Facile fabrication of PVA composite fibers with high fraction of multiwalled carbon nanotubes by gel spinning

Poly(vinyl alcohol) (PVA) composite fibers with high fraction of multiwalled carbon nanotubes (MWCNTs) were prepared by gel spinning process. Here, a modified process was introduced to prepare concentrated PVA/MWCNTs/DMSO spinning dope, and to attain good dispersion of MWCNTs in the fibers. The final composite fibers were studied by thermogravimetric analyzer (TGA), Fourier transform infrared spectrometer (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC), and WAXD analysis. The total content of MWCNTs in PVA composite fibers, from 5 to 30 wt%, was confirmed by TGA analysis. FTIR and Raman measurements demonstrated the existence of strong hydrogen interaction between MWCNTs and PVA matrix. SEM images of composite fibers showed smooth surface, regular cross‐section shape and good dispersion of MWCNTs in the fibers. DSC analysis showed that the crystallinity first increased and then decreased with the increase of MWCNTs contents. It can be concluded that low concentration of MWNCTs can act as nucleation sites for crystallization of PVA component, and large amount of MWCNTs may impede the crystallization of PVA component. The WAXD analysis results indicated that the crystal orientation of the PVA component in PVA composite fibers is almost identical at the same drawn ratio. Polarized Raman analysis indicated a small increase in MWCNTs orientation for the composite fibers. The mechanical properties tests showed that the composite fibers exhibit significant improvement in tensile strength and modulus as compared to the neat PVA fibers. The composite fibers also showed sustained growth in electrical conductivity. POLYM. ENG. SCI., 58:37–45, 2018. © 2017 Society of Plastics Engineers     

Structure evolution of melt‐spun poly(vinyl alcohol) fibers during hot‐drawing

The drawability of melt‐spun poly(vinyl alcohol) (PVA) fibers and its structure evolution during hot‐drawing process were studied by differential scanning calorimetry (DSC), two dimensional X‐ray diffraction (2‐D WAXD) and dynamic mechanical analysis (DMA). The results showed that the water content of PVA fibers should be controlled before hot‐drawing and the proper drying condition was drying at 200°C for 3 min. PVA fibers with excellent mechanical properties could be obtained by drawing at 200°C and 100 mm/min. The melt point and crystallinity of PVA fibers increased with the draw ratio increasing. The 2‐D WAXD patterns of PVA fibers changed from circular scattering pattern to sharp diffraction point, confirming the change of PVA fibers from random orientation to high degree orientation. Accordingly, the tensile strength of PVA fibers enhanced by hot‐drawing, reaching 1.85 GPa when the draw ratio was 16. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Microstructure and characterization of electrospun poly(vinyl alcohol) nanofiber scaffolds filled with graphene nanosheets

Graphene nanosheets (GNSs) have attracted significant scientific attention because of their remarkable features, including exceptional electron transport, excellent mechanical properties, high surface area, and antibacterial functions. Poly(vinyl alcohol) (PVA) solutions filled with GNSs were prepared for electrospinning, and their spinnability was correlated with their solution properties. The effects of GNS addition on solution rheology and conductivity were investigated. The as‐spun fibers were characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC). The results revealed the effects of GNS on the microstructure, morphology, and crystallization properties of PVA/GNS composite nanofibers. The addition of GNSs in PVA solution increased the viscosity and conductivity of the solution. The electrospun fiber diameter of the PVA/GNS composite nanofiber was smaller than that of neat PVA nanofiber. GNSs were not only embedded at the fibers but also formed protrusions on the fibers. In addition, the crystallinity of PVA/GNS fiber decreased with higher GNS content. The possible application of PVA/GNS fibers in tissue engineering was also evaluated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41891.     

Effect of thermotropic liquid crystalline poly(ether ketone)arylates on the processibility and properties of poly(ether ether ketone)s fibers

A series of composite fibers based on poly(ether ether ketone)s (PEEK) and a thermotropic liquid crystalline poly(ether ketone)arylates (PEKAR) have been prepared by melt spinning. The structure, compatibility, and properties of these composite fibers were investigated in detail by rheological measurements, differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray diffraction, scanning electron microscopy, orientation degree test, and mechanical properties test. The results showed that the addition of PEKAR could reduce the apparent melt viscosity of the blends obviously, which is beneficial in improving the processibility of PEEK at a relatively low temperature. After adding 1 wt % PEKAR to PEEK, the tensile strength of the post‐treatment fiber improved by 8.8%, whereas the crystallinity of the as‐spun fiber increased from 21.76% to 31.51%, and the orientation degree also increased with the addition of PEKAR. The result of morphology research suggested that PEKAR had a good compatibility with PEEK resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40595.     

Crystallinity study of electrospun poly (vinyl alcohol) nanofibers: effect of electrospinning,filler incorporation,and heat treatment

This study aims to explore crystallinity variations of polyvinyl alcohol (PVA) as a result of electrospinning, filler addition, and heat treatment. Pure PVA and PVA nanocomposite fibers containing only nanohydroxy apatite (nHAp) and together with cellulose nanofibers (CNF) were electrospun. Electrospun nanofibers were heat treated at 180 °C for 8 h. The morphology of electrospun fibers was evaluated by scanning electron microscopy (SEM) while Fourier transform infrared spectroscopy, differential scanning calorimetry, and wide angle X-ray scattering were used to analyze nanofibers crystallinity. Un-treated electrospun nanofibers were shrank and lost their porous structure in water, while heat treatment of nanofibers caused stabilization of fibrous mats in boiling water. It was concluded that the crystallinity of electrospun PVA were considerably reduced compared to PVA powder due to formation of metastable—small and/or defective crystals. Adding small content (1 wt%) of nHAp led to increase in electrospun nanofibers crystallinity. However, incorporation of higher content of nHAp and CNF caused reduction of crystallinity most probably due to possible interactions among components which interrupt the orientation of macromolecules. All analyzing methods proved the crystallinity enhancement of nanofibers upon heat treatment which can be attributed mostly to water evaporation from electrospun fibers structure.     

Fabrication and characterization of poly(vinyl alcohol)/graphene oxide nanofibrous biocomposite scaffolds

Nanofibrous biocomposite scaffolds of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were prepared by using electrospinning method. The microstructure, crystallinity, and morphology of the scaffolds were characterized through X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The mechanical properties were investigated by tensile testing. Moreover, Mouse Osteoblastic Cells (MC3T3‐E1) attachment and proliferation on the nanofibrous scaffolds were investigated by MTT [3‐(4,5‐dimeth‐ylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide] assay, SEM observation and fluorescence staining. XRD and FTIR results verify the presence of GO in the scaffolds. SEM images show the three‐dimensional porous fibrous morphology, and the average diameter of the composite fibers decreases with increasing the content of GO. The mechanical properties of the scaffolds are altered by changing the content of GO as well. The tensile strength and elasticity modulus increase when the content of GO is lower than 1 wt %, but decrease when GO is up to 3 and 5 wt %. MC3T3‐E1 cells attach and grow on the surfaces of the scaffolds, and the adding of GO do not affect the cells' viability. Also, MC3T3‐E1 cells are likely to spread on the PVA/GO composite scaffolds. Above all, these unique features of the PVA/GO nanofibrous scaffolds prepared by electrospinning would open up a wide variety of future applications in bone tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study on the preparation and properties of aligned carbon nanotubes/polylactide composite fibers

The oriented carbon nanotubes (CNTs)/polylactic acid (PLA) composite fibers was prepared by the modified electrospinning technology, and characterized by Raman, X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetric (TG)/differential scanning calorimetric (DSC) analyses, respectively. Results showed that functionalized MWNTs have obvious orientation along the fiber axial in the interior of the electrospun PLA fibers, and improved the crystallization degree of PLA in the composite fibers due to the heterogeneous nucleation effect. The influences of polycaprolactone‐functionalized multiwalled carbon nanotubes (MWNTs‐PCL) on the performances of PLA fibers were studied. The crystallization region inside the MWNTs–PCL/PLA composite fibers was enlarged by increasing the MWNTs‐PCL content. As a result, enhanced crystallization temperature was obtained. Moreover, a small amount of MWNTs‐PCL (0.5%) improved the thermal stability of PLA matrix, while excess MWNTs‐PCL (3.0%) induced the decrease of the thermal stability of PLA resin due to the agglomeration of MWNTs‐PCL. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

The Preparation and Characterization of Esterified Banana Trunk Fibers/Poly(vinyl alcohol) Blend Film

Polymer composite using natural fiber as reinforcement material is getting attention due to easy availability and its low cost. In this work, poly(vinyl alcohol) (PVA)/fatty acid esterified banana trunk fibers (FAGBTF) of various compositions were produced by a solution casting method. The characteristic properties of PVA/ FAGBTF composite films were examined by Fourier Transform Infra-Red (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. On the whole, the increase in the amount of BTF in the composite systems improved the thermal properties and decreased percentage degree of swelling as compared to pure PVA.     

Electrospun polyvinyl alcohol/waterborne polyurethane composite nanofibers involving cellulose nanofibers

TEMPO‐oxidized cellulose nanofibers (TOCNs) were used as nanofillers in this work. Composite nanofibers of polyvinyl alcohol (PVA)/waterborne polyurethane (WPU) reinforced with TOCNs were produced by electrospinning. The reinforcing capability of TOCNs was investigated by tensile tests. Scanning electron microscopy (SEM), X‐ray diffraction, and thermogravimetry analyses were also carried out in order to characterize the appearance, crystallinity, and reinforcing effect of the cellulose nanofibers. SEM results showed that PVA/WPU/TOCNs composite nanofibers presented a highly homogeneous dispersion of TOCNs. The reinforced composites had about 44% increase in their mechanical properties with addition of only 5 wt % of TOCNs while about 42% decrease in elongation at break. The TOCNs reinforced composite nanofibers were more thermally stable than pure PVA/WPU nanofibers. The development of crystalline structure in the composite fibers was observed by XRD. Since PVA, WPU, and TOCNs are hydrophilic, non‐toxic, and biocompatible, and therefore, these nanocomposite nanofibers could be used for tissue scaffolding, filtration materials, and medical industries as wound dressing materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41051.     

Wetting behavior of electrospun poly(L‐lactic acid)/poly(vinyl alcohol) composite nonwovens

Poly(L ‐lactic acid) (PLLA) fibers have been extensively studied for various applications. In this work, PLLA and poly(vinyl alcohol) (PVA) were prepared by coelectrospinning to form composite nonwoven materials. The structures and diameter distribution of the electrospun PLLA/PVA composite nonwovens were examined by atomic force microscopy (AFM) and scanning electronic microscope (SEM). The wetting behavior of the electrospun PLLA/PVA composite nonwovens was also investigated using static contact angles and dynamic water adsorption measurements. It was observed that the addition of PVA in the electrospun PLLA/PVA composite nonwovens significantly alerted the contact angles and water adsorption of the composite materials. It was also found that the increase in the content of PLLA led to the increase in the surface contact angle and decrease in water adsorption of the electrospun PLLA/PVA nonwoven materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graphene oxide reinforced poly(vinyl alcohol) composite fibers via template-oriented crystallization

Here, a high breaking strength and high initial modulus fibers comprised of polyvinyl alcohol (PVA) and graphene oxide (GO) were fabricated via simple method of solution blending and wet-spinning. The structure and properties of these fibers were studied in details using two-dimensional X-ray diffractions, differential scanning calorimetry, one-dimensional X-ray diffractions, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis and tensile test. Compared with pure PVA fiber, a 43 % improvement of breaking strength and an 81 % improvement of initial modulus were achieved by addition of 0.1 wt% of GO, and the results indicated that crystallization and orientation of GO/PVA composite fibers were both increased. GO could not only promote PVA chains ordered arrangement for increasing crystallization, but also act as a template for polymer amorphous orientation via the interactions between PVA and GO in the process of hot drawing and heat setting, which were responsible for the significant improvement in the mechanical properties of GO/PVA composite fibers.

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Graphical abstract GO could not only promote PVA chains ordered arrangement for increasing crystallization, but also act as a template for PVA amorphous orientation in the process of hot drawing. The amorphous orientation degree and the crystallization degree of PVA fibers were increased by adding GO.

     

Processing,structure, and properties of multiwalled carbon nanotube–poly(phenylene sulfide) composite fibers

To improve the processability and properties of the poly(phenylene sulfide) (PPS) fibers at room temperature and high temperatures, a series of composite fibers based on PPS and multiwalled carbon nanotubes were prepared by melt spinning. We researched the processability with a high‐pressure capillary rheometer, and the properties of the composite fibers were investigated in detail by scanning electron microscopy, differential scanning calorimetry, fiber sonic velocity measurement, and single‐fiber strength testing. The results show that the carbon nanotubes (CNTs) had good interfacial adhesion with PPS and dispersed homogeneously in the PPS matrix. When the shear rate was higher than 500 s^?1, the oriented CNTs induced the orientation of PPS molecular chains; this resulted in a decline in the apparent viscosity and an increase in the orientation degree of the molecular chains. Meanwhile, the CNTs acted as nucleating agents to effectively improve the crystallization of PPS. The strength of the fibers at room temperature were improved by 28.8% after the addition of 0.2% CNTs, and the initial modulus was also significantly enhanced. The strength retention at 160 °C was promoted from 60.58 to 88.32% with the addition of 1.0% CNTs. The shrinking percentage decreased to almost zero from higher than 15%; this suggested that the CNTs could efficiently improve the dimensional stability at high temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44609.     

Electrospun gelatin/nylon‐6 composite nanofibers for biomedical applications

We describe the preparation and characterization of gelatin‐containing nylon‐6 electrospun fibers and their potential use as a bioactive scaffold for tissue engineering. The physicochemical properties of gelatin/nylon‐6 composite nanofibers were analyzed using field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, TGA and contact angle and tensile measurements. FE‐SEM and TEM images revealed that the nanofibers were well oriented and showed a good incorporation of gelatin. FTIR spectroscopy and TGA also revealed that there was good interaction between the two polymers at the molecular level. The adhesion, viability and proliferation properties of osteoblast cells on the gelatin/nylon‐6 composite nanofibers were analyzed by an in vitro cell compatibility test. Our results suggest that the incorporation of gelatin can increase the cell compatibility of nylon‐6 and therefore the composite mat obtained has great potential in hard tissue engineering. © 2012 Society of Chemical Industry     

Physical properties of poly(vinyl alcohol) fibers prepared from wet spinning/multi-step drawing

The preparation of poly(vinyl alcohol) (PVA) fibers by multi-step drawing was examined. The high draw ratio was attained when the drawing just before melting point was repeated. The influences of the draw ratio on mechanical and thermal properties of the fibers were studied. We utilized the wide angle x-ray diffraction (WAXD) as a medium to observe the erystallinity and the orientation of PVA fibers to study their effects on the physical properties of the fibers. With various coagulation bath concentration, both the tenacity and Young's modulus of fibers would increase as the draw ratios increased, the elongation would decrease at the same time. The tenacity was able to reach 41.0 cN/tex with the Young's modulus being 856.2 cN/tex; also, as the draw ratios increased, both crystallinity and orientation would increase. The crystallinity was about 67.2 % and the orientation was about 86.4%.     

冻胶法聚乙烯醇水溶纤维的结构研究

由冻胶纺丝制备聚乙烯醇 (PVA)水溶纤维 ,用X -衍射、双折射、扫描电镜、电子强伸仪等测试了纤维的结晶度、取向度、横截面形态、应力应变曲线和纤维的水溶温度。实验证明 :纤维的结晶度和取向度随拉伸倍数和热处理温度的增加而增加 ;在同一条件下醇解度较高的PVA纤维的结晶度和取向度高于醇解度较低的PVA纤维 ;纤维呈圆形截面 ,无皮芯层 ,结构均匀 ,具有良好的力学性能和宽的水溶温度范围。     

Crystallization behavior of melt-spun poly(vinyl alcohol) fibers during drawing process

The crystallization behavior of melt-spun poly(vinyl alcohol) (PVA) fibers during hot drawing process was studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and computer controlled electronic universal testing machine. The effects of drawing temperature and drawing speed on the crystallinity and the stress induced crystallization of PVA fibers were discussed. The results showed that the crystallization process of PVA fibers during hot drawing presented three stages: initial stage, stress induced crystallization stage and slowly increasing stage. And PVA fibers with high crystallinity can be obtained by properly increasing the drawing temperature and drawing speed, especially when the drawing temperature and speed were 453 K and 100 mm/min respectively. The stress induced crystallinity of PVA fibers during drawing process was the difference between the crystallinity of PVA fibers after drawing and after only heat treatment. At the low drawing speed, i.e. 50 mm/min, due to the strong molecular movement and orientation relaxation under high temperature, the effect of stress induced crystallization weakens with the increase of drawing temperature, the ratio between stress induced crystallinity and thermal induced crystallinity changed from 8.7%:0%(393 K) to 1.7%:5% (453 K). While at the high drawing speeds, i.e. 100 mm/min and 500 mm/min, with the decrease of available orientation relaxation time, the stress induced crystallization plays an important role during the drawing process, the ratio between stress induced crystallinity and thermal induced crystallinity were 8%:2.9% and 10.2%:0.5% at 453 K respectively.     

聚乙烯醇／水滑石共混纤维的制备及其性能研究

采用凝胶纺丝法制备聚乙烯醇／水滑石（PVA／HT）共混纤维。通过扫描电镜（SEM）观察水滑石在PVA／HT共混纤维中的分散状况和共混纤维的表面形态。从傅里叶变换红外光谱（FT-IR）可以看出HT和PVA之间存在明显的氢键作用;热重分析（TG）测试表明水滑石的加入可以有效提高PVA的热性能;加入适量的HT可以提高PVA纤维的断裂强度;随着HT含量的增加,PVA／HT共混纤维的最大拉伸倍数下降且表面易产生缺陷。     

Preparation and surface modification of electrospun aligned poly(butylene carbonate) nanofibers

In this study, aligned poly(butylene carbonate) nanofibers were fabricated by electrospinning with a high‐speed transfer roller as the receiving device. Cold plasma treatment technology was applied to improve its hydrophilicity and activity to expand its application in biological materials. The morphology of the fibers was investigated with scanning electron microscopy. X‐ray diffraction was used to research the impact of the rotation speed on the crystallization and orientation degree of the crystals. The tensile properties of the materials were evaluated by a universal tester. The surface properties of the fibers pretreated by Helium (He) and those grafted with gelatin were evaluated with water contact angle measurement and X‐ray photoelectron spectroscopy. The experimental results indicate that the order degree of fibers, crystallinity, and orientation of the crystalline region, including the mechanical properties, all increased correspondingly with the rotation speed. After plasma pretreatment, the hydrophilicity was improved significantly, and the grafting reaction was realized successfully. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Interfacial interaction and mechanical properties of chitin whisker–poly(vinyl alcohol) gel‐spun nanocomposite fibers

Nanocomposite fibers were prepared from chitin whiskers (ChWs) as the reinforcing phase and poly(vinyl alcohol) (PVA) as the matrix. Colloidal suspensions of ChWs, obtained by acid hydrolysis of chitin from crab shell, were thoroughly mixed with aqueous PVA. The homogeneous PVA–ChW suspensions were gel‐spun into a methanol coagulating bath. Wide‐angle X‐ray diffraction patterns evidenced the orientation of ChWs along the fiber axis. From differential scanning calorimetry, the crystallinity of the PVA component was found to increase with ChW loading due to the possible dragging of PVA chains adhering to ChWs during vertical extrusion. The non‐isothermal crystallization peak of PVA was observed to shift to lower temperature with ChW loading indicating interfacial interactions between PVA and ChW. Further interaction between PVA and ChW was evidenced by the shifting of the Fourier transform infrared bands of PVA to lower wavenumber and the dynamic tan δ peak, corresponding to α‐relaxation of PVA, shifting to higher temperature. The interaction of ChWs with the matrix PVA yielded a significant enhancement in the mechanical properties of the nanocomposites. Copyright © 2012 Society of Chemical Industry     

Effect of coupling agent on structure and properties of micro–nano composite fibers based on PET

Poly(ethylene terephthalate) (PET)/carbon black (CB) micro–nano composite fibers were manufactured by melt spinning method. To achieve good dispersion, nano‐CB particles were modified by coupling agent (CA). The effect of CA on structure and properties of the fibers were investigated via scanning electron microscopy (SEM), tensile testing, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), sonic orientation, and birefringence, respectively. At 2 wt % CA dosage, CB particles present the optimal dispersion in the fibers, shown in SEM images. Besides, the fibers possess the maximum breaking strength, the lowest crystallization temperature, and the highest crystallinity. After CA modification, the superior interfacial structure between PET and CB is beneficial to improve mechanical properties of the fibers. The well dispersed CB particles provide more heterogeneous nucleation points, resulting in the highest crystallinity. Furthermore, the fibers with 2 wt % CA dosage possess the maximum orientation and shrinkage ratio. According to Viogt–Kelvin model, the thermal shrinkage curves of the fibers can be well fitted using single exponential function. The three‐phase structure model of crystal phase–amorphous phase–CB phase was established to interpret the relationship among shrinkage, orientation, and dispersion of CB particles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43846.