Preparation and Characterization of Cellulose Nanofibril-Waterborne Polyurethane Composite Films

To improve the performance of polyurethane films,small amounts of cellulose nanofibrils(CNF)were physically blended with a waterborne polyurethane(WPU)emulsion,and then CNF/WPU composite films were prepared by cast-coating and drying.The particle size of the emulsions and the chemical structure,micromorphology,thermal stability,mechanical properties,and water resistance of the composite films were characterized using a Malvern laser particle size analyzer,Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),an electronic strength machine,water contact angle analysis(WCA),and water absorption tests,respectively.The results showed that at a low CNF content of 0.3 wt%,the particle size of the WPU emulsion and chemical structure of the film did not change significantly.In addition,the tensile strength of the composite film increased by up to 108%compared to the neat WPU film,and the thermal stability and water resistance were slightly improved.The addition of CNF greatly enhanced the tensile strength while maintaining the other original properties of the WPU film,which may greatly improve the service life and tear resistance of commercial coatings in the future.

Comparison of Nanofibrillated Cellulose and Hydroxyethyl Cellulose in Improving the Storage Stability of Waterborne Coatings

Waterborne coatings often delaminate and settle during long-term storage,requiring the addition of thickeners.The effects of nanofibrillated cellulose(NFC)and the commonly used thickener,hydroxyethyl cellulose(HEC),on the storage stability of waterborne coatings were compared in this study.The morphology of NFC was characterized using infrared spectroscopy(FT-IR)and scanning electron microscopy(SEM).The rotational viscosity and rheological properties of the waterborne coatings with NFC and HEC were tested.Stationary settling experiments were also conducted at different temperatures to compare the difference of NFC and HEC on improving the storage stability of the waterborne coatings.The results showed that the waterborne coating with NFC exhibited pseudoplastic fluid characteristics;a small addition of NFC can achieve the same improvement effect on the storage stability of waterborne coatings as HEC.Further,the improvement effect of NFC was not affected by temperature.The waterborne coating with NFC still exhibited good storage stability at high temperatures,which was significantly superior to that of HEC.Therefore,NFC is a feasible agent for improving the prolonged storage stability and warming-induced delamination of waterborne coatings.

Degradable Foam Tray Based on High-concentration Dispersed Cellulose Fibers Obtained by a Hot-press Baking Process

Degradable industrial packaging foam trays made from cellulose fibers were fabricated using a hot-press baking process.Bleached softwood pulp fibers with a concentration of 30%were dispersed at a high speed under the action of a dispersant.The effects of the dispersant dosage of the fibers on the porosity,foam density,and static compression characteristics were discussed.Furthermore,the effects of the reinforcing adhesive including polyvinyl alcohol(PVA),and cassava starch on the physical and mechanical properties of the foam trays were studied,as well as the relationship between these properties and the microstructure of the foam trays.The dispersant enhanced the rheological and blistering properties of the fiber dispersion.As the dispersant dosage increased from 2%to 4%,the foam density gradually increased and the compressive strain performance and residual compressive strain of the foam trays decreased.Under the condition of constant dosage of dispersant,increasing the fiber proportion from 67%to 77%improved the porosity and foam density and slightly reduced the static compression performance.In additioton,the static compression resistance of the foamed materials was improved by increasing the PVA dosage since PVA was beneficial for improving the strength of the foam trays.

Research Status and Prospects of Bio-based Materials for Grease Barrier Coatings on Paper Food Packaging

Increased environmental and health concerns over the use of plastic packaging or fluorine-containing coatings,in combination with increased market demand for products with a longer shelf life,make bio-based materials one of the most important research candidates for alternative paper packaging materials for oil resistance.These bio-based materials have excellent oxygen and oil barriers,which are critical for food packaging.Moreover,they are biodegradable,naturally renewable,and safe.In this artical,two main groups of bio-based oil repellents for paper food packaging,including polysaccharide-based biopolymers and protein-based biopolymers,are enumerated,and the advantages and weaknesses of bio-based oil repellents are discussed,and effective solutions are proposed.Finally,research status and prospects on the development of bio-based oil-resistant coatings for the food packaging industry are presented.

Mechanism of improving skin barrier function in a mouse model of atopic dermatitis using Mahuang Lianqiao Chixiaodou decoction and its disassembled formula

Objective: To reveal the mechanism of Mahuang Lianqiao Chixiaodou decoction and its disassembled formula for improving the skin barrier function in a mouse model of atopic dermatitis(AD).Methods: Sixty specific-pathogen free male BALB/c mice were randomly divided into the control group,model group, whole formula group(WF), exterior-releasing formula group(ERF), interior-clearing formula group(ICF), and positive control group(PC). A mouse model of AD was established using the semiantigen 2,4-dinitrofluorobenzene induction method. The lesion scores, transepidermal water loss and p H, and skin histopathology of mice in each group were observed. The expressions of filaggrin, loricrin,and involucrin were detected by the streptavidin peroxidase immunohistochemical method and western blotting, and their mRNA expressions were detected by quantitative polymerase chain reaction.Results: Mice in the WF, ERF, ICF, and PC groups showed reduced skin lesion performance, improved histopathology, decreased skin lesion score, transepidermal water loss and pH, and upregulated expressions of proteins including filaggrin, loricrin, and involucrin, and their mRNAs. The most obvious regulatory effect was observed in the WF group, followed by the ICF, ERF, and PC groups, accordingly.Conclusions: Mahuang Lianqiao Chixiaodou decoction and its disassembled formula can improve the skin barrier function in a mouse model of AD by upregulating filaggrin, loricrin, and involucrin, and their mRNA expressions, and the most optimal effect was noted in the WF group, followed by the ICF and ERF groups, which suggests that the effect of clearing heat and resolving dampness in improving the skin barrier function of AD is more obvious and is one of the key treatments for AD.

Conductive Polyaniline/Cellulose/Graphite Composite Films with High Thermal Stability and Antibacterial Activity

Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.

Pore Structure Regulation of Carboxyethylated Microfibrillated Cellulose Films

Carboxyethylation is a recent chemical pretreatment for preparation of microfibrillated cellulose(MFC).The carboxyethylated MFC film prepared by coating method has compact structure and high mechanical properties.In order to expand its application,three approaches including using organic solvents,different drying methods and cationic additives,have been adopted in this paper to enrich and regulate the pore structure of MFC film.The results show that all the approaches can improve the pore structure but decrease the mechanical properties of MFC film.When organic solvents such as ethanol,isopropanol and n-butanol were used to replace the water in MFC suspension or pre-dried MFC film,the pore structure of films were increased.Additionally,the film obtained by freeze-drying or air-drying after freezing in liquid nitrogen or freezer has high porosity but poor strength.The best drying process is to rewet dry MFC film,freeze in liquid nitrogen and then freeze-dry.Moreover,the addition of cationic polyelectrolytes or alkene ketone dimer(AKD)in MFC suspension can also significantly increase the film's porosity.Through the above approaches,the porosity of carboxyethylated MFC film can be regulated between 20% and 90%.

Eco-friendly PVA/Kaolin Clay Coating for Barrier Paper

The resistance of wood-fiber paper to water, grease, and water vapor is usually attained by immersing the base paper in hydrophobic oil, laminating with a plastic or metal film, or the application of a barrier coating. Oil impregnation and the addition of films may make the paper difficult to recycle or persistent in the environment owing to their strong binding force and nondegradability. Environmental concerns have attracted worldwide attention to eco-friendly barrier coatings. In this study, degradable polyvinyl alcohol(PVA) and kaolin clay pigment were used to prepare coatings that were applied to a base paper. By measuring the barrier properties of the coated paper, including the water absorptiveness(Cobb60 value), Hercules sizing degree, oil resistance(Kit rating), and water vapor transmission rate(WVTR), an optimal coating formulation and process were proposed. To examine the barrier mechanism of the PVA/kaolin clay coating, we characterized the coating microstructures using a scanning electron microscopy(SEM) and a mercury porosimeter. The results showed that the Cobb60 value and water vapor transmission rate of the coated paper decreased by 61.4% and 98.6%, respectively, compared with the base paper, for a pre-coating weight of 0.98 g/m^2 and a top-coating weight of about 3.23 g/m^2. Furthermore, the Hercules sizing degree rose by a factor of 337.2, while the oil resistance(Kit rating) increased from 0 to 12. The optimum drying temperature for a wet coating layer was found to be 170℃, and the optimum weight ratio of PVA to kaolin clay in the coating was determined to be 50∶50. It was assumed that the PVA/kaolin clay coating improved the smoothness of the paper considerably and decreased the pore size by filling the pores on the paper surface and forming an even film, thus enhancing the paper barrier performance. The coated paper also exhibited good repulpability.

Intervention of the Mahuang Lianqiao Chixiaodou decoction on immune imbalance in atopic dermatitis-like model mice

Objective:To explore the potential mechanism of intervention on the immune imbalance of atopic dermatitis(AD) by studying the effects of Mahuang Lianqiao Chixiaodou decoction(MLCD) on skin damage and inflammation factors in an AD-like mouse model.Methods:Ninety-six male BALB/c mice were divided into normal,model,positive control(mometasone furoate),and traditional Chinese medicine treatment(MLCD) groups by a random number table.2,4-dinitrofluorobenzene was used to induce AD-like mice in all groups except the normal group.The treatment or intervention was administered for seven consecutive days on days 4,18,32,and 39.The mRNA relative expressions of interleukin-4(IL-4),IL-10,interferon-γ(IFN-γ),thymic stromal lymphopoietin(TSLP),and the TSLP receptor(TSLPR) were measured using quantitative real-time polymerase chain reaction,and the serum immunoglobulin E,IL-4,IL-10,and IFN-γ levels were detected using enzyme-linked immunosorbent assay.Results:Compared with the normal group,the hematoxylin-eosin staining of the skin lesions of the mice in the model group was significantly thickened on days 11,25,and 39.Compared with the model group,the epidermal thickness of the positive control group was significantly alleviated on day 39(P <.001),and that of the MLCD group was significantly improved on days 25 and 39(P <.001).Compared with the four observation time points,MLCD had the best treatment effect on day 39 of the experiment and significantly improved the skin damage performance and relieved pathological lesions.On day 39,compared with the model group,MLCD downregulated the skin mRNA relative expressions of IL-4(P=.009),TSLP(P=.030),and TSLPR(P <.001),and reduced the mouse serum levels of IL-4(P=.003).For other serum indicators,no significant difference was observed between the model and MLCD groups.Conclusion:MLCD improved AD-like mice skin damage by regulating the Th1/Th2 immune imbalance.

Different Kinds of Microfibrillated Cellulose as Coating Layers Providing Fiber-based Barrier Properties

In this study,we investigated the barrier properties of different kinds of microfibrillated cellulose(MFC)coating layers.The air,oxygen,and water vapor permeability,as well as the water contact angles(WCA),were measured to quantify the barrier efficacy of the applied coatings.The WCA data showed that the surfaces of MFC-coated cardboards are more hydrophilic than those of uncoated cardboards.However,different MFC coatings realize different oxygen transmission rates(OTRs)and water vapor transmission rates(WVTRs).The MFC coating derived from bleached bamboo pulp subjected to carboxyethylation pretreatment(MFCCBP)gave the best oxygen and water vapor barrier performances.The OTR of the virgin cardboard(>16500 cm^(3)/(m^(2)·24 h))decreased to 4638 cm^(3)/(m^(2)·24 h)after coating with the MFCCBP.The WVTR similarly decreased from 1016.7 g/(m^(2)·24 h)to 603.2 g/(m^(2)·24 h).

Carboxyethylated Microfibrillated Cellulose Fibers Prepared from Different Raw Materials

Carboxyethylation pretreatment was used to prepare microfibrillated cellulose(MFC)in this study.In order to evaluate the adaptability of this pretreatment method,carboxyethylated MFC was prepared from six different cellulosic materials.The carboxyl content,degree of polymerization,water retention value,charge density,chemical structure,size distribution,and micromorphology of the materials before and after pretreatment and grinding were studied and compared.The viscosity,ultraviolet(UV)transmittance,and thermal stability of the MFC samples at a certain concentration were determined.The results showed that the carboxyl content,water retention value,charge density,degree of polymerization,size distribution,and micromorphology of the pretreated and ground samples varied with those of the raw materials.The initial viscosity varied based on the type of raw material used.The MFC suspension prepared from cotton linter pulp had the highest UV transmittance,while the MFC prepared from bleached softwood kraft pulp had the highest viscosity at a low shear rate.After thermal degradation,the amount of residual char from the MFC prepared with the thermo-mechanical pulp was slightly higher than that of the other MFCs.This study demonstrates that carboxyethylation is an effective pretreatment method for different cellulosic materials.

Preparation of Ultrafine Starch Particle and its Application in Paper Coating

Despite its biodegradability, adequate cohesive strength and comparatively low cost, the use of cooked starch as a paper coating binder is limited due to its high viscosity and serious negative impact on the gloss. Starch-based bio-latex with size in the nanometer or sub-micrometer range has been developed recently to overcome these shortcomings. In this study, ultrafine starch particle(UFSP) was prepared by mechanical milling using a DYNO mill in combination with light chemical pretreatment. Model coating colors containing different dosages of UFSP were applied to base paper and the properties of the coated papers were evaluated. The results showed that the UFSP was disc-shaped with a median particle diameter of 167 nm. Water retention capacity of the coating colors was improved considerably with the addition of UFSP, i.e., the water retention value decreased by nearly 40% when styrene-butadiene latex was replaced by UFSP at a dosage of 3 pph(per hundred parts of pigment). The high shear rate viscosities of the coating colors containing no more than 2 pph of USFP were similar to that of the control coating color at shear strain rate higher than 2000 s^(-1). The properties and performances of the coated papers were comparable to the control coated paper with single synthesized latex binder. The gloss and the print gloss of paper samples with or without USFP were 59.7% and 58.2%, 79.0% and 78.8%, respectively. Surface strength of paper samples with or without USFP were 0.96 and 0.90 m/s, respectively, while the ink absorptivity values were 34% and 33%. This study demonstrates a promising approach to obtain submicrometer sized starch for paper coating.

Preparation and Application of Microfibrillated Cellulose-modified Ground Calcium Carbonate

Microfibrillated cellulose(MFC) was first prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO) oxidation pretreatment and mechanical grinding in the presence of a certain amount of ground calcium carbonate(GCC).The effects of GCC dosage and grinding concentration on the fibrillation were investigated.The obtained MFC was then added to the bulk GCC to form MFC-modified GCC fillers.The properties of MFCmodified GCC fillers were compared to those of the traditional GCC fillers.Results showed that the resulting fibrils became more uniform when the dosage of GCC was 10%~15% and the concentration of the suspension was 6.97%.Compared to traditional GCC,the average particle size of the MFCmodified GCC fillers was larger.Scanning electron microscopy images showed that GCC and MFC formed a bridge structure in the MFC-modified GCC fillers.In the process of papermaking,the MFC-modified GCC fillers decreased the drainage rate but increased the retention of fillers.The prepared papers filled with MFC-modified GCC fillers had higher tensile strength than those filled with traditional GCC fillers.

Lignin-containing Microfibrillated Cellulose Prepared from Corncob Residue via Calcium Hydroxide Co-grinding and Its Application in Paper Reinforcement

In this study,lignin-containing microfibrillated cellulose(MFC)was prepared from corncob residue after xylose extraction via co-grinding with calcium hydroxide.The product was then compared with the MFC obtained by direct grinding and applied to strengthen paper.The chemical composition and morphological structure analysis results showed that the corncob residue can be used to prepare lignin-containing MFC and does not require further purification.Moreover,the co-grinding with calcium hydroxide is easier to fibrillate corncob residue.The MFC obtained by cogrinding with calcium hydroxide had a higher aspect ratio,and its surface was coated with calcium carbonate nanoparticles.MFCs obtained by both the methods mentioned above had an obvious strengthening effect on paper.Compared with the paper without MFC,the tensile index,elongation,burst index,and folding strength of the paper with MFC obtained by co-grinding with calcium hydroxide significantly increased by 17.5%,22.1%,19.5%,and 157.1%,respectively.This study provides a novel idea for the utilization of corncob residue,which may enhance the value and promote the comprehensive utilization of corn by-products.

Octadecylamine Graft-modified Cellulose Nanofiber and Its Reinforcement to Poly(butylene adipate-co-terephthalate) Composites

Biodegradable polymers such as poly(butylene adipate-coterephthalate)(PBAT)have attracted great interest as alternatives to traditional petroleum-based polymers.Nonetheless,it is necessary to improve some properties of PBAT,such as mechanical strength.Cellulose nanofiber(CNF)can improve PBAT mechanical strength,but its dispersion and compatibility in the PBAT matrix require further improvement.In this study,octadecylamine(ODA)was utilized to graft-modify CNF to change the fiberto-fiber interaction and improve its compatibility with the PBAT matrix.PBAT composites with 1 wt%CNF were prepared using a masterbatch premixing method to avoid CNF aggregation during extrusion.The effects of ODA graft modification on CNF properties were studied;varying degrees of CNF modification were investigated for their effect on PBAT properties.ODA-modified CNF(OCNF)/PBAT melt-extruded composites possessing 17.2%higher tensile strength than pure PBAT polymer were obtained without affecting the thermal stability of PBAT.As a result,surface modification of CNF with ODA is an effective strategy for improving CNF-PBAT compatibility.

Effects of MFC-modified GCC as Filler on the Opacity of Pulp Handsheets

Microfibrillated cellulose(MFC)was obtained by mechanical grinding of different pulps.MFC-modified ground calcium carbonate(GCC)was prepared in two different ways,designated MFC-GCC composite filler and MFC-GCC flocs filler.The opacity of pulp handsheets loaded with MFCmodified GCC was measured.The effects of MFC originated from different pulps,pretreatment method,and filler modification on the opacity of handsheets loaded with MFC-modified GCC were discussed.The results show that MFC originated from alkaline peroxide mechanical pulp(APMP)was optimal for improving the opacity of the handsheets and PFI grinding pretreatment for MFC provided a denser structure in the corresponding MFCAPMP-GCC floc filler while enzyme pretreatment was more effective in increasing the opacity of the filled paper.Under the experimental conditions,the opacity of handsheets increased from 81.0%to 82.7%when the unmodified GCC was replaced by an equivalent amount of MFCAPMP-GCC composite filler,while other properties were unchanged.

中国减重代谢外科规范化建设的必要性和质量提升路径

近年,中国重度肥胖患者数量已高居全球首位。我国减重代谢手术量正在逐年增长,取得了突飞猛进的发展。随着越来越多的新医院、新团队、新医生加入减重代谢领域,必然伴随着不规范、不标准的操作和管理,引发减重手术相关问题与隐患。尽管这一定程度上符合事物发展的客观规律,却并不意味着可以放任不管、任其发展。为确保中国减重代谢外科未来能够持续、健康、有序地发展,规范化建设和质量提升成为当务之急。本文就当前国内外减重代谢外科规范化建设现状、中国减重代谢外科规范化建设的必要性及中国减重代谢外科质量提升的路径等方面作一述评,旨在为学科发展提供一定的思考并激发广泛的讨论。

Dry deposition velocity of total suspended particles and meteorological influence in four locations in Guangzhou,China

Dry deposition velocity of total suspended particles （TSP） is an effective parameter that describes the speed of atmospheric particulate matter deposit to the natural surface. It is also an important indicator to the capacity of atmosphere self-depuration. However, the spatial and temporal variations in dry deposition velocity of TSP at different urban landscapes and the relationship between dry deposition velocity and the meteorological parameters are subject to large uncertainties. We concurrently investigated this relationship at four different landscapes of Guangzhou, from October to December of 2009. The result of the average dry deposition velocity is （1.49 ± 0.77）, （1.44 ± 0.77）, （1.13 ±0.53） and （1.82± 0.82） cm/sec for urban commercial landscape, urban forest landscape, urban residential landscape and country landscape, respectively. This spatial variation can be explained by the difference of both particle size composition of TSP and meteorological parameters of sampling sites. Dry deposition velocity of TSP has a positive correlation with wind speed, and a negative correlation with temperature and relative humidity. Wind speed is the strongest factor that affects the magnitude of TSP dry deposition velocity, and the temperature is another considerable strong meteorological factor. We also find out that the relative humidity brings less impact, especially during the dry season. It is thus implied that the current global warming and urban heat island effect may lead to correlative changes in TSP dry deposition velocity, especially in the urban areas.

Amorphous red phosphorus anchored on carbon nanotubes as high performance electrodes for lithium ion batteries

Red phosphorus-carbon nanotube （P@CNT） composites were synthesized as anodes for advanced lithium ion batteries via a facile solution-based method at room temperature. In these composites, the entangled P@CNT nanostructure reduced the aggregation of both components and allowed their complete utilization in a synergetic manner. The highly conductive and porous CNT framework, along with the nanoscale red P particles intimately anchored on the CNT surface, conferred the composite with excellent ion/electron transport properties. Volume expansion within the red P particles was mitigated by their amorphous and nanoscale features, which can be well buffered by the soft CNTs, therefore maintaining an integrated electrode structure during cycling. When used as an anode in lithium ion batteries, the composite exhibited a reversible capacity of 960 mAh·g^-1 （based on the overall weight of the composite） after 120 cycles at 200 mA·g^-1. The composite also delivered excellent high-rate capability with capacities of 886, 847, and 784 mAh·g^-1 at current densities of 2,000, 4,000, and 10,000 mA·g^-1 respectively, which reveals its potential as a high performance anode for lithium ion batteries.

Starting materials, processes and characteristics of bio-based foams: A review

Biofoam products have attracted considerable attention lately because there is a growing demand for green/sustainable products.To this end,various biobased foams have either been developed or are currently in development,e.g.,bio-based polyurethanes(PUs),polylactic acid(PLA),starch,and polyhydroxyalkanotates(PHAs).Indeed,significant progress has been made;however,chal-lenges still persist,for example,biobased foam products have poor processability,inferior com-patibility,thermal and strength properties.In this review,we focus on five biofoam products:namely bio-based PUs,PLA,starch,PHAs,and cellulose biofoam products,along with their prop-erties and performance,as well as their manufacturing processes.Further efforts are still needed to unlock the full potential of these bio-based products and meet the goal of complementing and gradually replacing some of their fossil-based counterparts.Finally,the challenges,as well as arising opportunities of future research directions are discussed.