated by Microwave Radiation. Polymers 2024, 16, 3208. [Google Scholar] [CrossRef]
  44. Feldman, D. Wood—Chemistry, Ultrastructure, Reactions; Fengel, D., Wegener, G., Eds.; Walter de Gruyter: Berlin, Germany; New York, NY, USA, 1984; Volume 23, 613p. [Google Scholar]
  45. Nicholson, D.J.; Leavitt, A.T.; Francis, R.C. A Three-Stage Klason Method for More Accurate Determinations of Hardwood Lignin Content. Cellul. Chem. Technol. 2014, 48, 53–59. [Google Scholar]
  46. ASTM D1439-15; Standard Test Methods for Sodium Carboxymethylcellulose. ASTM International: West Conshohocken, PA, USA, 2022.
  47. Spiridonov, I.S.; Ushmarin, N.F.; Egorov, E.N.; Sandalov, S.I.; Kol’tsov, N.I. Influence Technological Additives On Properties Of Rubber Based On Butadiene-Nitrile Caoutchuc. Izv. Vyss. Uchebnykh Zaved. Khimiya Khimicheskaya Tekhnologiya 2017, 60, 53. [Google Scholar] [CrossRef][Green Version]
  48. Tapyev, S.A.; Dyakonov, A.A.; Okhlopkova, A.A.; Vasiliev, A.P.; Danilova, S.N.; Lazareva, N.N.; Kychkin, A.K.; Tuisov, A.G.; Vinokurov, P.V.; Spiridonov, A.M.; et al. Studying the Effects of the Butadiene Rubber and Nitrile Butadiene Rubber Ratio on the Elastomers Properties. Vopr. Materialoved. 2024, 89–98. [Google Scholar] [CrossRef]
  49. Cherezova, E.N.; Karaseva, Y.S.; Nakyp, A.M. Evaluation of the Durability of Limited Swelling Rubber Filled with Modified Powdered Cellulose from Cotton Waste. Polym. Sci. Ser. D 2023, 16, 681–686. [Google Scholar] [CrossRef]
  50. GOST 7087-75; 2,2′-Dibenzothiazol Disulphide. Specifications. USSR State Standards Committee: Moscow, USSR, 1975.
  51. Dykman, A.S.; Pinson, V.V.; Flegontov, A.M.; Shefter, V.E. The Structure of High-Boiling by-Products of Isoprene Production and the Chemistry of Their Formation. Oil Refin. Petrochem. 2013, 27–34. [Google Scholar]
  52. GOST 269-66; Rubber. General Requirements for Physical Mechanical Testing. USSR State Standards Committee: Moscow, USSR, 1966.
  53. GOST 12535-84; Raw Rubber. Method for Determination of Currating Characteristics by Cure. USSR State Standards Committee: Moscow, USSR, 1984.
  54. GOST R ISO 1817-2009; Rubber. Determination of Resistance to Liquids Effect. Federal Agency on Technical Regulating and Metrology (Rosstandart): Moscow, Russia, 2009.
  55. GOST 270-75; Rubber. Method for Determining Elastic and Tensile Stress-Strain Properties. USSR State Standards Committee: Moscow, USSR, 1975.
  56. GOST 27110-86; Rubber. Method for Determination of Rebound Elasticity on the Shob Type Machine. USSR State Standards Committee: Moscow, USSR, 1986.
  57. GOST 263-75; Rubber. Method for the Determination of Shore A Hardness. USSR State Standards Committee: Moscow, USSR, 1975.
  58. Kovalenko, V.I. Crystalline Cellulose: Structure and Hydrogen Bonds. Russ. Chem. Rev. 2010, 79, 231–241. [Google Scholar] [CrossRef]
  59. Marrinan, H.J.; Mann, J. A Study by Infra-red Spectroscopy of Hydrogen Bonding in Cellulose. J. Appl. Chem. 1954, 4, 204–211. [Google Scholar] [CrossRef]
  60. Md Salim, R.; Asik, J.; Sarjadi, M.S. Chemical Functional Groups of Extractives, Cellulose and Lignin Extracted from Native Leucaena Leucocephala Bark. Wood Sci. Technol. 2021, 55, 295–313. [Google Scholar] [CrossRef]
  61. Nelson, M.L.; O’Connor, R.T. Relation of Certain Infrared Bands to Cellulose Crystallinity and Crystal Latticed Type. Part I. Spectra of Lattice Types I, II, III and of Amorphous Cellulose. J. Appl. Polym. Sci. 1964, 8, 1311–1324. [Google Scholar] [CrossRef]
  62. Wang, Z.; McDonald, A.G.; Westerhof, R.J.M.; Kersten, S.R.A.; Cuba-Torres, C.M.; Ha, S.; Pecha, B.; Garcia-Perez, M. Effect of Cellulose Crystallinity on the Formation of a Liquid Intermediate and on Product Distribution during Pyrolysis. J. Anal. Appl. Pyrolysis 2013, 100, 56–66. [Google Scholar] [CrossRef]
  63. Susi, S.; Ainuri, M.; Wagiman, W.; Falah, M.A.F. Characterization and Selection of Microcrystalline Cellulose from Oil Palm Empty Fruit Bunches for Strengthening Hydrogel Films. J. Renew. Mater. 2024, 12, 513–537. [Google Scholar] [CrossRef]
  64. Stanciu, M.-C.; Tanasă, F.; Teacă, C.-A. Crystallinity Changes in Modified Cellulose Substrates Evidenced by Spectral and X-Ray Diffraction Data. Polysaccharides 2025, 6, 30. [Google Scholar] [CrossRef]
  65. Kljun, A.; Benians, T.A.S.; Goubet, F.; Meulewaeter, F.; Knox, J.P.; Blackburn, R.S. Comparative Analysis of Crystallinity Changes in Cellulose I Polymers Using ATR-FTIR, X-Ray Diffraction, and Carbohydrate-Binding Module Probes. Biomacromolecules 2011, 12, 4121–4126. [Google Scholar] [CrossRef] [PubMed]
  66. O’Connor, R.T.; DuPré, E.F.; Mitcham, D. Applications of Infrared Absorption Spectroscopy to Investigations of Cotton and Modified Cottons. Text. Res. J. 1958, 28, 382–392. [Google Scholar] [CrossRef]
  67. Fang, J. The Preparation and Characterisation of a Series of Chemically Modified Potato Starches. Carbohydr. Polym. 2002, 47, 245–252. [Google Scholar] [CrossRef]
  68. Adinugraha, M.P.; Marseno, D.W. Haryadi Synthesis and Characterization of Sodium Carboxymethylcellulose from Cavendish Banana Pseudo Stem (Musa cavendishii LAMBERT). Carbohydr. Polym. 2005, 62, 164–169. [Google Scholar] [CrossRef]
  69. Zhou, Y.; Hu, X.; Zhang, M.; Zhuo, X.; Niu, J. Preparation and Characterization of Modified Cellulose for Adsorption of Cd(II), Hg(II), and Acid Fuchsin from Aqueous Solutions. Ind. Eng. Chem. Res. 2013, 52, 876–884. [Google Scholar] [CrossRef]
  70. El-Sakhawy, M.; Tohamy, H.-A.S.; Salama, A.; Kamel, S. Thermal Properties Of Carboxymethyl Cellulose Acetate Butyrate. Cellul. Chem. Technol. 2019, 53, 667–675. [Google Scholar] [CrossRef]
  71. Somseemee, O.; Saeoui, P.; Schevenels, F.T.; Siriwong, C. Enhanced Interfacial Interaction between Modified Cellulose Nanocrystals and Epoxidized Natural Rubber via Ultraviolet Irradiation. Sci. Rep. 2022, 12, 6682. [Google Scholar] [CrossRef]
  72. Kazemi, H.; Mighri, F.; Rodrigue, D. A Review of Rubber Biocomposites Reinforced with Lignocellulosic Fillers. J. Compos. Sci. 2022, 6, 183. [Google Scholar] [CrossRef]
  73. Kamide, K.; Saito, M.; Suzuki, H. Persistence Length of Cellulose and Cellulose Derivatives in Solution. Die Makromol. Chem. Rapid Commun. 1983, 4, 33–39. [Google Scholar] [CrossRef]
  74. Rahman, M.S.; Hasan, M.S.; Nitai, A.S.; Nam, S.; Karmakar, A.K.; Ahsan, M.S.; Shiddiky, M.J.A.; Ahmed, M.B. Recent Developments of Carboxymethyl Cellulose. Polymers 2021, 13, 1345. [Google Scholar] [CrossRef] [PubMed]
  75. Bhandari, P.N.; Jones, D.D.; Hanna, M.A. Carboxymethylation of Cellulose Using Reactive Extrusion. Carbohydr. Polym. 2012, 87, 2246–2254. [Google Scholar] [CrossRef]
  76. Palanisamy, K.A.; Tahir, M.; Chanda, J.; Ghosh, P.; Mukhopadhyay, R.; Kundu, A.; Mandal, S.; Wießner, S.; Banerjee, S.; Das, A. A Comparative Study of the Reinforcing Behavior of Lignin in Polar and Non-Polar Rubbers. ChemistrySelect 2025, 10, e202404875. [Google Scholar] [CrossRef]
  77. Intapun, J.; Rungruang, T.; Suchat, S.; Cherdchim, B.; Hiziroglu, S. The Characteristics of Natural Rubber Composites with Klason Lignin as a Green Reinforcing Filler: Thermal Stability, Mechanical and Dynamical Properties. Polymers 2021, 13, 1109. [Google Scholar] [CrossRef] [PubMed]
  78. Litvinov, V.M.; Orza, R.A.; Klüppel, M.; van Duin, M.; Magusin, P.C.M.M. Rubber–Filler Interactions and Network Structure in Relation to Stress–Strain Behavior of Vulcanized, Carbon Black Filled EPDM. Macromolecules 2011, 44, 4887–4900. [Google Scholar] [CrossRef]
  79. Daud, S.; Lik, O.Y.H.; Azura, A.R. The Effects of Nano-Cellulose Filler on Tensile and Thermal Properties of Natural Rubber Latex Films. AIP Conf. Proc. 2020, 2267, 020079. [Google Scholar] [CrossRef]
  80. Ioelovich, M.Y. Models of Supramolecular Structure and Properties of Cellulose. Polym. Sci. Ser. A 2016, 58, 925–943. [Google Scholar] [CrossRef]
  81. Seddiqi, H.; Oliaei, E.; Honarkar, H.; Jin, J.; Geonzon, L.C.; Bacabac, R.G.; Klein-Nulend, J. Cellulose and Its Derivatives: Towards Biomedical Applications. Cellulose 2021, 28, 1893–1931. [Google Scholar] [CrossRef]
  82. Tian, R.; Wang, C.; Jiang, W.; Janaswamy, S.; Yang, G.; Ji, X.; Lyu, G. Biodegradable, Strong, and Hydrophobic Regenerated Cellulose Films Enriched with Esterified Lignin Nanoparticles. Small 2024, 20, 2309651. [Google Scholar] [CrossRef] [PubMed]
  83. Karimov, O.K. Modification of Lignin for Rubber Composites. Prom. Proizv. Ispol’z. Elastom. 2022, 12–16. [Google Scholar] [CrossRef]
  84. Mohamad Aini, N.A.; Othman, N.; Hussin, M.H.; Sahakaro, K.; Hayeemasae, N. Lignin as Alternative Reinforcing Filler in the Rubber Industry: A Review. Front. Mater. 2020, 6. [Google Scholar] [CrossRef]
  85. Thakur, V.K.; Thakur, M.K.; Raghavan, P.; Kessler, M.R. Progress in Green Polymer Composites from Lignin for Multifunctional Applications: A Review. ACS Sustain. Chem. Eng. 2014, 2, 1072–1092. [Google Scholar] [CrossRef]
Polysaccharides 07 00016 g001
Figure 1. FTIR (ATR mode) spectra of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Figure 1. FTIR (ATR mode) spectra of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Polysaccharides 07 00016 g001
Polysaccharides 07 00016 g002
Figure 2. TG-curves of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Figure 2. TG-curves of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Polysaccharides 07 00016 g002
Polysaccharides 07 00016 g003
Figure 3. Particle size distribution of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Figure 3. Particle size distribution of the swelling fillers: 1—NaCMC, 2—LC-Alf, 3—CMLC-Alf.
Polysaccharides 07 00016 g003
Polysaccharides 07 00016 g004
Figure 4. Micrographs of the vulcanizates.
Figure 4. Micrographs of the vulcanizates.
Polysaccharides 07 00016 g004
Polysaccharides 07 00016 g005
Figure 5. Rheometric vulcanization curves.
Figure 5. Rheometric vulcanization curves.
Polysaccharides 07 00016 g005
Polysaccharides 07 00016 g006
Figure 6. Effect of the swelling filler on the swelling degree of the samples in formation water: 1—WSR-1, 2—WSR-2, 3—WSR-3, 4—WSR-4, 5—WSR-5, 6—WSR-6.
Figure 6. Effect of the swelling filler on the swelling degree of the samples in formation water: 1—WSR-1, 2—WSR-2, 3—WSR-3, 4—WSR-4, 5—WSR-5, 6—WSR-6.
Polysaccharides 07 00016 g006
Polysaccharides 07 00016 g007
Figure 7. Illustration of the swelling of carboxymethylated cellulose.
Figure 7. Illustration of the swelling of carboxymethylated cellulose.
Polysaccharides 07 00016 g007
Table 1. Formulations and designations of the rubber compounds.
Table 1. Formulations and designations of the rubber compounds.
NIngredients Sample Designation
BRCWSR-1WSR-2WSR-3WSR-4WSR-5WSR-6
Composition of the base rubber compound (BRC)Content, phr (Parts per Hundred Rubber)
1BNKS-28 AMN100.0100.0100.0100.0100.0100.0100.0
2Sulfur1.51.51.51.51.51.51.5
3MBTS0.80.80.80.80.80.80.8
4Stearic acid1.51.51.51.51.51.51.5
5ZnO5.05.05.05.05.05.05.0
6CB P 32445.045.045.045.045.045.045.0
7Oxal T-923030.030.030.030.030.030.0
Additional ingredients of the rubber compound
8NaCMC-100.0--150.0--
9LC-Alf--100.0--150.0-
10CMLC-Alf---100.0--150.0
Table 2. Mineral composition of the formation water from the Romashkinskoye field (Leninogorsky District, Russia).
Table 2. Mineral composition of the formation water from the Romashkinskoye field (Leninogorsky District, Russia).
Mineral Composition of the Formation Water, g/L
Na+Ca2+Mg2+Cl−CO32−SO42−
701131390.20.7
Table 3. Absorption bands in the FTIR spectra of the swelling filler samples.
Table 3. Absorption bands in the FTIR spectra of the swelling filler samples.
Functional Groups, cm−1NaCMCLC-AlfCMLC-Alf
ν(OH)341533363343
ν(CH2)2970/287129262979/2831
ν(C=O)1723-1715
δ(HOH)159515991595
δ(CH2OH) + δ(CH)13731418/13701383
δ(OH) + δ(CH) + γ(CH2)115713171231
δ(OH) + δ(CH2)108111651061
ν (C–O–C) of the pyranose ring, +9891027-
ν(C–O–C) bridge,898896890
ν(COC)-мoстик + δ(C1H)840-841
(C–C) skeletal vibrations,674656696/654
Note. Absorption bands: ν—stretching vibrations; δ—in-plane deformation vibrations; γ—out-of-plane deformation vibrations.
Table 4. Crystallinity indices of the samples.
Table 4. Crystallinity indices of the samples.
ν, cm−1NaCMCLC-AlfCMLC-Alf
D1430/D9000.12 ± 0.010.42 ± 0.020.18 ± 0.01
D1375/D29000.15 ± 0.020.48 ± 0.020.22 ± 0.03
Table 5. Rheometric characteristics of the rubber compounds filled with the swelling fillers (T = 160 °C, τ = 30 min).
Table 5. Rheometric characteristics of the rubber compounds filled with the swelling fillers (T = 160 °C, τ = 30 min).
Sample Designationts, minML, dN·mMH, dN·mt90, min
BRC1.2154012
100 phr of the swelling filler
WSR-11.3215316
WSR-21.4245820
WSR-31.3144616
150 phr of the swelling filler
WSR-41.5225717
WSR-51.6296719
WSR-61.5185317
Table 6. Effect of the type and amount of the swelling filler on the physical and mechanical properties of the rubber samples.
Table 6. Effect of the type and amount of the swelling filler on the physical and mechanical properties of the rubber samples.
Sample DesignationTS, MPaε, %Rebound Resilience, %Hardness, Shore A
BRC13.84803465
100 phr of the swelling filler
WSR-14.02802972
WSR-29.1602295
WSR-36.41602579
150 phr of the swelling filler
WSR-43.52202578
WSR-57.95019102
WSR-65.81302284
Table 7. Tensile strength of the rubbers containing swelling fillers and its change after exposure to formation water for 3 days.
Table 7. Tensile strength of the rubbers containing swelling fillers and its change after exposure to formation water for 3 days.
Sample DesignationTS, MPa
100 phr of the swelling filler
WSR-11.9
WSR-28.1
WSR-35.2
150 phr of the swelling filler
WSR-42.0
WSR-57.3
WSR-65.0
Change in the parameter
TS—TS0((TS—TS0)/TS0) × 100, %
100 phr of the swelling filler
WSR-1−2.153
WSR-2−1.013
WSR-3−1.219
150 phr of the swelling filler
WSR-4−1.543
WSR-5−0.68
WSR-6−0.814
TS—tensile strength after swelling; TS0—tensile strength before swelling.
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

Nakyp, A.; Cherezova, E.; Karaseva, Y.; Akylbekov, N.; Turmanov, R.; Kuandykova, A. Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers. Polysaccharides 2026, 7, 16. https://doi.org/10.3390/polysaccharides7010016

AMA Style

Nakyp A, Cherezova E, Karaseva Y, Akylbekov N, Turmanov R, Kuandykova A. Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers. Polysaccharides. 2026; 7(1):16. https://doi.org/10.3390/polysaccharides7010016

Chicago/Turabian Style

Nakyp, Abdirakym, Elena Cherezova, Yulia Karaseva, Nurgali Akylbekov, Rakhymzhan Turmanov, and Akbota Kuandykova. 2026. "Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers" Polysaccharides 7, no. 1: 16. https://doi.org/10.3390/polysaccharides7010016

APA Style

Nakyp, A., Cherezova, E., Karaseva, Y., Akylbekov, N., Turmanov, R., & Kuandykova, A. (2026). Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers. Polysaccharides, 7(1), 16. https://doi.org/10.3390/polysaccharides7010016

Article Metrics

Back to TopTop