Composite films of N,O‐carboxymethyl chitosan and bamboo fiber

To obtain an antibacterial chitosan derivative, composite films of N,O‐Carboxymethyl Chitosan (N,O‐CMCS) and bamboo fiber were prepared. A water‐soluble chitosan derivative‐N,O‐CMCS was synthesized from chitosan with chloroacetic acid in alkaline solution. Composite films with 1–5 wt % N,O‐CMCS content were prepared in NaOH/urea/thiourea solution. The DS of N,O‐CMCS reached 1.70 and the water solubility increased with the increasing of DS. The carboxymethyl group was introduced into chitosan, which led to the decrease of thermal stability and crystallinity. The structural characterization confirmed that N,O‐CMCS was adsorbed on the surface of bamboo fiber. The antibacterial performance of the composite films were enhanced with the increasing of N,O‐CMCS content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39851.     

Effects of graphene oxide on the formation,structure and properties of bionanocomposite films made from wheat gluten with chitosan

Graphene oxide (GO) was combined with wheat gluten (WG) and chitosan (CS) to prepare bionanocomposite films using a casting method. The films were characterized using a variety of techniques, including scanning and transmission electron microscopies, atomic force microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, mechanical testing, water swelling, oxygen permeability and contact angle measurements, to determine the effects of GO on the formation, structure and properties of the bionanocomposites. Their formation and properties were found to be dependent on the mixing order of the three components. The added GO was found to strengthen the films, as well as to decrease water absorption and oxygen permeability. These effects were attributed to the good dispersion of GO in the WG/CS matrix enabled by hydrogen bonds. The decreased water absorption could be explained by the increased hydrophobicity. The notable improvement of the properties of the WG/CS films as a result of GO addition makes the films suitable as packaging materials. © 2016 Society of Chemical Industry     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

Preparation and optical properties of nanocomposite film of CdS:Cu with biomacromolecules

Nanocomposite films of CdS:Cu nanoparticles with chitosan and sodium alginate were prepared using spin‐coating method, and characterized by X‐ray diffraction, transmission electron microscopy, atomic force microscopy (AFM), ultraviolet–visible (UV–vis), and photoluminescent spectrum. The CdS:Cu nanoparticles have a cubic structure with an average crystal size of ∼2 nm, which show blue shift in UV–vis absorption spectra compared to bulk CdS. Furthermore, the CdS:Cu nanoparticles are formed steadily with increasing number of composite layers and homogeneously distributed between the chitosan and alginate layer. AFM measurement shows that the average height of a mono‐layered composite film is 25 nm. Emissions ascribed to the electron–hole recombination of CdS and the t₂‐like energy level of Cu was observed for the multi‐layered composite films. POLYM. COMPOS., 35:477–481, 2014. © 2013 Society of Plastics Engineers     

Graphene oxide–polyoctahedral silsesquioxane–chitosan composite films with improved mechanical and water-vapor-transport properties

Graphene oxide (GO) and ball-milled maleamic acid–isobutyl polyoctahedral silsesquioxanes (MAIPSs) were incorporated simultaneously into chitosan (CS) via solution blending to evaluate their combined effects on the structures and properties of composite films. GO and MAIPS aggregates were homogeneously dispersed in CS and affected the crystallinities of the composite films. The binary addition of GO and MAIPS resulted in synergistic enhancements of the tensile strength and elongation at break of the composite films. Composite films containing 3% w/w MAIPS and 0.25% w/w GO (CS–GO–MAIPS-3) exhibited the highest strength and modulus, which were 48 and 42.2% higher, respectively, than the values of the CS film. The water-vapor-sorption isotherms revealed that monolayer sorption sites decreased with the addition of GO or/and MAIPS, but the dissolution process was not significantly influenced. The water-vapor permeability reached its lowest value for the CS–GO–MAIPS-3 film because of hindered diffusion with the presence of impermeable nanoparticles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47748.     

Effects of halloysite nanotubes and kaolin loading on the tensile,swelling, and oxidative degradation properties of poly(vinyl alcohol)/chitosan blends

[Halloysite nanotubes (HNT)]‐filled and kaolin filled composite films based on poly(vinyl alcohol) (PVA)/chitosan (CS) blend were prepared via solution casting method. Tensile properties, fracture morphology, FTIR spectra, thermal stability, swelling properties, moisture absorption, and oxidative degradation of the composite films were investigated. Addition of 0.5 wt% of filler led to the optimum tensile properties of the films. Increased roughness and tearing in the fracture surface morphology supported the tensile results. The FTIR results indicated there were physical interactions present in the composite films. Thermal stability of the composite films differed slightly where PVA/CS/HNT composite films showed better thermal stability than PVA/CS/kaolin composite films. Moreover, the presence of HNT and kaolin fillers in the blend reduced the swelling and moisture absorption properties of the films. Finally, the composite films were degraded by using Fenton's reagent. Degradation percentage of the composite films decreased with increasing filler loading. J. VINYL ADDIT. TECHNOL., 19:55–64, 2013. © 2013 Society of Plastics Engineers     

Physicochemical and antibacterial properties of chitosan‐polyvinylpyrrolidone films containing self‐organized graphene oxide nanolayers

Chitosan films have a great potential to be used for wound dressing and food‐packaging applications if their physicochemical properties including water vapor permeability, optical transparency, and hydrophilicity are tailored to practical demands. To address these points, in this study, chitosan (CS) was combined with polyvinylpyrrolidone (PVP) and graphene oxide (GO) nanosheets (with a thickness of ～1 nm and lateral dimensions of few micrometers). Flexible and transparent films with a high antibacterial capacity were prepared by solvent casting methods. By controlling the evaporation rate of the utilized solvent (1 vol % acidic acid in deionized water), self‐organization of GO in the polymer matrix was observed. The addition of PVP to the CS/GO films significantly increased their water vapor permeability and optical transmittance. A blue shift in the optical absorption edge was also noticed. Thermal analysis coupled with Fourier transform infrared spectroscopy suggested that the superior thermal stability of the nanocomposite films was due to the formation of hydrogen bonds between the functional groups of chitosan with those of the graphene oxide. An improved bactericidal capacity of the nanocomposite films against gram‐positive Staphylococcus aureus and gram‐negative Escherichia coli bacteria was also observed. Highly flexible, transparent (opacity of 6.95), and antimicrobial CS/25 vol % PVP/1 wt % GO films were prepared. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43194.     

Preparation and properties of β‐phase graphene oxide/PVDF composite films

We report preparation of graphene oxide (GO) from expanded graphite (EG) via a modified Hummers method. GO/PVDF composites films were obtained using solvent N, N‐Dimethylformamide (DMF) and cosolvent comprising deionized water/DMF combination. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the main crystal structure of the composite films is β‐phase, and use cosolvent method tends to favor the formation of β‐phase. Scanning electron microscopy (SEM) was used to investigate the microstructure of composite films. Storage modulus and loss modulus were measured by Dynamic mechanical analysis (DMA). Broadband dielectric spectrum tests showed an increase in the dielectric constant of the GO/PVDF composite films with the rising content of GO, and by cosolvent method could improve the dielectric constant while reducing the dielectric loss. Our method that uses GO as an additive and deionized water/DMF as the cosolvent provides a promising and low‐cost pathway to obtain high dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41577.     

In situ Synthesis and mechanical,thermal properties of polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) and chemical modified graphene oxide nanocomposite films are prepared by in situ polymerization from solutions of pyromellitic dianhydride and 4,4′‐oxydianiline with various amount (0.5–2 wt%) of 3‐aminopropyltriethoxysilane (APTS) functionalized graphene oxide (GO) sheets in dimethylacetamide. The APTS functionalized GO (GO‐APTS) is a versatile platform for polymer grafting, improving excellent dispersion of GO in the PI matrix, and forming strong interaction with the PI matrix. The GO‐APTS/PI nanocomposites exhibited improvement in mechanical and thermal properties by addition of a small amount of GO‐APTS. With the addition of a small amount of GO‐APTS (1.5 wt%) to PI matrix, mechanical properties with the tensile strength and Young's modulus improved by 45% and 15%, respectively. The thermal analysis showed that the thermal stability of PI was slightly enhanced by the incorporation of GO‐APTS (1.5 wt%). This approach provides a strategy for developing high performance functionalized GO‐polymer composite materials. POLYM. COMPOS., 37:907–914, 2016. © 2014 Society of Plastics Engineers     

Green fabrication of porous chitosan/graphene oxide composite xerogels for drug delivery

Porous chitosan (CS)/graphene oxide (GO) composite xerogels were prepared through a simple and “green” freeze‐drying method. Scanning electron microscopy, Fourier transform infrared spectrometry, powder X‐ray diffraction, and compressive strength measurements were performed to characterize the microstructures and mechanical properties of as‐prepared composite xerogels. The results show that the incorporation of GO resulted in an observable change in the porous structure and an obvious increase in the compressive strength. The abilities of the composite xerogels to absorb and slowly release an anticancer drug, doxorubicin hydrochloride (DOX), in particular, the influence of different GO contents, were investigated systematically. The porous CS/GO composite xerogels exhibited efficient DOX‐delivery ability, and both the adsorption and slow‐release abilities increased obviously with increasing GO content. Additionally, the best adsorption concentration of DOX was 0.2 mg/mL, and the cumulative release percentage of DOX from the xerogels at pH4 much higher than that at pH 7.4. Therefore, such porous CS/GO composite xerogels could be promising materials as postoperation implanting stents for the design of new anticancer drug‐release carriers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40006.     

In situ preparation of transparent polyimide nanocomposite with a small load of graphene oxide

Polyimide (PI) nanocomposites with 4,4′‐bisphenol A dianhydride, 4,4′‐oxydiphthalic anhydride, and diaminodiphenyl methane (MDA) as comonomers and functionalized with graphene oxide (GO), were prepared by in situ polymerization. Only a small amount of GO (0.03–0.12 wt %) is added to improve the mechanical properties of PI and to avoid a substantial decrease of PI transparence. The nanocomposites are characterized by FTIR, X‐ray diffraction, thermogravimetric analysis, transmission electron microscope, tensile test, and UV‐vis spectroscopy. It is demonstrated that the PI/GO composite films possess transmittance of above 80% at wavelengths of 500–800 nm when the GO content is under 0.12 wt %, while the stress intensity and Young's modulus are improved by 29 and 25%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of wool nanoparticles incorporation in chitosan/gelatin composite films

The aim of this work was to develop chitosan/gelatin composite films embedded with various amounts of wool nanoparticles, which were produced by an environmental friendly process. Films loaded with wool nanoparticles were subjected to physiochemical, biological, and mechanical characterization. The obtained results showed that incorporation of wool nanoparticles into chitosan/gelatin composite led to a reduction in swelling, moisture content and dissolution degree of the films. In vitro degradation test revealed that the nanoparticles‐embedded composites had a lower degradation rate than that of chitosan/gelatin composite. Besides, composite films containing wool nanoparticles showed an improvement in the stability in phosphate buffered saline. On the other hand, tensile strength and elongation at break decreased upon loading the films with wool nanoparticles. The biocompatibility of the produced composites was also confirmed by MTT test. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40294.     

Effects of graphene on the behavior of chitosan and starch nanocomposite films

The objective of this study was to prepare chitosan and starch composite films by the addition of 0–3 wt% graphene nanosheets. The film's tensile strength (TS), tensile modulus (TM), elongation at break (E), moisture uptake (Mu), and water vapor transmission rate (WVTR) were investigated. The surface morphology of the composite films was studied using scanning electron microscopy (SEM). Regardless of biopolymer type, both the TS and TM of the composite films first increased and then decreased with graphene loading. Composite film made with native (unmodified) starch showed lower TS and TM than those with chitosan. Composite films exhibit lower E values than pure chitosan and starch; this is attributed to the increase in the hardness of the films. SEM micrographs indicated that, the surface roughness and phase separation increased with increasing graphene content. This is due to the aggregation of graphene nanosheets, leading to the reduced compatibility of biopolymers. The addition of graphene considerably decreased WVTR and Mu of the composite films. These results indicated that graphene is a promising reinforcing agent for biopolymer composite films. POLYM. ENG. SCI., 54:2258–2263, 2014. © 2013 Society of Plastics Engineers     

Multifunctional polyimide/graphene oxide composites via in situ polymerization

In this article, we detail an effective way to improve electrical, thermal, and gas barrier properties using a simple processing method for polymer composites. Graphene oxide (GO) prepared with graphite using a modified Hummers method was used as a nanofiller for r‐GO/PI composites by in situ polymerization. PI composites with different loadings of GO were prepared by the thermal imidization of polyamic acid (PAA)/GO. This method greatly improved the electrical properties of the r‐GO/PI composites compared with pure PI due to the electrical percolation networks of reduced graphene oxide within the films. The conductivity of r‐GO/PI composites (30:70 w/w) equaled 1.1 × 10¹ S m^?1, roughly 10¹⁴ times that of pure PI and the oxygen transmission rate (OTR, 30:70 w/w) was reduced by about 93%. The Young's modulus of the r‐GO/PI composite film containing 30 wt % GO increased to 4.2 GPa, which was an approximate improvement of 282% compared with pure PI film. The corresponding strength and the elongation at break decreased to 70.0 MPa and 2.2%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40177.     

Properties and structural characterization of oxide starch/chitosan/graphene oxide biodegradable nanocomposites

Novel chitosan (CS)/oxidized starch (OST)/graphene oxide (GO) nanocomposites (COST/GO‐n) films are prepared in a casting and solvent evaporation method. Fourier transform infrared spectroscopy, X‐ray diffractions, atomic force microscopy, scanning electron microscopy, transmission electron microscopy, thermal gravimetric analysis, tensile testing, and moisture uptake are used to study the structure and properties of these nanocomposites. To indicate the effect of carboxyl groups of OST, some results of the properties of CS/starch/GO nanocomposite (CST/GO‐n) were selected for control experimentation. Compared with the control CST/GO‐n series, COST/GO‐n films, which have the same component ration showed higher tensile strength (σ_b) and lower elongation at break (ε_b). Additionally, in the COST/GO‐n series, the σ_b increased with an increase of GO loading. However, higher proportion of GO could result in aggregations of GO nanosheets and deterioration of the film properties. Compared with the COST/GO‐0, the values of σ_b and water resistance of the COST/GO‐4 containing 2.0 wt % of GO were improved by 57.7 and 20.1%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Graphene oxide reinforced chitosan/polyvinylpyrrolidone polymer bio‐nanocomposites

Bio‐nanocomposite films based on chitosan/polyvinylpyrrolidone (CS/PVP) and graphene oxide (GO) were processed using the casting/evaporation technique. It has been found that the three components of bio‐nanocomposites can be easily mixed in controlled conditions enabling the formation of thick films with high quality, smooth surface and good flexibility. Structural and morphological characterizations showed that the GO sheets are well dispersed in the CS/PVP blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and GO sheets thus improving their properties. It has been found that the water resistance of the CS/PVP blend is improved, and the hydrolytic degradation is limited by addition of 0.75 and 2 wt % GO. The modulus, strength, elongation and toughness of the bio‐nanocomposites are together increased. Herein, the steps to form new bio‐nanocomposite films have been described, taking the advantage of the combination of CS, PVP and GO to design the aforementioned bio‐nanocomposite films, which allow to have extraordinary properties that would have promising applications as eventual packaging materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41042.     

Preparation,characterization, antibacterial properties,and hemostatic evaluation of ibuprofen‐loaded chitosan/gelatin composite films

Ibuprofen‐loaded chitosan/gelatin (CS/GE) composite films were fabricated in this work. The morphology of the composite film was investigated using scanning electron microscopy. The functional groups of the composite film before and after crosslinking were characterized using Fourier transform infrared spectroscopy. Meanwhile, the mechanical properties, antibacterial performance, cytocompatibility, and hemostatic activity of the composite films were investigated. The results show that the amount of CS affected the mechanical properties and liquid uptake capacities of the composite films. The composite film showed better bactericidal activity against Staphylococcus aureus than Escherichia coli. In vitro drug‐release evaluations showed that crosslinking could control the drug‐release rate and period in wound healing. Both types of CS/GE and drug‐loaded CS/GE composite films also showed excellent cytocompatibility in cytotoxicity assays. The hemostatic evaluation indicated that the composite film crosslinked by glutaraldehyde in rabbit livers had a dramatic hemostatic efficacy. Therefore, ibuprofen‐loaded CS/GE composite films are potentially applicable as a wound dressing material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45441.     

壳聚糖/壳聚糖接枝氧化石墨烯复合气凝胶的制备及性能研究

以壳聚糖（CS）和壳聚糖接枝氧化石墨烯（CS-g-GO）为主要原料,通过真空冷冻干燥技术分别制备了CS气凝胶和CS/CS-g-GO复合气凝胶吸附膜,并通过扫描电子显微镜、红外光谱仪和接触角测量仪等对吸附膜的性能进行了测试和表征,结果表明,CS/CS-g-GO复合气凝胶的接触角较纯CS大,亲水基团减少;当CS-g-GO和CS质量比（WCSg-GO∶WCS）为100∶1 556、CS-g-GO的接枝率为76.04%时制备的复合气凝胶吸附膜对细颗粒物（PM2.5）过滤效率可达到94.1%;与CS气凝胶相比,过滤效率提高了4.4%。     

Influence of graphene oxide on thermal,electrical, and morphological properties of new achiral polyimide

In this study, a new diamine N‐[2‐(1H‐indol‐3‐yl)ethyl]‐3,5‐diaminobenzamide (IEDAB) was synthesized using tryptamine as starting material and characterized by FT‐IR, ¹H‐NMR, ¹³C‐NMR, and mass spectroscopy. Then, it was polymerized with 3,3',4,4'‐benzophenone tetracarboxylic dianhydride (BTDA) via thermal imidization to produce polyimide (PI). A series PI/GO nanocomposite films were prepared by incorporating different ratios (1, 3, and 5 wt%) of synthesized GO by solution casting method. The synthesized PI was confirmed by Ubbelohde viscometer and FT‐IR spectroscopy. SEM and Raman spectroscopy showed that GO was well dispersed in the PI matrix. XRD patterns indicated the PI and PI/GO nanocomposite films were highly amorphous in nature. The synthesized PI and their nanocomposites show high thermal stability as their T_10% weight loss are in the range of 498 to 563°C with 30.6 to 40% of char yield and the glass transition temperatures (T_g s) are in the range of 188 to 262°C. The limited oxygen index (LOI) values increased from 31.4% to 56.0% with increases of 5% GO content in the PI/GO nanocomposite. They have high dielectric constant in the range of 2.6 to 5.1 at 1 MHz and also good mechanical properties with tensile strength of 81 to 116 MPa, elongation at break 5 to 9%. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Packaging‐related properties of alkyd‐coated,wax‐coated,and buffered chitosan and whey protein films

Packaging‐related properties of coated films of chitosan–acetic acid salt and whey protein concentrate (WPC) were studied. Chitosan (84.7% degree of deacetylation) and WPC (65–67% protein) were solution cast to films. These films are potential oxygen barriers for use in packaging. Coatings of wax or alkyds were used to enhance the water‐barrier properties. The packaging‐related properties of chitosan films treated in a buffering solution, with a pH of 7.8, were also investigated. The coated films were characterized with respect to Cobb absorbency, overall migration to water, water vapor transmission rate, and oxygen permeability. The creasability and bending toughness were determined. The wax was a more efficient barrier to liquid water and 90–95% relative humidity than the alkyd. However, the alkyd‐coated material had superior packaging‐converting properties. The alkyd‐coated WPC and chitosan–salt films were readily folded through 180° without any visible cracks or delamination. The overall migration from the alkyd‐coated materials was below the safety limit, provided the coat weight was higher than 7.5 mg/cm² on WPC and 2.1 mg/cm² on chitosan–salt. The barrier properties of chitosan film under moist conditions were improved by the buffer treatment. However, the buffering also resulted in shrinkage of the film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 60–67, 2004