Optimization of Cellulose Nanocrystal Isolation from Ayous Sawdust Using Response Surface Methodology

This study focuses on the extraction of cellulose nanocrystals (CNC), from microcrystalline cellulose (MCC), derived from Ayous sawdust. The process involves multiple steps and a large amount of chemical products. The objective of this research was to determine the effects of factors that impact the isolation process and to identify the optimal conditions for CNC isolation by using the response surface methodology. The factors that varied during the process were the quantity of MCC, the concentration of sulfuric acid, the hydrolysis time and temperature, and the ultrasonic treatment time. The response measured was the yield. The study found that with 5.80 g of microcrystalline cellulose, a sulfuric acid concentration of 63.50% (w/w), a hydrolysis time of 53 minutes, a hydrolysis temperature of 69˚C, and a sonication time of 19 minutes are the ideal conditions for isolation. The experimental yield achieved was (37.84 ± 0.99) %. The main factors influencing the process were the sulfuric acid concentration, hydrolysis time and temperature, with a significant influence (p < 0.05). Infrared characterization results showed that nanocrystals were indeed isolated. With a crystallinity of 35.23 and 79.74, respectively, for Ayous wood fiber and nanocrystalline cellulose were observed by X-ray diffraction, with the formation of type II cellulose, thermodynamically more stable than native cellulose type I.

Surface-functionalized cellulose nanocrystals(CNC)and synergisms with surfactant for enhanced oil recovery in low-permeability reservoirs

Nanocellulose,a natural polymeric nanomaterial,has attracted significant attention in enhanced oil recovery(EOR)applications due to its abundance,nanoscale,high oil-water interfacial adsorption ef-ficiency.In this study,surface-functionalized cellulose nanocrystals(SF-CNCs)were prepared via hy-drochloric acid hydrolysis and chemical modification,with adaptable nanosize and considerable dispersion stability in low-permeability reservoirs.The SF-CNCs were structurally characterized by FT-IR,Cryo-TEM,which have a diameter of 5-10 nm and a length of 100-200 nm.The SF-CNC dispersions possessed higher stability and stronger salt-tolerance than those of corresponding CNC dispersions,due to the strong hydrophilicity of the sulfonic acid group.It was synergistically used with a non-ionic surfactant(APG1214)to formulate a combined flooding system(0.1 wt%SF-CNC+0.2 wt%APG1214).The combined flooding system exhibits strong emulsification stability,low oil-water interfacial tension of o.03 mN/m,and the ability to alter the wettability for oil-wetting rocks.Furthermore,the combined system was_able to provide an optimum EOR efficiency of 20.2%in low-permeability cores with 30.13×10^(-3)μm^(2).Notably.it can enlarge the sweep volume and increase the displacement efficiency simultaneously.Overall,the newly formulated nanocellulose/surfactant combined system exhibits a remarkable EoR performance in low-permeability reservoirs.

Interconnected and high cycling stability polypyrrole supercapacitors using cellulose nanocrystals and commonly used inorganic salts as dopants

Polypyrrole(PPy)is wildly used as electrode material in supercapacitors due to its high conductivity,low cost,ease of handling,and ease of fabrication.However,limited capacitance and poor cycling stability hinder its practical application.After developing carboxylated cellulose nanocrystals(CNC-COO^(-))as immobile dopants for PPy to improve its cycling stability,we investigated the effect of different commonly used salts(KCl,NaCl,KBr,and NaClO_(4))as dopants during electrode fabrication by electropolymerization.The film’s capacitance increased from 160.6 to 183.4 F g^(-1)after adding a combination of KCl and NaClO_(4) into the electrodeposition electrolyte.More importantly,the porous and interconnected PPy/CNC-COO^(-)-Cl-(Cl O_(4)^(-))_0.5 electrode film exhibited an excellent capacitance of 125.0 F g^(-1)(0.78 F cm^(-2))at a high current density of 2.0 Ag^(-1)(20 m A cm^(-2),allowing charging in less than 1 min),increasing almost 204%over PPy/CNC-COO-films.A symmetric PPy/CNC-COO^(-)-Cl-(ClO_(4)^(-))_0.5 supercapacitor retained its full capacitance after 5000 cycles,and displayed a high energy density of 5.2 Wh kg^(-1)at a power density of 25.4 W kg^(-1)(34.5μWh cm^(-2) at 1752.3μW cm^(-2)).These results reveal that the porous structure formed by doping with CNC-COO-and inorganic salts opens up more active reaction areas to store charges in PPy-based films as the stiff and ribbon-like CNC-COO-as permanent dopants improve the strength and stability of PPy-based films.Our demonstration provides a simple and practical way to deposit PPy based supercapacitors with high capacitance,fast charging,and excellent cycling stability.

CNC/GENR自修复复合材料的制备

为获得兼顾力学性能和自修复性能的弹性体复合材料,将不同质量分数纤维素纳米晶(CNC)分别添加到甘氨酸改性的环氧化天然橡胶(GENR)基体中,制备了一系列基于CNC表面羟基和GENR分子链上羟基、羧基之间界面氢键作用的CNC/GENR复合材料,利用X射线光电子能谱、扫描电子显微镜、万能拉伸试验机等对CNC/GENR复合材料的界面氢键作用、机械强度、自修复性能进行了表征和分析。结果表明:CNC的引入显著提高了环氧化天然橡胶的机械性能,当添加质量分数为10%时,复合材料具备优异的力学性能和自修复性能,拉伸强度为4.4 MPa、断裂伸长率为1500%、自修复效率为90%,与未添加CNC样品相比分别增加了2倍、0.93倍和1.43倍。CNC/GENR复合材料实现了同时提高复合材料机械性能和自修复性能的目标。

Rheological and DSC Studies on the Interaction between κ-Carrageenan and Cellulose Nanocrystals (CNC)

Rheometer and differential scanning calorimetry （DSC） have been used to probe the mechanism of gelation in gels formed by mixture of k-carrageenan and cellulose nanocrystals （CNC）. The results indicated that an association occurred between CNC chains and aggregated k-carrageenan helices.

pH响应性气体渗透CNC/PBAT复合膜的制备与性能

具有可调控气体渗透的薄膜对包装保鲜领域发展具有重要意义,而设计具有pH响应性渗透和高力学性能的薄膜仍然是一个挑战。设计琥珀酸酐酯化与二乙烯三胺酰胺化的两步取代反应,实现纤维素纳米晶表面胺基(A-CNC)与羧基(S-CNC)功能化修饰,进一步与聚对苯二甲酸-己二酸丁二醇酯(PBAT)复合,制备具有互反pH响应性气体渗透的复合薄膜。结果表明,通过扫描电镜(SEM)、红外光谱(FTIR)和核磁共振^(13)C谱(^(13)C NMR)对纤维素纳米晶及其功能化修饰进行表征,证实改性成功。对复合薄膜性能表征:在力学性能方面,S-CNC/PBAT(3/97)与A-CNC/PBAT(5/95)复合薄膜拉伸强度达到最高,比PBAT分别增加40.44%与50.56%,但断裂伸长率下降,断裂模式由韧性向脆性断裂转变。在气体渗透性方面,复合薄膜展现出互反pH响应渗透特征。S-CNC/PBAT(5/95)复合薄膜渗透性出现正响应变化趋势,随着缓冲液pH(3~12)升高,CO_(2)与O_(2)渗透性分别增加67.98%和48.34%,水蒸气渗透性从2.467×10^(-13)变化到3.039×10^(-13)g·cm/(cm^(2)·s·Pa);而A-CNC/PBAT(5/95)复合薄膜渗透出现pH负响应性现象,CO_(2)与O_(2)渗透性分别降低63.00%与54.61%,水蒸气渗透性从2.747×10^(-13)变化到2.043×10^(-13)g·cm/(cm^(2)·s·Pa)。这种具有pH响应性渗透的复合薄膜在智能包装领域具有广阔的前景。

Polycaprolactone (PCL) Chains Grafting on the Surface of Cellulose Nanocrystals (CNCs) during <i>In Situ</i>Polymerization of <i>ε</i>-Caprolactone at Room Temperature

This work aimed at investigating the feasibility of surface modification of cellulose nanocrystals (CNCs) using in situ ring opening polymerization of ε-caprolactone (ε-CL) at room temperature. Residues of flax and milkweed (Asclepias syriaca) stem fibers were used as a source of cellulose to obtain and isolate CNCs. The cationic ring opening polymerization (CROP) of the monomer ε-CL was used to covalently graft polycaprolactone (PCL) chains at the CNCs surface. Silver hexafluoroantimonate (AgSbF6) was used in combination with the extracted CNCs to initiate, at room temperature, the polymerization and the grafting reactions with no other stimulus. Fourier-Transform InfraRed (FTIR), X-ray Photoelectron Spectrometry (XPS), UV/visible absorption and Gel Permeation Chromatography (GPC) analyses evidenced the presence of PCL chains covalently grafted at CNCs surface, the formation of Ag(0) particles as well as low or moderate molecular weight free PCL chains.

接枝反应温度和时间对NBR/CNC-g-AA复合材料性能的影响

利用溶液法,以硝酸铈铵为引发剂,将丙烯酸(AA)接枝到纤维素纳米晶(CNC)上进行改性得到接枝产物丙烯酸接枝纤维素纳米晶(CNC-g-AA),并且与丁腈橡胶(NBR)共混,制备NBR/CNC-g-AA复合材料,研究接枝反应温度和反应时间对NBR/CNC-g-AA复合材料硫化特性、力学性能和耐磨性能的影响。结果表明,CNC-g-AA在1720 cm-1处出现红外吸收峰,说明CNC-g-AA制备成功;接枝反应温度和反应时间对NBR/CNC-g-AA复合材料的硫化特性无明显影响规律,但是对其拉伸性能和耐磨性能有着不同影响规律,并且当接枝反应温度为35℃、反应时间为60 min时,NBR/CNC-g-AA复合材料的拉伸性能和耐磨性能均达到最优值。

Surface Chemical Modification of Cellulose Nanocrystals and Its Application in Biomaterials

Cellulose nanocrystals(CNCs) have been widely applied in biomaterials and show great biocompatibility and mechanical strength. In this review, the chemical reactions applied in CNC surface modification and their application in CNC based biomaterials are introduced. Furthermore, the conjugation of different functional molecules and nanostructures to the surface of CNCs are discussed, with focus on the binding modes, reaction conditions, and reaction mechanisms. With this introduction, we hope to provide a clear view of the strategies for surface modification of CNCs and their application in biomaterials, thus providing an overall picture of promising CNC-based biomaterials and their production.

Nanocellulose-Based Biosensors: Design, Preparation, and Activity of Peptide-Linked Cotton Cellulose Nanocrystals Having Fluorimetric and Colorimetric Elastase Detection Sensitivity

Nanocrystalline cellulose is an amphiphilic, high surface area material that can be easily functionalized and is biocompatible and eco-friendly. It has been used singularly and in combination with other nanomaterials to optimize biosensor design. The attachment of peptides and proteins to nanocrystalline cellulose and their proven retention of activity provide a route to bioactive conjugates useful in designs for point of care biosensors. Elastase is a biomarker for a number of inflammatory diseases including chronic wounds, and its rapid sensitive detection with a facile approach to sensing is of interest. An increased interest in the use of elastase sensors for point of care diagnosis is resulting in a variety of approaches to elsastase sensors utilizing different detection technologies. Here elastase substrate peptide-celluose conjugates synthesized as colorimetric and fluorescent sensors on cotton cellulose nanocrystals are compared. The structure of the sensor peptide-nanocellulose crystals when modeled with computational crystal structure parameters demonstrates the spatio-stoichiometric features of the nanocrystalline surface that allows ligand to active site protease interacttion. An understanding of the structure/function relations of enzyme and conjugate substrate of the peptides covalently attached to nancellulose has implications for enhancing the biomolecular transducer. The potential applications of both fluorescent and colorimetric detection to markers like elastase using peptide cotton cellulose nanocrystals as a transducer surface to model point of care biosensors for protease detection are discussed.

Thermal and Crystallization Behavior of PLA/PLLA-Grafting Cellulose Nanocrystal

PLLA-modified cellulose nanocrystals (CNC) were produced from commercial CNC by tin-catalyzed polymerization of lactide in presence of CNC. FTIR spectroscopy demonstrated that the result of the reaction produced the grafting of PLLA chains onto CNC surface (CNC-g-PLLA). Films of poly(lactic acid) (PLA) and PLA/CNC nanocomposites (with non-modified CNC and CNC-g-PLLA) containing 0.5% and 5% (w/w) of the nanofillers were prepared by casting in chloroform solution and the crystallization behavior and thermal properties investigated. All nano-composites had similar thermal stability when analyzed by TGA analyses under an inert nitrogen atmosphere. Addition of both types of CNC influenced crystallization, the higher crystallization rate being observed for 5% (w/w) CNC. Nanocomposites with 5% (w/w) CNC-g-PLLA had the strain resistance of PLA improved in the rubbery state. PLLA-modification of CNC surface increased the crystallization of PLA in PLA/CNC nanocomposites and improved the rigidity at temperatures above the glass transition, properties which are desirable for hot drinking application.

Regulating the Function of Nanocomposite Made from Hydroxypropyl Methyl Cellulose with Bacterial Cellulose Nanocrystal

Hydroxypropyl methyl cellulose(HPMC)-based hybrid nanocomposites reinforced with bacterial cellulose nanocrystals(BCNC) were prepared and characterized.The HPMC nanocomposites exhibited good thermal stability,with a thermogravimetric peak temperature of around 346℃.The addition of BCNC did not significantly affect the thermal degradation temperature or improve the transparency of HPMC nanocomposites.However,the addition of BCNC favorably affected the light scattering properties of the nanocomposites and enhanced mechanical properties such as tensile stress and Young's modulus from 65 MPa and 1.5 GPa up to 139 MPa and 3.2 GPa,respectively.The oxygen permeability of the HPMC nanocomposites also increased with increase in the amount of BCNC added.

Isolation of Thermally Stable Cellulose Nanocrystals from Spent Coffee Grounds via Phosphoric Acid Hydrolysis

As the world's population exponentially grows,so does the need for the production of food,with cereal production growing annually from an estimated 1.0 billion to 2.5 billion tons within the last few decades.This rapid growth in food production results in an ever increasing amount of agricultural wastes,of which already occupies nearly 50%of the total landfill area.For example,is the billions of dry tons of cellulose-containing spent coffee grounds disposed in landfills annually.This paper seeks to provide a method for isolating cellulose nanocrystals(CNCs)from spent coffee grounds,in order to recycle and utilize the cellulosic waste material which would otherwise have no applications.CNCs have already been shown to have vast applications in the polymer engineering field,mainly utilized for their high strength to weight ratio for reinforcement of polymer-based nanocomposites.A successful method of purifying and hydrolyzing the spent coffee grounds in order to isolate usable CNCs was established.The CNCs were then characterized using current techniques to determine important chemical and physical properties.A few crucial properties determined were aspect ratio of 12±3,crystallinity of 74.2%,surface charge density of(48.4±6.2)mM/kg cellulose,and the ability to successfully reinforce a polymer based nanocomposite.These characteristics compare well to other literature data and common commercial sources of CNCs.

Edible Coatings Based on Apple Pectin,Cellulose Nanocrystals,and Essential Oil of Lemongrass:Improving the Quality and Shelf Life of Strawberries(Fragaria Ananassa)

In this work,nine different types of edible coating based on pectin,cellulose nanocrystals,glycerol,and essential oil of lemongrass were prepared and used to coat strawberries with a film formed directly on the surface of the coated fruit.The effects of the different edible coatings on refrigerated fruits in terms of weight loss,titratable acidity,total soluble solids,pH,and anthocyanin content was evaluated after 2 days,4 days,6 days,and 8 days of storage.Application of the edible coatings reduced the weight loss of the coated strawberries and the anthocyanin content.The total soluble solids content of or uncoated fruit increase more markedly than that of coated fruit.In contrast,pH was maintained for both coated and uncoated strawberries.The edible coatings were effective in minimizing of the weight loss,without worsening the physical chemistry attributes.The treatments T5 and T9 presented the best results.

Preparation of Dicarboxyl Cellulose Nanocrystals from Agricultural Wastes by Sequential Periodate-Chlorite Oxidation

Agricultural waste straw is the renewable resource with the highest annual yield in the world.In value-added applications of agricultural waste,dicarboxyl cellulose nanocrystals(DCCs)are prepared from rice,wheat,and corn straw by sequential periodate-chlorite oxidation.In this study,DCCs from rice,wheat,and corn straw were characterized by transmission electron microscopy(TEM),Fourier transform infrared spectrometer,X-ray diffractometer(XRD),and thermal gravimetric analysis(TGA).The carboxyl content of the DCCs was also investigated.XRD results show that the crystallinity index decreased after sequential periodate-chlorite oxidation;however,the cellulose I structure was maintained.TEM results show that rod-shaped DCCs with an average length and width of 287.0 nm and 9.9 nm,respectively,were successfully prepared by sequential periodate-chlorite oxidation.The carboxyl content of the DCCs was around 3.9 mmol/g,and not affected by the type of straw.Experiments to study the removal of copper ions in aqueous medium were performed with the prepared DCCs.The adsorption capacities of copper ions were 131,162,and 144 mg/g for DCCs prepared from rice,wheat,and corn straws,respectively.The results show that DCCs prepared from rice,wheat,and corn straws by sequential periodatechlorite oxidation have potential for the removal of copper ions from aqueous medium.

Preparation and Application of Anionic and Cationic Waterborne Polyurethanes and Graphene-Cellulose Nanocrystal as an Antistatic Agent for Cashmere

The main purpose of this research work is to improve anti-static properties of Cashmere fabric by introducing application comprising anti-static agent by foaming which was made with cationic waterborne polyurethane and graphene-CNC. Cashmere fabric was cut into 10 pieces of sample cloth of 5 cm * 5 cm size, washed with acetone solution, and then dried in an oven at 60℃. Three forms of waterborne polyurethanes such as two forms of Cationic waterborne polyurethane (CWPU) and a form of Anionic waterborne polyurethane (AWPU) were synthesized. Cellulose nanocrystalline (CNC)/graphite powder solution with the ratio of 0.5/1, 1/1, 2/1 was prepared by ultrasonic probe stripping method, and the concentration of graphite powder was ensured to be 1 mg/ml. The fabric was treated with anionic and cationic WPUs foaming solution until the weight gain reached 2.5 - 3.5 wt%. After drying, the elastic cloth was foamed with graphene solution until the graphite content of the cloth was close to 10%, 20%, 40%, 60% respectively, and then dried for reserving. Characterization properties of pure graphite powder, pure CNC and graphene solution with different proportions of three components were tested by Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), Thermalgravitimetric analysis (TGA) and scanning electron microscopy (SEM). Take the original cloth, only WPU treated cloth and four clothes with different graphite content for the fabric performance test.

Review on Cellulose Nanocrystal Assembly for Optical Applications

Cellulose nanocrystals(CNCs)can self-assemble in suspension to form chiral cholesteric structure of liquid crystal with unique birefringence phenomena,and the structural parameters strongly depend upon the aspect ratio,surface structure,and physicochemical properties of CNC,along with suspension media.Many attempts have been carried out to keep this cholesteric structure in solid state via removing solvent,such as slower solvent-evaporation,rapid vacuum-filtration,and spin-casting under centrifugal force.The solid-state iridescence of the cholesteric CNC arrays has been used as structural color,and showed a great potential for the coding and securing of optical information.Moreover,to promote practical applications of such structural iridescence,the cholesteric CNC arrays have been embedded into many kinds of substrates via in-situ reaction of monomers or physical blending with polymers.However,this kind of structural iridescences may lead to misreading information.The uniaxial-orientation assembly of CNC has thus been proposed via regulating external force fields of CNC self-assembly,and successfully achieved nanoparticle assembly-induced solid-state monochrome emission based on enhanced inelastic collision theory of CNC dipoles and photons.This method can eliminate the chiral arrangement of CNC and the corresponding iridescence,and the structural monochromaticity can contribute to enhancing the accuracy of optical information.Overall,the CNC can be controllably assembled as the ordered arrays in solid state and presented structural color,and support optical anti-counterfeiting strategies different from the fluorescent technologies.

CNCs增强相分离法构建PVDF/PDMS超疏水表面

采用非诱导相分离法,将纤维素纳米晶(CNCs)与两种聚合物(聚偏二氟乙烯和聚二甲基硅氧烷)进行结合,利用CNCs之间的静电排斥力及其大比表面积特性有效降低相分离过程中聚合物的聚集,减小了粒子尺寸,增强了粒子分散性,在棉布、木板和玻璃表面构造了精细、均匀的微纳米粗糙结构。采用FTIR、SEM、AFM、接触角测量仪、3D光学轮廓仪对CNCs和超疏水表面的形貌、结构和超疏水性进行了表征。结果发现,棉布、木板和玻璃表面的水接触角最高分别可达158.0°、156.8°和153.8°,滚动角最低分别为2.0°、2.7°和3.4°,呈现出明显的超疏水特征。经过机械摩擦(约500次)、酸碱处理(pH 1~13)、温度变化(–40~40℃)以及紫外光照射(0~320 h)后,基材表面仍具有较好的超疏水性。此外,基材具有优异的自清洁性和油水分离效率,超疏水棉布的最高分离效率可达98.4%。

Poly(Butylene Adipate-Co-Terephthalate)and Poly(ε-Caprolactone)and Their Bionanocomposites with Cellulose Nanocrystals:Thermo-Mechanical Properties and Cell Viability Study

Although nanocomposites have recently attracted special interest in the tissue engineering area,due to their potential to reinforce scaffolds for hard tissues applications,a number of variables must be set prior to any clinical application.This manuscript addresses the evaluation of thermo-mechanical properties and of cell proliferation of cellulose nanocrystals(CNC),poly(butylene adipate-co-terephthalate)(PBAT),poly(ε-caprolactone)(PCL)films and their bionanocomposites with 2 wt% of CNC obtained by casting technique.Cellulose nanocrystals extracted from Balsa wood by acid hydrolysis were used as a reinforcing phase in PBAT and PCL matrix films.The films and pure CNC at different concentrations were cultured with osteoblasts MG-63 and the cell proliferation was assessed by AlamarBlue?assay.The thermal-mechanical properties of the films were evaluated by dynamic-mechanical thermal analysis(DMTA).It was found by DMTA that the CNC acted as reinforcing agent.The addition of CNCs in the PBAT and PCL matrices induced higher storage moduli due to the reinforcement effects of CNCs.The cell viability results showed that neat CNC favored osteoblast proliferation and both PBAT and PCL films incorporated with CNC were biocompatible and supported cell proliferation along time.The nature of the polymeric matrix or the presence of CNC practically did not affect the cell proliferation,confirming they have no in vitro toxicity.Such features make cellulose nanocrystals a suitable candidate for the reinforcement of biodegradable scaffolds for tissue engineering and biomedical applications.

Green Modification of Cellulose Nanocrystals and Their Reinforcement in Nanocomposites of Polylactic Acid

Cellulose nanocrystals(CNCs) of rod-like shape were prepared from degreased cotton using sulfuric acid hydrolysis. The obtained CNC suspension was neutralized using a sodium hydroxide solution to remove the residual sulfuric acid and improve the thermal stability of the CNC particles. Then, poly(ethylene oxide)(PEO) was employed to modify the nanocrystals through entanglement and physical adsorption. The goal was to further improve the thermal stability and weaken the hydrophilicity of CNCs. Original and modified CNCs were dosed into a polylactic acid(PLA) matrix to prepare nanocomposites using a hot compression process. Results of the thermogravimetric analysis showed that the initial thermal decomposition temperature of the modified CNCs showed a 120℃ improvement compared to the original CNCs. That is, the thermal stability of the modified CNCs improved because of their shielding and wrapping by a PEO layer on their surface. Results from scanning electron microscopy and ultraviolet-visible spectrophotometry showed that the compatibility of the modified CNCs with organic PLA improved, which was attributed to the compatibility of the PEO chains adsorbed on the surface of the CNCs. Finally, the results of tensile tests indicated a significant improvement in terms of breaking strength and elongation at the break point.