Nano‐carbon black filled Lyocell fiber as a precursor for carbon fiber

In this work, Lyocell fibers filled with various amounts of carbon black were prepared. Wide angle X‐ray diffraction (WAXD) results showed that carbon black filled Lyocell fibers still had a cellulose II crystal structure and kept the characteristic peak of carbon black at the same time. The results of mechanical properties showed a slight reduction in the carbon black filled Lyocell fiber. Moreover, the heat stabilities of the carbon black filled Lyocell fibers showed no obvious change. The residue of carbon black filled Lyocell fiber at 1000°C was higher than that of Lyocell fiber, implying higher carbon yield could be obtained for the carbon black filled Lyocell precursor. Scanning electron microscopy (SEM) experiments showed that the surface and the cross section of carbon black filled Lyocell fiber were smooth and round, which are consistent with the carbon fiber precursor. The WAXD pattern of carbon black filled Lyocell‐based carbon fiber was different from that of Lyocell‐based carbon fiber. The addition of carbon black transfers the diffraction peak of carbon fiber while keeping the characteristic structure of carbon black. The results of mechanical properties of carbon fibers show that, if an appropriate amount of carbon black was chosen, carbon fiber with better properties than Lyocell‐based carbon fiber could be obtained by using the carbon black filled Lyocell fibers as the precursor. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 65–74, 2006     

Effect of heat treatment on the structure and properties of Lyocell fibers

Lyocell fibers were heat‐treated under different conditions. The tensile strength and initial modulus of the heat‐treated Lyocell fibers increased sharply, whereas the elongation at break decreased. Moreover, applying tension to the fibers during the heat treatment further improved the tensile strength and initial modulus. In addition, the crystallinity of the heat‐treated fibers increased slightly, and there was no obvious change with an increase in the tension; the general orientation of the heat‐treated fibers increased, the crystalline orientation little changed, and the amorphous orientation improved. Also, the improved mechanical properties of the Lyocell fibers via the heat treatment could not be preserved for long. The reason may be that the crystalline structure of the Lyocell fibers was not destroyed and no new crystallites were formed during the heat‐treatment process. Therefore, the heat‐treated Lyocell fibers reverted to their original state with time because there was no crosslinking point to fix the orientation, although the cellulose molecules of the amorphous region of the Lyocell fibers were more oriented by the heat treatment with tension. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1738–1743, 2006     

Plasticizer effect of dibutyl phthalate on the morphology and mechanical properties of hard elastic poly(vinylidene fluoride) fibers

To improve the structure and hard elasticity of poly(vinylidene fluoride) (PVDF) fibers, a small amount of the plasticizer dibutyl phthalate (DBP) was added to PVDF. The PVDF/DBP blend fibers were prepared by melt spinning and subsequent annealing. The crystalline structure and thermal properties of the blend fibers were analyzed in terms of the long‐period lamellar spacing, crystal structure, and degree of crystallinity with X‐ray diffraction, differential scanning calorimetry, and small‐angle X‐ray scattering. The results indicated that stacked crystalline lamellae, which were aligned normal to the fiber axis, existed in the blend fibers, and they were in the form of an α‐crystal phase. The total crystallinity of the blend fibers was higher than that of the pure PVDF fibers, and it reached its highest value when the DBP concentration was 2 wt %; then, it decreased with an increase in the DBP content. The morphology and mechanical properties of the fibers were also investigated with scanning electron microscopy and electronic tensile experimentation. The results of scanning electron microscopy apparently exhibited a small porous structure on the surface of the blend fibers, and the more DBP there was in the PVDF fibers, the more porous structure was obtained. Mechanical experiments indicated that the fibers with a 5 wt % concentration of DBP had better elastic recovery and breaking strain than the pure PVDF fibers. These results all indicated that DBP‐modified PVDF fibers have potential applications in preparing microporous membranes by a melt spinning and stretching process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison of the structures and properties of Lyocell fibers from high hemicellulose pulp and high α‐cellulose pulp

Lyocell fibers were produced from a cheap pulp with a high hemicellulose content and from a conventional pulp with a high α‐cellulose content. The mechanical properties, supermolecular structure, fibrillation resistance, and dyeing properties as well as the fibril aggregation size of the high hemicellulose Lyocell fiber and high α‐cellulose Lyocell fiber were compared. The results showed that the high hemicellulose spinning solution could be processed at a higher concentration, which improved the mechanical properties and the efficiency of the fiber process. Compared with the high α‐cellulose Lyocell fiber, the high hemicellulose Lyocell fiber had better fibrillation resistance and dyeing properties. Therefore, it is feasible that this cheap pulp with a high hemicellulose content can be used as a raw material for producing Lyocell fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Producing high‐quality precursor polymer and fibers to achieve theoretical strength in carbon fibers: A review

The precursor fiber quality has a large impact on carbon fiber processing in terms of its performance, production yield, and cost. Polyacrylonitrile precursor fibers have been used commercially to produce strong carbon fibers with average tensile strength of 6.6 GPa. There is a scope to improve the average tensile strength of carbon fibers, since only 10% of their theoretical strength has been achieved thus far. Most attempts to increase the tensile strength of carbon fibers have been made during the conversion of precursor fiber to carbon fiber. This review highlights the potential opportunities to enhance the quality of the polyacrylonitrile‐based precursor fiber during polymer synthesis, spinning, and postspinning. These high‐quality precursor fibers can lead to new generation carbon fibers with improved tensile strength for high‐performance applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43963.     

Evolution of polyacrylonitrile precursor fibers and the effect of stretch profile in wet spinning

Wet spinning of polyacrylonitrile-based polymers is a common technique to manufacture carbon fiber precursors. Understanding the role of stretch profile on structural evolution will support efforts to reduce cost and improve process robustness. Fiber stretch generally occurs in three sequential stages: jet stretch, wet stretch (first draw), and hot draw (second draw). In this study, total fiber stretch was kept constant, but distributed differently across the stretch stages yielding three different fiber variants. Samples were collected and analyzed after each stretch stage in order to correlate process parameters to structural information. For all variants, orientation of the ordered phase increases gradually for each stage of stretch while activation energy for the structural relaxation decreases. Alternatively, crystallite size increases substantially during hot draw, which is shown to have the most pronounced effect on cyclization behavior. Given the process conditions, the variant with the lowest jet stretch and highest hot draw demonstrates the highest tenacity and modulus along with the greatest orientation, crystallite size, and highest peak exotherm temperature.     

Effects of hydrolysis of precursor on the structures and properties of polymer-derived SiBN ceramic fibers

In this paper, polyborosilazane precursor was synthesied from HMDZ, HSiCl₃, BCl₃ and CH₃NH₂ using a multistep method. By controlling the storage conditions, parts of the polyborosilazane fibers were hydrolyzed. FT-IR, NMR, XRD, TEM and monofilament tensile strength test were employed to study the effects of hydrolysis of precursor on the structures and properties of polymer-derived SiBN ceramic fibers. FT-IR and NMR results indicate that Si-N group in PBSZ reacts with H₂O to form Si-O-Si group. After pyrolysis reaction at 1400℃, Si-O-Si group will finally transformed into highly ordered cristobalite and β-quartz, resulting in formation of the wrinkled surface of the obtained SiBN ceramic fiber. The strip-like defects on fiber surface, according to monofilament tensile strength test, had a significant effect on mechanical property of the obtained SiBN ceramic fiber and caused no increase in fiber tensile strength of hydrolytic polyborosilazane fiber before and after pyrolytic process.     

Influence of different functionalized multiwall carbon nanotubes on the mechanical properties of poly(ethylene terephthalate) fibers

Master batches with four different kinds of functionalized multiwall carbon nanotubes (MWCTs) were prepared through the mixing of MWCTs with poly(ethylene terephthalate) (PET) (0.01 : 0.99 w/w) in trifluoroacetic acid/dichloromethane mixed solvents (0.7 : 0.3 v/v) followed by the removal of the solvents in the mixture by flocculation. The results of scanning electron microscopy showed that a good dispersion of MWCTs in PET was achieved. The reinforced fibers were fabricated by the melt spinning of PET chips with small amounts of the master batch and then further postdrawing. The optimal spinning conditions for the reinforcement of fibers were a 0.6-mm spinneret hole and a 250 m/min wind-up speed. Among the four master batches, the fibers obtained from PET/master batch B made by acid-treatment had the highest enhancement of mechanical properties. For a 0.02 wt % loading of acid-treated MWCT, the breaking strength of the PET/master batch B composite fibers increased by 36.9% (from 4.45 to 6.09 cN/dtex), and the initial modulus increased by 41.2% (from 80.7 to 113.9 cN/dtex). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of spinning conditions on the mechanical properties of polyacrylonitrile fibers modified with carbon nanotubes

Carbon nanotubes (CNTs) were used to modify polyacrylonitrile (PAN) polymer. The PAN/CNT composite fibers were spun from dimethylformamide solutions containing different types of CNTs. The effect of nanotube addition to the fiber precursor on the resulting mechanical properties is discussed. In this study, we examined the relationship of the rheological properties of PAN spinning solutions containing various types of CNTs and the tensile strength of the resulting PAN fibers. The presence of CNTs in the PAN spinning solution enhanced its deformability during the drawing stage. This effect resulted in a higher tensile strength in the fibers containing nanotubes, as compared to the pure fibers. The use of a three‐stage drawing process resulted in a significant increase in the tensile strength of PAN fibers modified with multiwalled nanotubes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Carbon fibers derived from UV‐assisted stabilization of wet‐spun polyacrylonitrile fibers

A rapid, dual‐stabilization route for the production of carbon fibers from polyacrylonitrile (PAN) precursor fibers is reported. A photoinitiator, 4,4′‐bis(diethylamino)benzophenone, was added to PAN solution before the fiber wet‐spinning step. After a short UV treatment that induced cyclization and crosslinking at a lower temperature, precursor fibers could be rapidly thermo‐oxidatively stabilized and successfully carbonized. Scanning electron microscopy micrographs show no deterioration of the microstructure or hollow‐core formation in the fibers due to UV treatment or presence of photoinitiator. Fast‐thermally stabilized pure PAN‐based carbon fibers show hollow‐core fiber defects due to inadequate thermal stabilization, but such defects were not observed in carbon fibers derived from fast‐thermally stabilized fibers that contained photoinitiator and were UV treated. Tensile testing results confirm that fibers containing 1 wt % photoinitiator and UV treated for 5 min display higher tensile modulus than all other sets of thermally stabilized and carbonized fibers. Wide‐angle X‐ray diffraction results show a higher development of the aromatic structure and molecular orientation in thermally stabilized fibers. No significant increase in interplanar spacing or decrease in crystals size were observed within the UV‐stabilized carbon fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation when compared with control fibers. These results establish for the first time, the positive effect of the external addition of photoinitiator and UV treatment on the properties of the PAN‐based fibers, and may be used to reduce the precursor stabilization time for faster carbon fiber production rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40623.     

Effect of precursor composition on the activation of pitchbased carbon fibers

Pure and silver-containing carbon fibers were prepared from isotropic pitch precursors supplied by Conoco, Inc., and a Korean research team and activated in carbon dioxide to varying degrees of burn-off. The specific activation rates for the carbon fibers were measured as well as the nitrogen adsorption characteristics of the activated carbon fibers. Scanning electron microscopy was used to investigate the surface morphology and the behavior of silver particles during the activation process. Molecular composition of the two pitch precursors was determined using a gas chromatograph mass spectrometer and a MALDI TOF mass spectrometer. Results showed that specific surface area increased with the burn-off, and the trends were similar for the pure and silver-containing fibers formed from both isotropic pitch precursors. However, the catalytic behavior of silver during activation, the activation rate, and even the pore characteristics of the activated fiber were found to be dependent on the molecular composition of the precursor pitch.     

Tensile strength and its variation for PAN‐based carbon fibers. II. Calibration of the variation from testing

The tensile behavior of carbon fibers shows large scattering. This is due to the fiber itself and the testing operations. Because of the high tenacity and modulus, low strain, and easy breakability in bending, not only is the tensile test for single carbon fibers extremely difficult, but the measured results are also oppugned. To achieve a reliable and accurate characterization, several factors influencing the objective and exact testing of single carbon fibers have been measured and discussed, including the wrong pretension, nonaxial stretching, and adhesion effects. The experimental results indicate that the error of strain causing them ranges from 1.5 to 12.3%. Because of the typical linear stress–strain curves of carbon fibers, the ratio of the strain error to the modulus error is approximately equal to 1 : 1, so the calibration of the measured strain must be conducted for the accurate evaluation of the modulus and itself. The calibration is put forward. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2625–2632, 2007     

Enhancing the strength of polypropylene fibers with carbon nanotubes

Single‐walled carbon nanotubes were added to two different grades of polypropylene to produce composites. The composites were then melt‐spun into fibers, and the fibers were tested with both a conventional tensile pull tester and dynamic mechanical analysis. The changes in tensile properties were related to the grade of polypropylene used. In addition to fibers being made from the mixes, coarse extrudates (i.e., undrawn, gravity‐spun filaments) were also produced. Density measurements on these extrudates showed that the addition of nanotubes increased the composite density in a highly nonlinear manner, which suggested interaction between the polypropylene and the carbon nanotubes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2926–2933, 2004     

Evaluation of improvement of physical and mechanical properties of bamboo fibers due to alkali treatment

Bamboo strips treated with caustic solutions of different concentrations, e.g., 5%, 10%, 15%, 20%, 25%, and 50%, were subjected to mechanical testing giving stresses on tensile strength, percent elongation at break, flexural strength, flexural modulus, and toughness. The change in average density was ?15%, and the weight loss value shows a maximum of 21.94% at 50% alkali treatment. The mechanical properties of bamboo strips increase steadily with increasing concentration of caustic soda, showing a comparable increased value at 15 and 20%, and then exhibiting a gradual fall. The percent elongation at break corroborates these observations showing a continuous decreasing trend. The properties under investigation exhibit a clear transition in between 15 and 20% alkali concentration. The morphology of strips was studied by scanning electron microscope and polarizing light microscope. The crystal structure of both untreated and treated strips was compared by XRD analysis. In both cases, the breakdown of the crystal structures of the cellulose fibers and the recrystallization or reorientation of the degraded chains that are devoid of hemicellulose are quite apparent. However, at a very high concentration (to the extent of 25%) the breakdown of structure predominates much more over the reorientation or recrystallization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tensile strength and its variation of PAN‐based carbon fibers. I. Statistical distribution and volume dependence

The effects of the diameter, gauge length, and volume of carbon fibers on the tensile properties and their variation are discussed on the basis of the weak‐link theory and Weibull distribution in a single‐filament test. As far as variation is concerned, the stress of carbon fibers should be obtained by the division of the force not by the mean cross section of all the fibers but by the cross section of individual fibers because of the diameter variation. The volume effect of carbon fibers influences not only the mean of the tensile properties but also their variation. The experimental results indicate that the volume dependence in the radial direction is much bigger than that in the axial direction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3175–3182, 2006     

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.     

Structure–property relationship of polyimide fibers containing ether groups

The copolyimide (co‐PI) fibers with outstanding mechanical properties were prepared by a two‐step wet‐spinning method, derived from the design of combining 4,4′‐oxydianiline (ODA) with the rigid 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA)/p‐phenylenediamine (p‐PDA) backbone. The mechanical properties of PI fibers were drastically improved with the optimum tensile strength of 2.53 GPa at a p‐PDA/ODA molar ratio of 5/5, which was approximately 3.7 times the tensile strength of BPDA/p‐PDA PI fibers. Two‐dimensional wide‐angle X‐ray diffraction indicated that the highly oriented structures were formed in the fibers. Two‐dimensional small‐angle X‐ray scattering revealed the existence of the needle‐shaped microvoids aligned parallel to the fiber axis, and the introduction of ODA led to the reduction in the size of the microvoids. As a result, the significantly improved mechanical properties of PI fibers were mainly attributed to the gradually formed homogeneous structures. The co‐PI fibers also exhibited excellent thermal stabilities of up to 563°C in nitrogen and 536°C in air for a 5% weight loss and glass transition temperatures above 279°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42474.     

Effect of the concentration of the sizing agent on the carbon fibers surface and interface properties of its composites

The effect of the concentration of the sizing agent on performances of carbon fiber and carbon fiber composites has been investigated. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were applied to characterize carbon fiber surface topographies. At the same time, the single fiber strengths and Weibull distribution were also studied. The interlaminar shear strength and hygrothermal ageing test have been used to study the effect of fiber coatings on the interface of the composites. The analysis of the results shows that the sizing level is essential for improving the surface of carbon fibers and its composite performance. Different concentrations of the sizing agent have different contributions to the wetting performance of carbon fibers. Among the three concentrations of sizing agent studied (1 wt %, 1.5 wt %, and 2 wt %), the optimal sizing level is 1.5 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 125:425–432, 2011     

Polyacrylonitrile based carbon fibers: Spinning technology dependent precursor fiber structure and its successive transformation

In this study, the effects of different spinning methods including traditional wet and dry-jet wet spinning, and newly developed dry-jet gel spinning, on the structures and performances of polyacrylonitrile fibers, as well as the structural evolution during stabilization and carbonization, are compared in detail. The structural differences along radial direction, surface roughness, and chain orientation of carbon fibers are inherited from their precursor fibers, and these factors are determined by spinning technologies and processing conditions. Among all spinning methods, dry-jet gel spinning could prepare fibers with the best chain orientation, the highest tensile properties, and the lowest surface roughness, which would be favorable for achieving higher mechanical performance. Additionally, for the resultant carbon fibers, the surface modification of dry-jet gel spun carbon fibers is easier than dry-jet wet spun carbon fibers, and comparable to wet spun carbon fibers. Overall, dry-jet gel spinning is promising to make carbon fibers with both excellent tensile properties and good interfacial adhesion with epoxy matrix.     

Morphological and local mechanical surface characterization of ballistic fibers via AFM

As‐received morphologies, defect structures, and contact moduli of Kevlar KM2 Plus and three other ballistic fibers varying in chemistry and processing, were observed and compared using atomic force microscopy (AFM) and instrumented nanoindentation (NI) techniques. Surface features and defects were defined and measured for each fiber chemistry: p‐phenylene terephthalamides (PPTA including KM2 Plus and Twaron), co‐polymer aramid (AuTx), and ultra high molecular weight polyethylene (UHMWPE including Dyneema). Although a multitude of surface defects were observed in each fiber, the types of defects were similar from one fiber type to another. It was found that surface defects generally map to a more compliant local modulus value. Contact modulus values were compared with NI elastic modulus values to demonstrate validity for the AFM technique. Challenges and limitations of the AFM technique for cataloging defects are discussed. This study is the first which attempts to outline the various morphologies found on several fiber surfaces. These local property studies will enable future comparisons with single filament and bulk fiber properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40880.