Effect of pullulan/poly(vinyl alcohol) blend system on the montmorillonite structure with property characterization of electrospun pullulan/poly(vinyl alcohol)/montmorillonite nanofibers

Nanofibers of the composite of pullulan (PULL), poly(vinyl alcohol) (PVA), and montmorillonite clay (MMT) were prepared using electrospinning method in aqueous solutions. Pullulan is an interesting natural polymer for many of its merits and good properties. Because of biocompatibility and non-toxicity of PVA, it could be used in numerous fields. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA) were done to characterize the PULL/PVA/MMT nanofibers morphology and properties. XRD patterns and FTIR data demonstrated that there were good interactions between PULL and PVA caused by possibly hydrogen bonds. Moreover, XRD data and TEM images indicated that intercalated and exfoliated MMT nanoplatelets can be obtained within the PULL/PVA/MMT nanofibers depending on the PULL/PVA blend ratios. Furthermore, the thermal stability and mechanical property (tensile strength) of PULL/PVA/MMT nanofibers could be enhanced more by exfoliated MMT nanoplatelets than intercalated structures of that nanoplatelets.     

Electrospinning and characterization of poly(vinyl alcohol)/chitosan oligosaccharide/clay nanocomposite nanofibers in aqueous solutions

Submicron fibers of the composite of poly(vinyl alcohol) (PVA), chitosan oligosaccharide [COS, (1→4)2-amino-2-deoxy-β-d-glucose], and montmorillonite clay (MMT) were prepared using electrospinning method with aqueous solutions. Scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), thermal gravimetric analyzer, and tensile strength testing machine (Zwick) were utilized to characterize the PVA/COS/MMT nanofiber mats morphology and properties. The PVA/COS ratio and MMT concentration play important roles in nanofiber mat properties. XRD and TEM data demonstrated that exfoliated MMT layers were well-distributed within nanofiber. It was also found that the mechanical property and thermal stability were increased with COS and MMT contents.     

Preparation and Properties of Poly（vinyl alcohol）/Chitosan Blend Bio-nanocomposites Reinforced by Cellulose Nanocrystals

The aim of this paper is to report the effect of the addition of cellulose nanocrystals（CNCs） on the mechanical, thermal and barrier properties of poly（vinyl alcohol）/chitosan（PVA/Cs） bio-nanocomposites films prepared through the solvent casting process. The characterizations of PVA/Cs/CNCs films were carried out in terms of X-ray diffraction（XRD）, transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, thermogravimetric analysis（TGA and DTG）, oxygen transmission rate（OTR）, and tensile tests. TEM and SEM results showed that at low loading levels, CNCs were dispersed homogenously in the PVA/Cs matrix. The tensile strength and modulus in films increased from 55.1 MPa to 98.4 MPa and from 395 MPa to 690 MPa respectively, when CNCs content went from 0 wt% to 1.0 wt%. The thermal stability and oxygen barrier properties of PVA/Cs matrix were best enhanced at 1.0 wt% of CNCs loading. The enhanced properties attained by incorporating CNCs can be beneficial in various applications.     

Preparation and properties of poly(vinyl alcohol)/silica nanocomposites derived from copolymerization of vinyl silica nanoparticles and vinyl acetate

Nanocomposites of poly(vinyl alcohol)/silica nanoparticles (PVA-SNs) were prepared by in-situ radical copolymerization of vinyl silica nanoparticles functionalized by vinyltriethoxysilane (VTEOS) and vinyl acetate with benzoyl peroxide (BPO, i.e., initiator), subsequently saponified via direct hydrolysis with NaOH solution. The resulting vinyl silica nanoparticles, PVA-SNs were characterized by means of fourier transformation spectroscopy (FTIR), transmission electron microscopy (TEM) and the elemental analysis method. Effects of silica nanoparticles on viscosity and alcoholysis of PVA-SNs were studied by a ubbelohode capillary viscometer and the back titration method. The morphological structure of PVA-SN films was investigated by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile test were used to determine the thermal and mechanical properties of PVA-SN films. The results indicated that the content of vinyl groups on the surface of the vinyl silica nanoparticles was up to 3.02 mmol/g and vinyl silica nanoparticles had been successfully copolymerized with vinyl acetate. Furthermore, compared to pure PVA, silica nanoparticles bonded with polymer matrix in a low concentration affected the viscosity and alcoholysis of the PVA-SNs materials. At the same time, it resulted in the improvement of the thermal and mechanical properties of the PVA-SN materials due to a strong interaction between silica nanoparticles and the polymer matrix via a covalent bond. It could be found that the optical clarity of the membrane was changed through UV-Vis absorption spectrum due to the introduction of silica nanoparticles.     

Poly(vinyl alcohol)/GO-MMT nanocomposites: Preparation,structure and properties

A facile, efficient and environment friendly method is established to prepare poly(vinyl alcohol)(PVA) based graphene oxide-montmorillonite(GO-MMT) nanocomposites in aqueous media. GO-MMT nanohybrid is obtained by the combination of GO and MMT in water without any reducing or stabilizing agents. The formation of GO-MMT nanohybrid is due to the hydrogen bonding and crosslinking effects. The sodium ions within MMT sheets act as crosslinkers between GO sheets and MMT platelets. The resultant nanocomposites are characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and mechanical testing. Compared to that of pure PVA, PVA nanocomposites show enhanced thermal stabilities and mechanical properties, which results from strong interfacial adhesion of the nanoadditives in PVA matrix. The further increase in the tensile strength and modulus results from strong interaction between PVA chains and layered GO-MMT as well as good mechanical properties of GO-MMT hybrid, compared to PVA/GO and PVA/MMT nanocompsoites.     

聚乙烯醇/氟基蒙脱土纳米复合材料的合成及性能研究

采用水热方法,在493 K条件下反应72小时,合成了氟基蒙脱土(F-MMT),在这种F-MMT中,硅酸盐结构中的一些OH-被F-取代。采用溶液插层方法,制备了聚乙烯醇/F-MMT纳米复合材料(PVA/F-MMT)。采用X 射线衍射、扫描电镜和透射电镜对F-MMT 和 PVA/F-MMT纳米复合材料进行了表征;结果表明,片状结构的F-MMT均匀分散于PVA中,形成了层离结构的纳米复合材料。热重分析、力学性能和紫外可见光谱的测试结果表明,在没有牺牲光学性能情况下,PVA/F-MMT纳米复合材料的热稳定性和力学性能都得到了提高。力学和热学性能的提高归功于F-MMT均匀而好的分散于聚合物基体中,以及PVA中的 OH- 和F-MMT 中F-之间强的氢键作用。     

Synthesis and Characterization of Polyaniline/Partially Phosphorylated Poly（vinyl alcohol） Nanoparticles

The polyaniline/partially phosphorylated poly（vinyl alcohol）（PANI/P-PVA） nanoparticles were prepared by the chemical oxidative dispersion polymerization of aniline monomer in 0.5 mol/L HC1 aqueous media with the partially phosphorylated poly（vinyl alcohol） （P-PVA） as the stabilizer and co-dopant. The PANI/P-PVA nanoparticles were characterized by transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy （FTIR）, thermal gravimetric analysis （TGA）, X-ray diffraction （XRD）, electrical conductivity measurements and re-dispersion stability testing. All the results were compared with the properties of the conventional polyaniline in the emeraldine salt form （PANI ES）. It was found that the feeding ratio of P-PVA obviously affected the morphology, re-dispersion stability and electrical conductivity of the PANI/P-PVA nanoparticles. When the feeding ratio of P-PVA ranged from 40 wt% to 50 wt%, the PANI/P-PVA nanoparticles showed spherical shape with good uniformity, significant re-dispersion stability in aqueous media and good electrical conductivity.     

Thermal properties and flammability performance of poly (vinyl alcohol)/α-zirconium phosphate nanocomposites

Nanocomposites of poly (vinyl alcohol) with ethylamine modified zirconium phosphate (ZrP-EA) were prepared by solution blending. Their morphologies were elucidated with X-ray diffraction and transmission electron microscopy, while the thermal stability and flammability performance were characterized by thermogravimetric analysis, Fourier transform infrared spectra and microscale combustion calorimetry. It was established that the morphology of the nanocomposites evolved as ZrP-EA content increased. In the nanocomposites, catalytic degradation of the acetate groups remaining in poly (vinyl alcohol) occurred and catalytic carbonization was observed. Microscale combustion calorimetry revealed that the flammability performance of poly (vinyl alcohol) was improved by the introduction of zirconium phosphate nanoplatelets.     

Stabilization of electrospun poly(vinyl alcohol) nanofibrous mats in aqueous solutions

<正>The stability ofpoly(vinyl alcohol)(PVA) nanofibrous mats in water media was improved by post-electrospinning treatments.Bifunctional glutaraldehyde(GA) in methanol was used as a crosslinking agent to stabilize PVA nanofiber,but fiber twinning was observed frequently,and the highly porous structure of PVA nanofibrous mats was destroyed when the crosslinked fiber was soaked in water.To overcome this shortcoming,chitosan(CS) was introduced into the PVA spinning solution to prepare PVA/CS composite nanofibers.Their treatment in GA/methanol solution could retain the fiber morphology of PVA/CS nanofibers and porous structure of PVA/CS nanofibrous mats even if they were soaked in aqueous solutions for 1 month.Scanning electron microscopy(SEM),X-ray diffraction(XRD),thermal gravimetric analysis(TGA) and differential scanning calorimetry(DSC) were applied to characterize the physicochemical structure and thermal properties of PVA nanofibers.It was found that the water resistance of PVA nanofibrous mats was enhanced because of the improvement of the degree of crosslinking and crystallinity in the electrospun PVA fibers after soaking in GA/methanol solution.     

Preparation and characterization of rigid poly(vinyl chloride)/MMT nanocomposites. II. XRD,morphological and mechanical characteristics

A Haake torque rheometer equipped with an internal mixer is used to study the influence of the amount of sodium montmorillonite (Na⁺‐MMT) and organically modified MMT (O‐MMT) on X‐ray diffraction (XRD), morphology, and mechanical characteristics of rigid poly (vinyl chloride) (PVC)/Na⁺‐MMT and PVC/O‐MMT nanocomposites, respectively. Results of XRD and transmission electron microscopy (TEM) indicate that MMT is partially encapsulated and intercalated in the rigid PVC/Na⁺‐MMT nanocomposites. However, results of XRD and TEM show MMT is partially intercalated and exfoliated in the rigid PVC/O‐MMT nanocomposites. Tensile strength, yield strength, and elongation at break of the rigid PVC/MMT nanocomposites were improved simultaneously with adding 1–3 wt % Na⁺‐MMT or O‐MMT with respect to that of pristine PVC. However, the addition of Na⁺‐MMT or O‐MMT should be kept as not more than 3 wt % to optimize the mechanical properties and the processing stability of the rigid PVC/MMT nanocomposites. SEM micrographs of the fractured surfaces of the rigid PVC/Na⁺‐MMT and PVC/O‐MMT nanocomposites both before and after tensile tests were also illustrated and compared. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2145–2154, 2006     

Preparation and characterization of poly(vinyl alcohol)/organo-modified cloisite Na+ with chiral L-leucine amino acid/TiO2 nanocomposites

Poly(vinyl alcohol)/organo-clay/TiO₂ nanocamposites films were prepared with 10 wt % of organo-nanoclay and various amount of TiO₂ nanoparticles. Cloisite Na⁺ has been modified via cation exchange reaction using ammonium salt of natural L-leucine amino acid as a cationic surfactant. After that poly(vinyl alcohol)/organo-nanoclay/TiO₂ nanocomposites were synthesized by dispersion of TiO₂ on the surfaces of organo-nanoclay in poly(vinyl alcohol) matrix by using ultrasonic energy. Three nanocomposites with different loading of TiO₂ were prepared and characterized by X-ray diffraction, fourier transform infrared spectroscopy, field emission type scanning electron microscope, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis and ultraviolet-visible transmission spectra. The results showed that the organo-nanoclay and TiO₂ were dispersed homogeneously in poly(vinyl alcohol) matrix and also showed improvement in their thermal properties compared with the pure poly(vinyl alcohol).     

Folic acid modified electrospun poly(vinyl alcohol)/polyethyleneimine nanofibers for cancer cell capture applications

Capture and detection of metastatic cancer cells are crucial for diagnosis and treatment of malignant neoplasm. Here, we report the use of folic acid (FA) modified electrospun poly(vinyl alcohol) (PVA)/polyethyleneimine (PEI) nanofibers for cancer cell capture applications. Electrospun PVA/PEI nanofibers crosslinked by glutaraldehyde vapor were modified with FA via a poly(ethylene glycol) (PEG) spacer, followed by acetylation of the fiber surface PEI amines. The formed FA-modified nanofibers were well characterized. The morphology of the electrospun PVA/PEI nanofibers is smooth and uniform despite the surface modification. In addition, the FA-modified nanofibers display good hemocompatibility as confirmed by hemolysis assay. Importantly, the developed FA-modified nanofibers are able to specifically capture cancer cells overexpressing FA receptors, which were validated by quantitative cell counting assay and qualitative confocal microscopy analysis. The developed FA-modified PVA/PEI nanofibers may be used for capturing circulating tumor cells for cancer diagnosis applications.     

Poly(vinyl acetate)/poly(vinyl alcohol)/montmorillonite nanocomposite microspheres prepared by suspension polymerization and saponification

Poly(vinyl acetate) (PVAc)–poly(vinyl alcohol)–montmorillonite (MMT) nanocomposite microspheres were prepared through suspension polymerization followed by the heterogeneous saponification. The effects of MMT on the polymerization rate and the saponification rate of PVAc were studied. It was found that the rate of polymerization decreased when MMT content was increased. However, the saponification rate of PVAc significantly increased in the presence of nanoclay particles. The XRD measurement illustrated that the clay particles are intercalated in the polymer matrix.     

Optimization and characterization of electrospun chitosan/poly(vinyl alcohol) nanofibers as a phenol adsorbent via response surface methodology

Fabrication and characterization of chitosan/poly(vinyl alcohol) electrospun nanofibers for adsorption of phenol from water were investigated. The effects of voltage (15–30 kV), solution injection flow rate (0.5–1.5 ml/hr), distance of needle and collector (10–20 cm) and chitosan/poly(vinyl alcohol) ratio (25/75, 50/50, 75/25) were studied to obtain the optimum electrospinning conditions for the maximum adsorption capacity of phenol. Central composite design (CCD) was used to investigate and optimize the processing factors for production of chitosan/poly(vinyl alcohol) nanofibers from aqueous solutions. The nanofibers were characterized using scanning electron microscopy and Fourier transform infrared spectroscopy (FTIR). Uniform beadless nanofibers with the minimum diameters of 3–11 nm were obtained at chitosan/poly(vinyl alcohol) ratio of 50/50, voltage of 22.5 kV, distance of 15 cm and injection flow rate of 1.99 ml hr^?1. Fourier transform infrared spectrum of chitosan/poly(vinyl alcohol) exhibited the existence of relevant functional groups of both poly(vinyl alcohol) and chitosan in the blends. Results of CCD show that among all processing factors, rate of electrospinning will highly affect the nanofiber adsorption. The response surface quadratic order model presented correlation coefficient explaining 69.5% of the variability in the adsorption. Copyright © 2017 John Wiley & Sons, Ltd.     

Miscibility and thermal stability of poly(vinyl alcohol)/chitosan mixtures

The miscibility and the thermal behaviour of chitosan acetate (ChA) with poly(vinyl alcohol) (PVA) have been investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Chitosan is blended with poly(vinyl alcohol) in acetic acid solution and this solution is cast to prepare the blend film. From thermal curves the thermal transitions: T_g, T_m and characteristic temperatures of decomposition: T_di, T_max have been determined and compared. The influence of the degree of PVA hydrolysis on the thermal properties of blend systems has been discussed.Based upon the observation on the DSC analysis, the melting point of PVA is decreased when the amount of ChA in the blend film is increased. Though some broadening of the transition curves could be noticed (DSC, TGA and DMA), the obtained results suggest that in the solid ChA/PVA blends the components are poorly miscible. Only PVA sample with relatively low DH = 88% and hence low degree of crystallinity shows partial miscibility with ChA of relatively low molecular weight.     

Morphology and crystallinity of particles formed from dilute solutions of poly(vinyl alcohol-b-acrylonitrile), poly(vinyl alcohol) and polyacrylonitrile

The morphology of agglomerates and particles of poly(vinyl alcohol-b-acrylonitrile), poly(vinyl alcohol) (PVA) and polyacrylonitrile (PAN) formed from their dilute solutions and the variation of the morphology with the composition of the block copolymers were examined using transmission electron microscopy. The crystalline nature of these particles was studied by an electron diffraction method. Electron diffraction for copolymers containing AN lower than 30 wt% mainly showed a single-crystal diffraction pattern of the PVA component. With the copolymer containing 38.90 wt% AN, a mixed pattern of a blend of PVA polycrystal and PAN polycrystal as well as a PVA single-crystal pattern were simultaneously observed.     

Development of poly(vinyl chloride)/montmorillonite nanocomposites using chelating agents

Different chelating agents such as poly(ethylene glycol), propylene glycol monooctadecanoate and palm oil were used for modification of the surface-treated montmorillonite (MMT). The work also included the development of a technique for mixing chelating agents with MMTs using different methods and different proportions of MMT/chelating agent/ethanol. Evaluation of the result of mixing was performed by thermogravimetric analysis, X-ray diffraction and high-resolution scanning electron microscopy (HR-SEM). The results showed that the chelating agents used were intercalated in MMT, increasing the interlayer spacing. The OMMT was used in the manufacture of composites with rigid PVC using a microcompounder. The master batch concept turned out to be promising in terms of dispersion and delamination of clay, as observed in HR-SEM photographs. However, despite good dispersion and exfoliation of MMT, poor compatibility between clay platelets and PVC matrix remains to be solved to enable full exploitation of its engineering potential. Despite this drawback, good thermal stability and mechanical properties have already been achieved.     

Preparation,characterization and thermal behavior of poly(vinyl alcohol)/organic montmorillonite nanocomposites through solid-state shear pan-milling

In this study, the solid-state shear pan-milling was employed to prepare a series of polymer/layered silicate (PLS) nanocomposites. During the process of pan-milling at ambient temperature, poly(vinyl alcohol)/organic montmorillonite (PVA/OMMT) can be effectively pulverized, resulting in coexistence of intercalated and exfoliated OMMT layers. The obtained PLS nanocomposites were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM analysis indicated that OMMT dispersed homogeneously in PVA matrix and XRD results illustrated that pan-milling had an obvious effect on increase in the interlayer spacing of OMMT, and resulted in coexistence of intercalated and exfoliated OMMT layers formed. Thermal gravimetric analysis showed that thermal stability of PVA was improved owing to the incorporation of OMMT. Thermal decomposition kinetics of PVA/OMMT nanocomposites with different milling cycles of OMMT was also studied. Two types of OMMT are chosen to compare the effect of hydrophilicity of OMMT on PVA/OMMT nanocomposites.     

Alignment effect of attapulgite on the mechanical properties of poly(vinyl alcohol)/attapulgite nanocomposite fibers

Poly(vinyl alcohol) (PVA)/attapulgite (AT) nanocomposite fibers have been prepared by wet spinning. The morphology and mechanical properties of the modified PVA fibers have been characterized with transmission electron microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), birefringence measurements, and mechanical testing. The PVA/AT nanocomposite fibers show much higher tensile strength, initial modulus, and work to break than pure PVA fibers with the same draw ratio. SEM observations demonstrate that the AT nanorods can align orderly along the fiber axis by stretching and have good adhesion to the fiber matrix. The results of birefringence measurements prove that the modified fibers have higher orientation than pure PVA fibers after stretching. The results of DSC analysis indicate that the crystallinity of the PVA fibers can be increased by the addition of AT. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1995–2000, 2006     

Electrospinning fabrication and characterization of poly(vinyl alcohol)/montmorillonite/silver hybrid nanofibers for antibacterial applications

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT)/silver (Ag) nanoparticles have been electrospun for fabricating PVA/MMT/Ag nanofiber in aqueous solutions. Since PVA is a water-soluble and biocompatible polymer, it is one of the best materials for preparation of antibacterial nanofiber. MMT has been used as an inorganic filler to enhance properties of homopolymeric nanofiber. The PVA/MMT/Ag nanofiber diameter increases with increasing contents of MMT clay and Ag nanoparticles. In preservation test, the PVA/MMT/Ag nanofiber confirms an excellent antibacterial performance, elucidating for practical uses as a new preservative. Moreover, the PVA/MMT/Ag nanofiber shows improved thermal properties.