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CHINESE JOURNAL OF POLYMER SCIENCE · 2022 ·Vol. 40 ·期 3 ·299-309 · IF 3.815

Cellulose Nanocrystals-mediated Phase Morphology of PLLA/TPU Blends for 3D Printing

Wu Xiao,Liu Yun-Xiao,Wu Hai-Peng,Wu Hao,Wang Hai-Jun,Duan Yong-Xin,Zhang Jian-Ming

Incorporation of nanoparticles into polymer blend to obtain finely dispersed morphology has been considered as an effective strategy to prepare nanocomposites. Owing to the renewable and degradable characters, cellulose nanocrystals (CNCs) have been proposed to tailor the phase morphology of poly(L-lactic acid) (PLLA) blend for producing high-performance fused deposition modeling (FDM) consumables. However, the main challenge associated with the ternary systems is the dispersion of the highly hydrophilic CNCs in non-polar PLLA blend by industrial melt blending without involving solution. Herein, with poly(vinyl acetate) (PVAc) modified CNCs powder (a mixture of PVAc grafted from CNCs and PVAc homopolymer latex), the selective dispersion of CNCs in PLLA has been achieved by simple melt processing of PLLA/TPU (polyether polyurethane)/CNCs blend. This results in the ultra-fine TPU droplets at nanoscale in PLLA and improves the melt processibility of composites in FDM due to the decreased viscosity ratio of the dispersed/matrix and the enhanced melt elasticity of PLLA. Combined with the intensive shear and continuous stretch effect during FDM, aligned TPU nanofibers (TNFs) were in situ formed along the elongational flow direction during deposition, which in turn contributed to the improvement of PLLA/TPU/CNCs with 5 wt% filler loading in tensile ductility by 418%, inter-layer adhesion strength and notched impact toughness by 261% and 210%, respectively, as well as achieved good dimensional accuracy and very fine surface quality.

CAS / MDL: 16774-21-3 108-05-4
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Mechanistic investigation of cellulose formate to 5-hydroxymethylfurfural conversion in DMSO-H2O

Shen Zhang,Caidi Jin,Kuichuan Sheng,Ximing Zhang

5-hydroxymethylfurfural (HMF) primary can be synthesized from monosaccharides including glucose and fructose, cost is one of barriers to realize HMF large-scale production. In this study, a high HMF yield of 69.6 mol% was obtained at 180℃ for 5 min using biomass derived cellulose formate as reactant, which was prepared by formylation of cellulose using recyclable formic acid, and sequentially catalyzed by hydrochloric acid (HCl) and aluminum chloride (AlCl 3 ) in dimethyl sulfoxide (DMSO) and H 2 O system. To investigate the effect of cosolvents and formyl groups on the cellulose formate conversion, kinetics analysis and molecular dynamics simulations were conducted. Reaction kinetics study shows that the rate constant of hydrolysis of cellulose formate to glucose increased by almost three times in DMSO-H 2 O and the reaction rates’ constants of glucose, fructose and HMF to humins decreased with the presence of DMSO. Molecular dynamics simulations show that formyl group and DMSO increased its hydrophilicity around the reactive hydroxyl group on the carbon ring and steric hindrance of formyl group affect the distribution of water molecular and DMSO molecular around formylated glucose, resulting in facilitating the formation of a precursor to fructose and inhibiting the formation of humins during formylated glucose conversion.

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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Bulk cross-linked hydroxyethyl cellulose-silica composite membrane for acid-stable nanofiltration

Shengpeng Jiang,Jiahui Wu,Bingrong Ma,Meihong Liu,Sanchuan Yu,Congjie Gao

This work focused on the construction of an acid-resistant composite nanofiltration membrane with the selective layer of bulk cross-linked hydroxyethyl cellulose (HEC)-silica and a support of porous polypropylene . Membranes were fabricated through in-situ sol-gel reaction and slot-die coating method employing tetraethyl orthosilicate (TEOS) as the silica precursor and cross-linking agent of HEC. Membrane structure and performance were tuned by controlling the hydrolysis time of TEOS and differentiating TEOS and HEC contents, and systematically characterized in terms of physico-chemical property, permeation attribution and acid stability. It was found that membrane performance was strongly correlated with the relative contents of C–O–Si and Si–O–Si bonds of the formed HEC-silica selective layer. High content of C–O–Si bond formed via condensation reaction of HEC and TEOS endowed the selective layer with denser network structure and good rejection ability. Both insufficient and excessive hydrolysis led to a poor rejection ability of formed membrane. The optimized HEC-silica membrane possessed an average pore size of about 1.43 nm within the scope of nanofiltration membrane, a high pure water permeability coefficient of around 10.5 LMH/bar, and a medium rejection of 85.2% to 500 mg/l Na 2 SO 4 aqueous solution at 5.0 bar. No changes in both chemical structure and separation performance occurred with the HEC-silica composite membrane after being soaked in aqueous H 2 SO 4 solution of 4.9 wt% for 7 days, while evident structure destruction and serious performance degradation occurred with the compared polyamide-based commercial membrane NF270. Long-term soaking test using 15.0 wt% H 2 SO 4 aqueous solution for 30 days also demonstrated that the acid resistance HEC silica membrane was comparable with those reported acid stable nanofiltration membranes. Furthermore, the HEC-silica membrane also maintained its water permeation and solute rejection abilities during a 30-day continuous filtration of aqueous solution of 4.9 wt% H 2 SO 4 and 50 mg/l polyethylene glycol fraction (PEG2000). The good acid resistance of the HEC-silica composite membrane was attributed to its bulk cross-linked network structure composed of C–O–Si, Si–O–Si and C–C bonds.

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Membranes · 2022 ·Vol. 12 ·期 2 ·122 · IF 4.562

Desalination Characteristics of Cellulose Acetate FO Membrane Incorporated with ZIF-8 Nanoparticles

Tong Li,Yuhong Wang,Xinyan Wang,Caixia Cheng,Kaifeng Zhang,Jie Yang,Guangshuo Han,Zhongpeng Wang,Xiuju Wang,Liguo Wang

Forward osmosis membranes have a wide range of applications in the field of water treatment. However, the application of seawater desalination is restricted, so the research of forward osmosis membranes for seawater desalination poses new challenges. In this study, zeolitic imidazolate framework-8 (ZIF-8) was synthesized by a mechanical stirring method, and its crystal structure, surface morphology, functional group characteristics, thermochemical stability, pore size distribution and specific surface area were analyzed. The cellulose acetate (CA)/ZIF-8 mixed matrix forward osmosis membrane was prepared by using the synthesized ZIF-8 as a modified additive. The effects of the additive ZIF-8 content, coagulation bath temperature, mixing temperature and heat treatment temperature on the properties of the CA/ZIF-8 forward osmosis membrane were systematically studied, and the causes were analyzed to determine the best membrane preparation parameters. The structure of the CA membrane and CA/ZIF-8 mixed matrix forward osmosis membranes prepared under the optimal conditions were characterized by Fourier Transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), contact angle and Atomic force microscope (AFM). Finally, the properties of the HTI membrane (Membrane manufactured by Hydration Technology Innovations Inc.), CA forward osmosis membrane and CA/ZIF-8 mixed matrix forward osmosis membrane were compared under laboratory conditions. For the CA membrane, the water flux and reverse salt flux reached 48.85 L·m−2·h−1and 3.4 g·m−2·h−1, respectively. The reverse salt flux and water flux of the CA/ZIF-8 membrane are 2.84 g·m−2·h−1and 50.14 L·m−2·h−1, respectively. ZIF-8 has a promising application in seawater desalination.Keywords:desalination;ZIF-8;forward osmosis membranes

CAS / MDL: 9004-35-7
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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Bubble-Templated Design of Superelastic Cellulose Foam as a Durable Ionotropic Sensor

Xue An,Xiaofang Zhang,Mingjie Li,Danfeng Pei,Xiaomei Ma,Chaoxu Li

Introduction of superelasticity and electric conductivity into ecofriendly and biocompatible cellulose-based foams is highly in pursuit for applications in wearable sensors, artificial skin, and soft robotics. Nevertheless, producing superelastic materials with electric conductivity often fails due to the mechanical brittleness and dielectric feature. Herein, we designed a novel type of regenerated cellulose foam with electric conductivity, superelasticity, and negative Poisson’s ratio by combining an air bubble template and ionic liquid modification process. The pore size and density could be controlled between 60 and 750 μm and 74.4 and 125.5 mg cm–3, respectively, by tuning the vacuum degree during the regeneration process. With the presence of cellular microstructures and ionic liquid, this regenerated cellulose foam could reach a high compression strain of up to 90% with a negligible plastic deformation and showed superflexible mechanical performance (tensile yield strain of ∼25%, torsion to 720°, and bending to 180°), together with stable ionotropic conductivity. Both the superelasticity and conductivity could be maintained even after more than 103 cycles of periodic compression. Thus, this novel type of regenerated cellulose foam would be capable of serving as elastic biomaterials and promise applications in many flexible devices.

CAS / MDL: 151-21-3 75-65-0
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Journal of Nanostructure in Chemistry · 2022 ·Vol. 13 ·期 4 ·439-449 · IF 8

Cellulose in situ formation of three primary nanoparticles for polymer scalable colors

Zhang Yang,Xu Zhiqiang,Meng Zhichao,Shi Shan,Sui Guoxin

Polymer coloration technology has been receiving increasing attention in different fields including electronic packaging, artificial skin and 3D printing. Herein, we report a new strategy utilizing three primary nanocomposites (cellulose@Fe 3 O 4 , cellulose@FeOOH and cellulose@PB) as unique coloring components for scalable colored polymer-based composites. Taking the epoxy resin as polymer matrix for example, the as-made polymer-based composites present different colors, including red/yellow/blue colors and many spectral colors achieved by mixing the three primary nanocomposites. The nanocomposites act not only as the primary nanopigments, but also as the connected bridge to tightly stick polymer matrix through strong chemical bonding, respectively. In addition, the colored polymer-based composites show excellent opacity and UV protection. Our work offers a facile coloration approach for arbitrary colors over the whole visible spectra by mixing three primary nanocomposites at different ratios in the polymer field. With bright, uniform, and ratio-dependent color, we showcase three typical polymers to demonstrate the versatility of coloring strategy. Graphical abstract We have developed a simple strategy to fabricate cellulose in situ deposited three primary nanocomposites. Taking the polymer matrix for example, arbitrary color can be created by mixing them into polymer at different ratios over the whole visible spectra by dispersing three primary nanocomposites.

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Journal of Cleaner Production · 2022 · IF 11.072

Greener production of cellulose nanocrystals: An optimised design and life cycle assessment

Lei Zhang,Xuexiu Jia,Yusen Ai,Renliang Huang,Wei Qi,Zhimin He,Jiří Jaromír Klemeš,Rongxin Su

Cellulose nanocrystals (CNCs) are usually prepared by sulphuric acid hydrolysis in industrial production, resulting in a large amount of alkaline and water consumption. In this paper, three acid-CNCs separation methods, including gravity settling, centrifugation and microfiltration , are used to directly separate sulphuric acid from hydrolysate mixture to reduce alkaline and water consumption. Microfiltration was selected as the best method for acid-CNCs separation. Using microfiltration, the highest sulphuric acid recovery ratio was about 65.0%, with an acid concentration range of 8–10 wt% in the pilot-scale CNCs production. Continuous centrifugation was introduced to replace gravity settling to separate CNCs from the neutralised mixture for faster production and reducing water consumption. The consumption of alkaline and water decreased by 63.0% and 68.0%, and the cost was reduced by 26%. The result of life cycle assessment (LCA) showed that the process with acid-CNCs separation using microfiltration achieved a reduction of 33.4% in aquatic ecotoxicity, 38.1% in terrestrial ecotoxicity , 47.9% in aquatic acidification, 55.8% in aquatic eutrophication , 40.0% in global warming potential and 47.8% in non-renewable energy consumptions. This study provided a promising approach for separating sulphuric acid from hydrolysate mixture and reducing consumption of alkaline and water. Such clean and economic process has great potential in the industrial production of CNCs.

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Biomass Conversion and Biorefinery · 2022 · IF 4.05

Thermal behaviors and kinetics for cellulose pyrolysis using CexZr1−x-T catalysts

Liu Huiyu,Zhang Jun,Gu Jing,Yuan Haoran,Chen Yong

In the present study, a series of Ce-Zr binary metal oxides (Ce x Zr 1−x -T, x  = 0.2, 0.5, 0.8) with variable physicochemical characteristics were developed for fast pyrolysis of cellulose, wherein thermal decomposition behaviors and kinetics were investigated using TG-MS and Py-GC/MS methods. Comprehensive characterizations including XRD, NH 3 -TPD, CO 2 -TPD, and SEM were conducted to unveil the essential structural properties of as-prepared Ce x Zr 1−x -T materials. Ce x Zr 1−x -T calcined at 450 °C and 550 °C could supply suitable medium to strong acid–base sites and good porosity for the pyrolysis of cellulose into ketones, aldehydes, and hydrocarbons, especially for Ce 0.8 Zr 0.2 –550. Elevation of heating rate and catalyst usage significantly promoted the yielding of ketones, aliphatic hydrocarbons, and aromatic hydrocarbons. Moreover, the activation energy for cellulose pyrolysis was lowered to 96.9 kJ/mol in the presence of Ce 0.8 Zr 0.2 –550, due to the promotional role of existing acid–base sites.

CAS / MDL: 9004-34-6
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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

Preparation of chitosan-cellulose-benzyl isothiocyanate nanocomposite film for food packaging applications

Jinghui Jiang,Xiaoxia Chen,Gong-Liang Zhang,Hongshun Hao,Hong-Man Hou,Jingran Bi

To improve the mechanical and barrier properties of cellulose and chitosan (CS) and to allow the application of volatile antibacterial benzyl isothiocyanate (BITC) in active packaging, a double-layer nanocomposite film was prepared. Cellulose nanofibers (CNF) were crosslinked with CS via genipin to build the substrate. Quaternized cellulose nanocrystals (QCNC) were synthesized for carrying BITC as the coating material . By the layer-by-layer self-assembly approach, CS-CNF/QCNC-BITC film was fabricated. This film possessed the tensile strength of 33.75 MPa, low permeabilities of oxygen (6.9 × 10 −17  m 3 /s·m·Pa) and moisture (1.2 × 10 −11  g/s·m·Pa), and good antibacterial activity with the inhibition zone diameters of 4.9, 4.2 and 2.7 cm against Escherichia coli , Salmonella typhimurium and Staphylococcus aureus . The total viable count , total volatile basic nitrogen and thiobarbituric acid-reactive substances of the chicken wrapped CS-CNF/QCNC-BITC were only 4.4 log CFU/g, 17.7 mg/100 g and 0.44 mg/kg at 14 days, indicating a potential application of CS-CNF/QCNC-BITC for food packaging.

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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

An environmentally tolerant, highly stable, cellulose nanofiber-reinforced, conductive hydrogel multifunctional sensor

Miao Li,Dong Chen,Xia Sun,Zesheng Xu,Yutong Yang,Yongming Song,Feng Jiang

The application of flexible multifunctional sensors based on conductive hydrogels in human health detection has been widely studied. Herein, a facile one-pot method is proposed to prepare ionic conductive hydrogels by dissolving polyvinyl alcohol (PVA), cellulose nanofiber (CNF), and aluminum chloride hexahydrate (AlCl 3 ·6H 2 O) in a dimethyl sulfoxide (DMSO)/water binary solvent. The resulting ionically-conductive organohydrogels have high stretchability (up to 696%), fast response (130 ms), wide operating temperature (−50 °C to 50 °C), and long-term stability (30 days). The hydrogel sensor exhibits excellent signal sensing capability (human motion and sound detection signals) and cycling stability (1000 cycles) under extreme temperature and long-term storage conditions. Notably, the organohydrogel displays high sensitivity to both compressive deformation and temperature, resulting in multifunctional sensing performance. This work provides a viable approach for the long-term use of hydrogels as wearable devices in extreme environments and daily life.

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POLYMER COMPOSITES · 2023 ·Vol. 44 ·期 11 ·7865-7875 · IF 5.2

Preparing microcrystalline cellulose-reinforced polylactic acid composites by an energy saving method

Xue Jia,Boyu Cui,Shuang Li,Hao Xie,Weihong Wang,Yutong Cui,Jiayan Ding,Xianquan Zhang,Yongming Song

Microcrystalline cellulose (MCC) fibers are co mmonly used to reinforce polymers; however, their freeze-drying process consumes a lot of energy. In this study, MCC dried at different temperatures, oven-dried at 25, 50, 75, and 103°C and freeze-dried, was evaluated based on their effect on the reinforced composites. The dried MCC was compounded with polylactic acid (PLA) by melt extrusion and compressed into an MCC/PLA composite film. The morphology, structure, and crystallinity of the dried MCCs and MCC/PLA composites were analyzed using scanning electron microscopy, laser particle size analysis, x-ray diffraction, mechanical testing, and Fourier transform infrared spectroscopy. It was proved that MCC dried at 103°C was more uniformly dispersed and tightly bound to the PLA matrix than freeze-dried MCC. Tensile measurements showed that the MCC dried at 103°C had nearly the same tensile strength (58.35 MPa) as that of the freeze-dried MCC (58.7 MPa) and was higher than that of the other oven-dried MCC. Energy consumption evaluation revealed that oven-drying consumed much less energy than freeze-drying MCC for 24 h to obtain the same final moisture content. MCC dried at 103°C has significantly better properties than MCC dried at 25, 50, and 75°C, similar to freeze-drying. Concerning performance and energy consumption, drying at 103°C is determined the optimal choice to support the preparation of MCC-reinforced PLA composites. Highlights Drying temperature effects aggregation of MCC. MCC Dried at 103°C can present similar properties to freeze-dried MCC but save more energy. Oven-drying can be a good way to dry MCC for the preparation of MCC/PLA composite.

CAS / MDL: 67-48-1 6153-56-6
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Small · 2023 ·Vol. 19 ·期 50 ·2304674 · IF 13.3

Defect Engineered Microcrystalline Cellulose for Enhanced Cocatalyst-Free Piezo-Catalytic H2 Production

Kailai Zhang,Xiaodong Sun,Haijun Hu,Ge Yan,Anqi Qin,Yali Ma,Hongwei Huang,Tianyi Ma

Mechanical energy driven piezocatalytic hydrogen (H 2 ) production is a promising way to solve the energy crisis . But limited by the slow separation and transfer efficiency of piezoelectric charges generated on the surface of piezocatalysts , the piezocatalytic performance is still not satisfactory. Here, defect engineering is first used to optimize the piezocatalytic performance of microcrystalline cellulose (MCC). The piezocatalytic H 2 production rate of MCC with the optimal defect concentration can reach up to 84.47 µmol g −1 h −1 under ultrasonic vibration without any co-catalyst, which is ≈3.74 times higher than that of the pure MCC (22.65 µmol g −1 h −1 ). The enhanced H 2 production rate by piezoelectric catalysis is mainly due to the introduction of defect engineering on MCC, which disorders the symmetry of MCC crystal structure, improves the electrical conductivity of the material, and accelerates the separation and transfer efficiency of piezoelectric charges. Moreover, the piezocatalytic H 2 production rate of MCC with the optimal defect concentration can still reach up to 93.61 µmol g −1 h −1 in natural seawater, showingits commendable practicability. This study presents a novel view for designing marvelous-performance biomass piezocatalysts through defect engineering, which can efficiently convert mechanical energy into chemical energy .

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