Cellulose Nanocrystals Content Research Articles

Biogas purification by CO2 removal using facilitated transport mechanism of cellulose nanocrystals/polyvinyl alcohol layered hollow fiber membranes

AbstractBiogas can be a viable solution for replacing the conventional fuel for reducing pollution. However, the high CO2 content in biogas must be removed for its utilization. In this study, biogas purification is carried out employing cellulose nanocrystals (CNC)/polyvinyl alcohol (PVA) “selective layered” polysulfone hollow fiber membrane. The membrane chamber is designed such that the cross‐flow of the biogas can be ensured for the effective interaction of the biogas with membrane surface. From various characterization tools like field emission scanning electron microscope, FTIR, X‐ray diffraction, moisture absorption and tensile test, CNC1/PVA (1 wt% of CNC in PVA) nanocomposite film demonstrated optimum crystallinity and mechanical strength while retaining higher moisture absorption. The average selective layer thickness at this CNC concentration is 1169 nm. CO2 permeability of 17,858 barrer and the selectivity of 19 for CO2 over CH4 is observed, respectively.

Enhancing piezoelectric properties of PVDF-HFP composite nanofibers with cellulose nanocrystals

With the increasing interest in flexible self-powering energy devices, piezoelectric polymers such as poly(vinylidene fluoride) (PVDF), PVDF-trifluoroethylene (PVDF-TrFE and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) have garnered substantial research attention. Among these, PVDF-HFP has demonstrated immense research potential in harvesting mechanical energy and converting it to electric energy. It is also particularly attractive due to its low cost compared to some other PVDF co-polymers. In this study, PVDF-HFP nanofibers were produced by electrospinning with cellulose nanocrystal (CNC) employed as a filler to improve their piezoelectric performance. Smooth and bead-free fibers were obtained with up to 1 wt% of CNC in the solution. The inclusion of CNC increased the uniformity of fiber diameter and improved thermal stability. Higher CNC concentration (2–3 wt%) engendered agglomeration and adversely impacted the conversion of non-polar phase to electroactive phase for PVDF-HFP molecules. At the optimal CNC concentration of 1 wt%, the voltage and current sensitivities for 1 cm2 samples were obtained as 0.146±0.048 mV/mN and 0.009±0.003 nA/mN, respectively. The open-circuit voltage output of 2.69±1.11 V was achieved under an average impact force of 40 N, and this increased with increased magnitude and frequency of the applied force. The mechanical properties of composite nanofibers maximized at 0.5 wt% CNC with tensile strength of 37.85±4.35 MPa, elastic modulus of 124.96±42.17 MPa, and strain at failure of 82.32±14.84 %. The improved piezoelectric and mechanical properties of the CNC-aided electrospun PVDF-HFP fibers will open new pathways for flexible energy harvesting systems.

Flexible Sandwich-Shaped Cellulose Nanocrystals/Silver Nanowires/MXene Films Exhibit Efficient Electromagnetic-Shielding Interference Performance.

The electromagnetic pollution problem is becoming increasingly serious due to the speedy advance of electronic communication devices. There are broad application prospects for the development of flexible, wearable composite films with high electromagnetic interference (EMI)-shielding performance. The MX@AC composite films were prepared from MXene, silver nanowires (AgNWs) and cellulose nanocrystals (CNCs) with a sandwich structure. Benefiting from the upper and lower frame structure formed by winding 1D AgNWs and CNC, the tensile strength of the MX@AC was improved to 35 MPa (12.5 wt% CNC content) from 4 MPa (0 wt% CNC content). The high conductivity of MXene and AgNWs resulted in the MX@AC composite film conductivity up to 90,670 S/m, EMI SE for 90 dB, as well as SSE/t up to 7797 dB cm2 g-1. And the MX@AC composite film was tested for practical application, showing that it can effectively isolate electromagnetic waves in practical application.

A model for tensile strength of cellulose nanocrystals polymer nanocomposites

Cellulose nanocrystals (CNCs) are rod-shaped, highly crystalline, and possess a high aspect ratio, extensive surface area, and exceptional mechanical properties, making them ideal for reinforcing polymer matrices. However, few models exist for predicting the mechanical properties of CNC-based polymer nanocomposites (PNCs). Existing models often overlook the interphase's role in the mechanical performance of CNC-filled samples, leading to unreliable predictions. This study introduces a straightforward model emphasizing the interphase region and CNC properties to determine the strength of CNC-based system. The model is validated by experimental data and parametric analyses. The results indicate that interphase thickness and strength depending on the interfacial bonds between polymer chains and CNCs along with CNC volume fraction directly control the nanocomposite strength, while a larger CNC diameter diminishes it. Optimal strength in PNCs is achieved with thinner CNCs, thicker and stronger interphase, and higher CNC content. In addition, numerous experimental outputs of various samples show good fitting with model’s predictions.

3D vat photopolymerization printing of hydrophilic silicone-based microfluidic devices and the effect of cellulose nanocrystals as additives for improved printing accuracy

The lack of an ideal silicone-based ink material with optimal printability has significantly limited the potential to fabricate silicone-based microfluidic devices via 3D vat photopolymerization (VPP) printing. Oftentimes, photoabsorbers are incorporated into the ink material for better control of the photocuring depth in order to avoid excessive curing of unwanted parts. However, the search for a suitable photoabsorber without staining the ink material remains challenging due to the need to retain the clear interface in the final printed product. Herein, we present the fabrication of highly precise and transparent microfluidic devices using hydrophilic silicone-based ink via 3D VPP printing upon photocuring depth adjustment with cellulose nanocrystals (CNC). With the optimal CNC content, the ink material demonstrates enhanced printing accuracy with highly precise replication of channel patterns consisting of near zero deviation in width dimension down to 100 µm. Moreover, the addition of optimal CNC content exhibits no distinct final color and has no negative impact on the pre-gel viscosity and the gel point of the developed ink material. Moving on, the printed devices exhibit excellent fluid manipulation with various solvents for up to 24 hours, with incubation temperature up to 100ºC for 5 hours, and with a continuous flow rate up to 20 mL/min. The sustainable hydrophilicity, good organic solvent resistance, and excellent biocompatibility properties of the printed material further eliminate the need for additional surface modification to suit its application with either organic solvents or biological cells. To the best of our knowledge, the approach to tuning the photocuring depth of ink material with CNC is not widely reported. Besides, the successful fabrication of a highly detailed, neutral-colored, and highly functional hydrophilic silicone-based microfluidic device via 3D VPP printing upon the incorporation of CNC introduces a new avenue in terms of printing material and fabrication method for the mass production of microfluidic devices.

Fabrication of composite polymer microcapsules via the supercritical extraction of Pickering emulsion Method: Insights into emulsification and extraction

Polyphenylene oxide (PPO)/cellulose nanocrystal (CNC)/carbon black (CB) microcapsules were fabricated by the supercritical extraction of Pickering emulsion (SFEPE) method. The effects of Pickering emulsion formulations on the emulsion properties, emulsification kinetics, and CPM properties were investigated. The phase behaviors in the supercritical extraction process were studied, and the mass transfer between the emulsion droplet and supercritical carbon dioxide (SCCO2) was also interpreted. The results indicate that CNC concentration, CB concentration, and NaCl concentration can decrease the droplet size and creaming index of emulsions, while the water–oil ratio can decrease the droplet size but enhance the creaming index. The emulsion formulations of water–oil > 3, CNC concentration > 0.25 mg/mL, CB concentration < 2.5 mg/mL, and NaCl concentration > 2.5 mg/mL are conducive to the emulsion formation and emulsification kinetics. For the supercritical extraction on Pickering emulsions, the operation conditions slightly above the mixture critical point (9 MPa at 313 K, for example) are proved to be conducive to the extraction.

Characteristics of polypropylene-based antistatic bio-nano composites reinforced with mono-diacylglycerols and cellulose nanocrystals

Polypropylene (PP) is known as a polymer without antistatic properties that is susceptible to the use of high temperatures. Therefore, to improve the thermal and antistatic properties of PP, it is necessary to modify PP to antistatic bio-nanocomposites with mono-diacylglycerols (M-DAG) as an antistatic agent and cellulose nanocrystals (CNC) as a reinforcement. This research aimed to characterize the electrical resistivity and thermal properties of PP-based antistatic bio-nanocomposites reinforced with M-DAG and CNC at different concentrations of CNC (0%–5%), and 2% of M- DAG, compared to pure PP. The results showed that the addition of 2% CNC (AS-BNC-2) gave the melting temperature of 125.0 °C, which was higher than pure PP of 118.3 °C. The thermal stability of the antistatic bio-nano composites with 3% CNC (AS-BNC-3) was 457.10 °C, which was higher than pure PP of 441.56 °C. The electrical resistivity of the antistatic bio-nano composites from all treatments was still in the range of the antistatic category of 1010–1012 Ω/sq. The melting temperature and thermal stability of bio-nano composites were higher than those of pure PP and they have antistatic properties. This indicates the potential application of these materials in the electronics devices and packaging industries.

Effects and Analysis of Chytazone in the Process of Processing Paper from Natural polymeres

The paper obtained during the study was mainly obtained from wheat straw cellulose and Jerusalem artichoke cellulose, which contained chitosan of various concentrations. An increase in the mechanical properties of the obtained papers was observed in samples using the substance chitosan. A 1.0% chitosan was added to the paper, mainly based on various plant celluloses. It should be noted that the obtained paper products were used without bleaching due to the fact that it was recommended to use them for wrapping paper. The youngest results were observed in samples prepared from a composition of wheat straw and artichoke pulp. From the fiber morphology, it was observed that the sized paper fibers became stronger, denser and smoother. Keywords: chytazone, Natural polymers, fibers, cellulose. Biocomposites of chitosan (CS)/cellulose nanocrystals (CN) were prepared by using solution casting method. Influences of solution preparation method and CN content on the properties of composites were investigated. Mechanical stirring/ultrasonication or micro fluidization were used to disperse nanocrystals in the chitosan matrix. The prepared nanocomposites were characterized by FTIR, XRD, SEM, DSC, TGA, TMA and contact angle measurements.

Cellulose nanocrystals extracted from rice husk using the formic/peroxyformic acid process: isolation and structural characterization.

Cellulose derived from biomass is a renewable resource with numerous applications. Using formic/peroxyformic acid at atmospheric pressure, cellulose nanocrystals (CNC) were isolated from rice husk (RH) in this study. This method was an excellent way to get rid of lignin and hemicelluloses from RH. The cellulose was subsequently acid hydrolyzed by H2SO4 (64%) for 30 minutes at 45 °C. The chemical and microstructure analysis showed that the lignin and hemicellulose contents of raw RH had been eliminated, and the crystallinity content of CNC was 67.16%. According to transmission electron microscopy (TEM) morphological analysis, CNC measured 19 ± 3.3 nm in diameter, 195 ± 24 nm in length, and 10.2 ± 6.8 in aspect ratio. The thermal stability of RH and CNC was also investigated using thermogravimetric analysis (TGA). These encouraging findings demonstrated the potential for reusing RH agricultural waste to create CNC and include nanocomposites as a reinforcing material.

Pickering emulsions stabilized by cellulose nanocrystals extracted from hazelnut shells: Production and stability under different harsh conditions

Cellulose nanocrystals (CNCs) are biodegradable particles that have emerged as promising stabilizers for Pickering emulsions. This study investigated the effectiveness of CNCs in forming the Pickering emulsion from hazelnut shells (HS), an agricultural waste. Following the alkaline and bleaching treatments applied to HS, CNCs were obtained from treated hazelnut shell with acid hydrolysis. The physicochemical characteristics of CNCs were investigated using dynamic light scattering, XRD, FTIR, SEM, and TEM. A high crystalline (69.6 %) CNCs with a spherical shape were obtained. Contact angle and interfacial tension tests were conducted and showed that CNCs had amphiphilic nature. Pickering emulsions were investigated for their size, zeta potential, and stability under varying CNC concentrations. The results showed that when CNCs concentration increased from 0.5 to 2.0 wt%, droplet diameter decreased approximately 1.8 times and zeta potential increased. Creaming was not observed during 28 days of storage in a concentration of 2.0 wt% CNCs. The CNC stabilized emulsions exhibited high stability within a range of pH, temperatures, and salt concentrations. This study demonstrated that CNCs extracted from HS as environmentally friendly and cost-effective materials, could serve as a new stabilizer for Pickering emulsions especially for high temperature and low pH sensitive products such as mayonnaise.

Application of cellulose nanocrystals in 3D printed alkali-activated cementitious composites

With the rapid development of concrete 3D printing for construction projects, it is crucial to produce sustainable 3D-printed cementitious composites that meet the required fresh and hardened properties. This study develops sustainable 3D-printed cementitious composites of ordinary portland cement and alkali-activated materials using cellulose nanocrystals (i.e., green natural nanomaterials). The extrudability and buildability of the alkali-activated slag-fly ash mixtures were improved and the extrusion pressure was reduced by ~ 35 % by increasing the cellulose nanocrystals content (up to 1 %) suggesting their viscosity-modifying properties in alkali-activated materials. The inclusion of cellulose nanocrystals improves the overall mechanical performance (8–20 % increase) and reduces the porosity of ordinary portland cement and heat-cured alkali-activated samples. Further, the addition of cellulose nanocrystals (up to 0.30 %) in sealed-cured alkali-activated samples improves their flexural strength by 20 %. The ordinary portland cement sample with cellulose nanocrystals densifies the microstructure and has an approximately 25 % increase in the degree of hydration at inner depths indicating cellulose nanocrystals' internal curing potential. The developed 3D-printable alkali-activated composites with cellulose nanocrystals can provide an overall reduction in the environmental impacts by eliminating/reducing the need for chemical admixtures to improve material consistency and stability, and replacing 100 % of portland cement.

The Effect of Temperature and Shear on the Gelation of Cellulose Nanocrystals in Deep Eutectic Solvents.

With the flourishing development of 3D printing technology, the demand for printing materials has been increasing rapidly in recent years. In particular, physical gels formed by cellulose nanocrystals (CNCs) exhibit suitable shear-thinning behavior, high storage moduli, and high yield stresses for extrusion-based printing. While most studies use water as the dispersing medium to form CNC percolated gels, the dispersing behavior of CNCs in alternative solvents, such as deep eutectic solvents (DESs), has not been fully explored. Especially, DESs have low volatility and good ionic conductivity to form functional ionogels. Precise control of the rheological properties and selection of suitable dispersion processes continue to pose significant challenges. In light of this, we have devised a novel dispersion process employing thermal and shear treatments to facilitate the gelation of CNCs within DESs. A crude dispersion of CNCs in the DES underwent thermal treatment to partially remove the surface sulfate ester on CNCs. As a result, the repulsive force between CNCs decreases. A second shear then significantly increases the strength of CNC/DES gels potentially because of the increased rod-rod contacts. This approach enables the formation of high-strength gels at low concentrations of CNCs. Both thermal treatment and a second shear are crucial to forming strong percolated CNC gels. In short, we showed a simple strategy to facilitate the dispersion and gelation of CNCs for direct ink writing.

Two-dimensional strain rate imaging study using a polarization camera and birefringent aqueous cellulose nanocrystal suspensions

The birefringence response of aqueous cellulose nanocrystal (CNC) suspensions in a two-dimensional laminar flow is measured and studied. The suspensions have CNC concentrations of 1.0 wt% (weight percentage) and 1.2 wt%. Cellulose nanocrystals are optically anisotropic rod-like particles that align when subjected to local velocity gradients, whereas at rest, they remain randomly orientated by Brownian motion. The alignment causes birefringence, a phenomenon also known as flow-induced birefringence. We study the flow through an additively manufactured flow channel and measure the amount of birefringence as well as the position of the refractive index axes by using polarizers and a polarization camera. With the help of reference data published in a previous study (Lane, Rode, et al., 2022a), strain rates are derived from the birefringence measurements and compared with numerical simulations. Two flow situations are studied, a plane Poiseuille flow and the flow around a cosine-shaped constriction. The experimentally derived shear rates for the plane Poiseuille flow are consistent with theoretical and computational results. The derived strain rates for the flow around the cosine-shaped constriction show an unexpected asymmetric profile, with the strain rates in the contraction zone being larger than in the expansion zone. The averaged orientation of the CNCs in the flow is linked to the position of the refractive index axes. In the contraction zone, the CNCs tend to align parallel to the flow, whereas in the expansion zone, the CNCs tend to align perpendicular to the flow. The results of this study are discussed in the context of previous, similar studies. The asymmetric strain rate profile around the cosine-shaped constriction is thought to originate from history effects, and the alignment of the CNCs is influenced by extensional rates.

Characterization of cellulose nanocrystal extracted from household waste and its application for seed germination

Cellulose nanocrystals (CNCs) were extracted from waste corrugated cardboard (WCC), waste paper towel (WPT), and waste paper towel cardboard roll (WPTR) using modified chemical methods. Instead of being discarded in landfills, these household waste materials were recognized as cost-effective and readily available sources for producing CNCs, which can serve as efficient water adsorbents in agricultural applications. Despite the inherent impurities and contaminants in household waste, the pretreatment and acid hydrolysis processes were found to be effective in removing a significant portion of these undesirable substances, as confirmed by FTIR spectra analysis. The extracted CNCs displayed a needle/whisker-shaped morphology with diameters ranging from 4 to 15 nm. Crystallinity levels of the CNCs extracted from WCC, WPT, and WPTR were determined to be 81.11 %, 85.29 %, and 80.68 %, respectively. The CNCs were then tested for their role as promoters of seed germination in plant starter plugs under different relative humidity conditions. Results indicated that under high relative humidity (above 70 %), seeds exhibited rapid germination (within 3–4 days) when the plugs were coated with CNCs at a minimum concentration of 5 %. However, under moderate relative humidity (50 %), germination occurred within 5–6 days at CNC concentrations of 10–15 %.

Preparation and characterization of electrospun cellulose nanocrystals-reinforced trans-1,4-polyisoprene nanocomposite elastomeric fiber membranes

To overcome the limitations of low strength of conventional electrostatic spinning trans-1,4-polyisoprene (TPI) fiber membranes, cellulose nanocrystals (CNC) were added into the TPI spinning solution as a backbone material, and CNC/TPI nanocomposite elastomeric fiber membranes were prepared using electrostatic spinning. This study examined the effect of CNC content on the morphology, mechanical properties, and hydrophilicity of the electrostatically spun CNC/TPI nanocomposite elastomeric fiber membranes. The prepared CNC/TPI nanocomposite elastomeric fiber membranes were characterized using 3D measurement laser microscopy, tensile testing, Fourier-infrared spectrometry, thermogravimetric analysis, differential scanning calorimetry, and water contact angle. With increase in CNC content, the tensile strength of the nanocomposite elastomeric fiber membrane increased from 1.79 MPa (without CNC) to 10.28 MPa (with 1 wt% CNC), the average diameter first decreased and then increased, the thermal stability and water vapor transmission rate decreased, and the water contact angle gradually increased. The maximum water contact angle was 124.27° and the minimum water vapor transmission rate was 851.41 g/m2·24 h. The proposed high-strength hydrophobic breathable fiber membrane preparation method can be used in various fields such as high-strength waterproof/breathable protective clothing and wearable electronic devices.

Yield stress analysis of cellulose nanocrystals (CNCs) in hyaluronic acid suspensions

Due to their biodegradability features, cellulose nanocrystals (CNCs) and hyaluronic acid (HA) have been simultaneously used in the matrix of hydrogels for biomedical applications, such as corneal transplantation, and skin regeneration. Although rheology of these hydrogels may provide useful information for their applications, little to no attention has been paid to rheological characterization. In this study, we analyzed the rheology of HA-CNC suspensions and more specifically their yielding behavior. Through different rheological experiments, known as stress ramp, shear rate ramp and amplitude sweep; it was observed that HA-CNC gels possessed two yield points. Reproducible magnitudes of yield stress were obtained by optimizing the experimental conditions. The rheo-optics characterizations confirmed that the first and second yield points could be attributed to the bond and cage breakage phenomena. Studying the effect of concentration, the second yield stress increased linearly by CNC concentration, whereas the first yield point manifested a power-law dependence on concentration (exponent of 0.5). This power-law relationship was further justified by the evolution of average distance between the CNC individual particles (d), calculated through SAXS analysis.

Influence of low contents of cellulose nanocrystals on the crystallization behavior of biobased Poly(propylene 2,5-furandicarboxylate)

To address the slow crystallization problem of poly(propylene 2,5-furandicarboxylate) (PPF), fully biobased PPF/cellulose nanocrystals (CNC) composites were prepared via a solution and casting method in this work at low CNC contents. The influence of CNC on the crystallization of PPF was studied in detail under various conditions, including nonisothermal and isothermal melt crystallization as well as nonisothermal and isothermal cold crystallization. The results revealed that the crystallization of PPF was enhanced under various crystallization conditions by CNC due to the heterogeneous nucleating agent role. From the isothermal crystallization kinetics study, the presence of CNC did not alter the crystallization mechanism of PPF. In addition, the thermogravimetric analysis results showed that both PPF and PPF/CNC composites displayed an excellent thermal stability. On the basis of the wide angle X-ray diffraction study, CNC did not change the crystal structure of PPF.

Properties of sodium alginate-based nanocomposite films: Effects of aspect ratio and surface charge of cellulose nanocrystals

Three cellulose nanocrystals (CNCs) were prepared to reinforce sodium alginate (SA) films. This study investigated effects of aspect ratio (L/D) and surface charge of three CNCs (CCNC, MCNC, and WCNC) on the properties of films. At CNC concentrations ≤3 wt%, MCNC, with a medium L/D but the lowest surface charge density among the three CNCs, exhibited the highest efficiency in enhancing the Young's modulus and tensile strength of films. This indicated that, apart from L/D, CNC's surface charge density also affected its reinforcing effects in anionic SA-based films. Compared with other CNCs, MCNC with the lowest charge density exhibited weaker repulsion with SA, potentially contributing to stronger interfacial interactions between them. At concentrations >3 wt%, the reinforcing efficiency of MCNC was extremely close to that of WCNC, which had the highest L/D but medium charge density. This was possibly because, according to SEM results, MCNC with the lowest absolute value of zeta potential aggregated more severely than other CNCs. However, both MCNC and WCNC were consistently more efficient than CCNC. Moreover, FTIR results revealed that WCNC formed more hydrogen bonds with SA than other CNCs. Consequently, adding WCNC was more effective in reducing films' water vapor permeability and hydrophilicity.

Efficient (Bio)emulsification/Degradation of Crude Oil Using Cellulose Nanocrystals

This study has investigated the influence of cellulose nanocrystals (CNCs) with partially acetylated surfaces on the formation, stability, rheology and biodegradability of the Pickering emulsion in a crude oil/water (co/w) system. In all investigated systems, it was observed that the CNC concentrations of 7 mg/mL led to the emulsions showing stability over time. It was also noticed that the increase in concentration of background electrolyte (NaCl) leds to the droplets of emulsions becoming smaller. It was demonstrated that the rheology of the o/w emulsions of the oil products and crude oil stabilized by CNCs depends, to a large extent, on the colloid chemical properties of nanocellulose particles. Calculations and experimental methods were used to study the changes in the acid–base properties of CNCs on the surface of emulsion droplets, depending on a type of hydrophobic components (crude oil and liquid paraffin). The formation of Pickering emulsions leads to the oxidation of oil by Rhodococcus egvi in aerobic conditions becoming more effective, provided that the environment includes mineral salts of nitrogen, potassium and phosphorus. The results obtained present a scientific basis for the development of technologies for the disposal of oil spills on water surfaces.

Encapsulation of Camphor in Nanocellulose based Pickering Emulsion and Study of its Antibacterial Activity

Abstract: Camphor is a natural and renewable antimicrobial agent. However, it is highly sublime, which limits its practical application as an effective antibacterial agent. To improve camphor's stability and retention properties, we have microencapsulated camphor into an almond essential oil-based Pickering emulsion (AO-PE), stabilized by cellulose nanocrystals (CNC). The CNC was synthesized from corn husk using an eco-friendly homogenization approach to stabilize the AO-PE. Various factors affecting the formation and stability of Pickering emulsions (PE) were studied, such as the source of cellulose (corn husk and mung hull), oil type (sesame oil and almond oil), oil in water concentration, and stability with time and shear. Camphor-loaded CNC-stabilized AO-PE exhibited a small droplet size and had long-term stability at 6.67% by volume oil concentration, owing to the presence of 0.2 g of CNC at droplet interfaces. The results showed that the PE exhibited better antibacterial performance against Staphylococcus aureus than the equivalent concentrations of camphor, almond oil, CNC, and camphor dissolved in almond oil, individually. This research shall provide fresh insights into the significant enhancement of the antimicrobial properties of medicinal natural products by incorporating them into PEs. Graphical abstract