Fiber Spinning Process Research Articles

Mussel-Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity.

Inspired by mussel adhesive polydopamine (PDA), effective reinforcement of graphene-based liquid crystalline fibers to attain high mechanical and electrical properties simultaneously is presented. The two-step defect engineering, relying on bioinspired surface polymerization and subsequent solution infiltration of PDA, addresses the intrinsic limitation of graphene fibers arising from the folding and wrinkling of graphene layers during the fiber-spinning process. For a clear understanding of the mechanism of PDA-induced defect engineering, interfacial adhesion between graphene oxide sheets is straightforwardly analyzed by the atomic force microscopy pull-off test. Subsequently, PDA could be converted into an N-doped graphitic layer within the fiber structure by a mild thermal treatment such that mechanically strong fibers could be obtained without sacrificing electrical conductivity. Bioinspired graphene-based fiber holds great promise for a wide range of applications, including flexible electronics, multifunctional textiles, and wearable sensors.

Stability analysis of non-isothermal fibre spinning of polymeric solutions

The stability of fibre spinning flow of a polymeric fluid is analysed in the presence of thermal effects. The spinline is modelled as a one-dimensional slender-body filament of the entangled polymer solution. The previous study (Gupta & Chokshi,J. Fluid Mech., vol. 776, 2015, pp. 268–289) analysed linear and nonlinear stability behaviour of an isothermal extensional flow in the air gap during the fibre spinning process. The present study extends the analysis to take in to account the non-isothermal spinning flow in which the spinline loses heat by convection to the surrounding air as well as by solvent evaporation. The nonlinear rheology of the polymer solution is described using the eXtended Pom-Pom (XPP) model. The non-isothermal effects influence the rheology of the fluid through viscosity, which is taken to be temperature and concentration dependent. The linear stability analysis is carried out to obtain the draw ratio for the onset of instability, known as the draw resonance, and a stability diagram is constructed in the$DR_{c}{-}De$plane.$DR_{c}$is the critical draw ratio, and$De$is the flow Deborah number. The enhancement in viscosity driven by spinline cooling leads to postponement in the onset of draw resonance, indicating the stabilising role of non-isothermal effects. Weakly nonlinear stability analysis is also performed to reveal the role of nonlinearities in the finite amplitude manifold in the vicinity of the flow transition point. For low to moderate Deborah numbers, the bifurcation is supercritical, and the flow attains an oscillatory state with an equilibrium amplitude post-transition when$DR>DR_{c}$. The equilibrium amplitude of the resonating state is found to be smaller when non-isothermal effects are incorporated in comparison to the isothermal spinning flow. For very fast flows in the regime of high Deborah numbers, the finite amplitude manifold crosses over to a subcritical state. In this limit, the nonlinearities render the flow unstable even in the linearly stable regime of$DR<DR_{c}$.

Aquatic caddisworm silk is solidified by environmental metal ions during the natural fiber-spinning process.

Aquatic caddisfly larvae (caddisworms) wet-spin fibers to construct composite cases of silk and stone. The silk emerges from labial ducts as a nanofibrous fluid gel, flowing over the stone substrate and making intimate interfacial adhesive contacts before being drawn into tough fibers that rapidly solidify underwater to span gaps in the construction. Divalent metal ions are responsible for the unique mechanical properties of naturally spun silk fibers; however, when and where divalent metal ions are incorporated into the metallofibers and other aspects of the fiber solidification mechanism are poorly understood. To investigate, the elemental composition and secondary structure of silk precursors stored in the silk gland lumen were compared with naturally spun fibers by inductively coupled plasma optical emission spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. Naturally spun fibers contained near equimolar ratios of Ca2+ to P. In contrast, silk precursors stored in the silk gland lumen contained only traces of Ca2+ and other multivalent metal ions. Ca2+ was also undetectable in anterior lumenal silk using the histochemical Ca2+ indicator, alizarin S red. Addition of Ca2+ to isolated lumenal silk resulted in Ca2+ complexation by H-fibroin phosphoserines (pSs) and a shift in secondary structure from random coils to β-structures, creating infrared spectra in the phosphate and amide I regions nearly equivalent to those found in naturally spun Ca2+-containing silk fibers. Light and electron microscopy within distinct regions of the silk gland suggested that posterior gland silk colloidal complexes transition into a nanofibrous morphology as they pass into the chitin-lined anterior lumen. Altogether, the results suggest that environmental Ca2+ absorbed from natural water triggers silk fiber solidification postdraw by complexing H-fibroin pSs, creating Ca2+-stabilized crystalline β-nanodomains that cross-link and toughen the freshly drawn silk fibers.-Ashton, N. N., Stewart, R. J. Aquatic caddisworm silk is solidified by environmental metal ions during the natural fiber-spinning process.

Fabrication of Hierarchical V2O5 Nanorods on TiO2 Nanofibers and Their Enhanced Photocatalytic Activity under Visible Light

AbstractWe report photocatalytic activities of a set of mesoporous, hierarchical “nanorods‐on‐nanofiber” heterostructures produced from the organization of vanadium pentoxide (V2O5) nanorods on titanium dioxide (TiO2) nanofibers fabricated using gas jet fiber (GJF) spinning process. The precursor nanofibers spun from solutions of poly(vinylpyrrolidone), titanium tetraisopropoxide, and vanadium oxytriisopropoxide are calcined at 500–600 °C in air to yield the above hierarchical nanostructures. The calcination temperature and the composition of the spinning solutions are used as factors to obtain different sizes of the nanorods, nanofibers, and the crystallites. Photocatalytic oxidation of gas‐phase ethanol on the heterostructures under visible light at room temperature is studied. The materials calcined at 500 °C show oxidation of ethanol into carbon dioxide and water with about three orders of magnitude higher rate than single‐component V2O5 nanofibers and reference material V2O5 powder. The higher photocatalytic activity is attributed to the slowdown of the electron–hole charge recombination phenomena in the heterostructures as inferred from photoluminescence study. The heterostructure V2O5–TiO2 photocatalyst can be easily regenerated without sacrificing any photocatalytic performance.

Combination of Amorphous Silk Fiber Spinning and Postspinning Crystallization for Tough Regenerated Silk Fibers.

An artificial spinning system using regenerated silk fibroin solutions is adopted to produce high-performance silk fibers. In previous studies, alcohol-based agents, such as methanol or ethanol, were used to coagulate silk dope solutions, producing silk fiber with poor mechanical properties compared with those of native silk fibers. The alcohol-based coagulation agents induce rapid β-sheet crystallization of the silk molecules, which inhibits subsequent alignment of the β-sheet crystals. Here, we induce gradual β-sheet formation to afford adequate β-sheet alignment similar to that of native silk fiber. To this aim, we developed an amorphous silk fiber spinning process that prevents fast β-sheet formation in silk molecules by using tetrahydrofuran (THF) as a coagulation solvent. In addition, we apply postdrawing to the predominantly amorphous silk fibers to induce β-sheet formation and orientation. The resultant silk fibers showed a 2.5-fold higher extensibility, resulting in 1.5-fold tougher silk fibers compared with native Bombyx mori silk fiber. The amorphous silk fiber spinning process developed here will pave the way to the production of silk fibers with desired mechanical properties.

Preparation of carrageenan fibers with extraction of Chondrus via wet spinning process

Traditionally, the carrageenan fibers were prepared by process of extracting, drying, dissolving of carrageenan power and wet spinning process of fibers. However, in this study, carrageenan fibers were prepared by carrageenan solution directly from the extraction of Chondrus, without the steps of precipitation, and drying. The properties of carrageenan powder, spinning solution and carrageenan fibers were characterized with zeta potential, NMR, FTIR, dynamic light scattering (DLS), SEM, tensile testing and energy dispersive spectrometer (EDS). The results showed that the Chondrus contained mainly iota-carrageenan. The extraction of Chondrus was a uniform liquid with good properties of a solution, which was suitable as a spinning solution. The so prepared carrageenan fibers possessed good morphology and tensile properties. The excellent tensile properties of the carrageenan fibers were attributed to the combination of sulfate ester in the carrageenan and barium ions in the coagulation and then form a three-dimensional network structure.

Preparation and evaluation of isotropic and mesophase pitch-based carbon fibers using the pelletizing and continuous spinning process

The purpose of this study is to investigate the potential of using a pelletized pitch in a continuous process for the economical preparation of large-scale pitch-based carbon fibers. The pitch was pelletized before spinning because the pitch powder can agglomerate in the feed throat of a screw extruder, which can render uniform heating difficult. Using the pelletized pitch in a single-screw extruder spinning apparatus, the pitch fiber can be spun to a great length as long as the amount of pitch pellets is sufficient. To evaluate the benefits of using pitch pellets in the continuous carbon fiber spinning process, isotropic and mesophase pitch fibers were prepared by both the conventional batch process using pitch powder and continuous process using pitch pellets. Even with a huge difference in the thermal energy used, the carbon fibers prepared using the pelletized-pitch-based continuous process had better tensile properties than those prepared using the conventional process. This suggests that the continuous process using pitch pellets has the potential to be an economical large-scale process for carbon fiber preparation.

Analyses of closed porosity of carbon fiber precursors using a robust thermoporosimetric method

We investigated a major fiber spinning process parameter, the coagulation bath concentration, which has a critical effect on the porosity of the polyacrylonitrile (PAN) fibers. Utilizing thermoporosimetry, a calorimetric method based on the Gibbs–Thomson effect, this work details the correlation between coagulation bath concentration, porosity and pore size distribution. Pore size, as well as the pore size distribution, of the fibers throughout the wet spinning process were determined in detail. Moreover, the changes in the number of porous zones, pore size and fiber morphology during the wet spinning process were also examined by changing the coagulation bath composition. Two coagulation bath compositions, 77.5 wt% and 80 wt% DMAc/deionized water were considered. The fibers spun at 80 wt% coagulation bath solvent concentration displayed skinless rough surfaces with high porosity values compared to the fibers spun at 77.5 wt%. Attempts to spin into slightly more concentrated DMAc baths were unstable due to reduced tow tenacity, leading to fiber failure. The study showed that even minor changes in the coagulation bath composition can have a pronounced effect on the fiber properties such as cross-sectional shape, the integrity of the external skin, and the number and size of pores.

Stability analysis of bilayer polymer fiber spinning process

The linear stability of a bilayer fiber spinning process is analyzed for axisymmetric disturbances under isothermal conditions. The co-extruded fiber consists of two concentric layers of rheologically stratified polymeric fluids. While the core fluid is an entangled polymer melt described using the eXtended Pom-Pom (XPP) model, the sheath layer is a low molecular weight unentangled polymer modeled as an Upper Convected Maxwell (UCM) fluid. The analysis indicates that, for fast extensional flows, such an arrangement enhances the critical draw ratio of the process over that found from the spinning of XPP fluid alone, thus delaying the onset of draw resonance and stabilizing the system. Further, the range of flow Deborah number for stable spinning is found to be much broader than that for the UCM fluid alone. For low to moderately elastic flows, the stability behavior is governed mainly by the rheology of the more-elastic core layer (XPP fluid), whereas for the highly elastic flows, the stability behavior is dominated by the less-elastic sheath layer (UCM fluid). The sensitivity of the stability diagram with respect to various spinning flow parameters, like the relative fraction of core and sheath layers, the rheological stratification of two fluids, and the spine-line dimensions, has also been examined in order to identify the region of enhanced stability such that the draw resonance is suppressed.

Investigation of rheology and morphology to follow physical fibrillar network evolution through fiber spinning of PP/PA6 blend fiber

This work is aimed at investigating the influence of fibrillar morphology of deformed Polyamide 6 (PA6) droplets dispersed in Polypropylene (PP) matrix on the melt viscoelastic behavior of their blends. The blends of PP with various amounts of PA6 (1%, 6%, 10%, and 20%) were prepared by melt mixing in a co‐rotating twin screw extruder and fibrillated by fiber spinning process. Scanning Electron Microscopy revealed that the PA6 spherical droplets form fibrillar inclusions after fiber spinning. The steady and transient shear rheological responses of samples were evaluated in both linear and nonlinear ranges of deformation. Non‐terminal behavior of storage modulus at low frequency appeared as a typical characteristic of fibrillar morphology whose width and value depend on fibril growth. Storage modulus and complex viscosity of the blends containing PA6 fibrillated structure were remarkably enhanced compared to as‐extruded samples. The fibrillar‐induced elasticity of the fibers is a distinguishable behavior which was revealed by conducting transient stress and creep‐recovery measurements and upon appearing mature fibrils, elasticity of the polymer blend fibers increased significantly. POLYM. ENG. SCI., 58:1251–1260, 2018. © 2017 Society of Plastics Engineers

Non-terminal behavior as a finger print to follow droplet deformation

It is well-established that rheology can trace structural dynamics and conjectures the forming/formed morphology. The objective of this work is to trace the droplet deformation via conducting fiber spinning process. In this regard, two types of polymer blends Polypropylene (PP)/Polyamide6 (PA6) and Polypropylene/Polytrimethylene terephthalate (PTT) with various ratios (99/1, 94/6, 90/10, and 80/20) were melt-blended on co-rotating twin screw extruder and thereafter, were spun. Scanning electron microscopy (SEM) images represent a droplet and fibrillar morphologies for as-extruded samples and spun blend fibers respectively. Unlike PA6 as dispersed phase, PTT droplets in PP/PTT blend system shows improved spinnability. Linear melt viscoelastic data were gathered by performing rheological approaches in linear region. Conducting frequency sweep at 240°C is revealed a terminal behavior for Gʹ and a Newtonian plateau for η* at low frequencies. However, at 195°C dynamic rheological data pertinent to fibers represent a non-terminal trend for Gʹ and viscosity upturn at low frequencies respectively. These distinguishable characteristics can be considered as spinnability of droplets which reflect fibrillation mechanism, and fibrillar growth can be followed by scanning the viscoelastic responses at low frequency region which enhanced upon fibril growth. According to SEM and rheological test results, PTT, as an engineering plastics, manifests higher capability of forming nano fibrils.

Cellulose Aerogel Fibres for Thermal Encapsulation of Diesel Hybrid Engines for Fuel Savings in Cars

A Cellulose Aerogel fibre spinning process was investigated based on coagulation of a spinning dope out of aqueous zinc chloride salt hydrate melts into different coagulants. It has been shown that coagulants with less solubility of zinc chloride are more suitable for the production of fibres. The lower the solubility of zinc chloride the slower is the diffusion from the gel fibre into the coagulant. It has been shown that to fast diffusion is contra productive to the fibre strength. Therefore conditions with low diffusion rates are favorable to increase the mechanical properties of aerogel fibres. The fibres were supercritical dried and investigated due to their inner surface with BET analysis, pore structure via SEM images and mechanical properties. The described aerogel fibre synthesis is a promising step to the encapsulation of combustion engines with drapable aerogel structures to supress the cooling of hybrid cars during urban driving. It has been shown that this bears the potential of increasing the efficiency of hybrid engines and decreasing the amount of emissions during driving.

Use of Rheological Characteristics of Viscoelastic Polymer Systems to Optimize the Fiber-Spinning Process

The rheological characteristics (complex viscosity, equilibrium relaxation time, equilibrium shear modulus) of a viscoelastic spinning solution obtained in a viscometer and under actual fiber-spinning conditions are examined. It is shown that the optimal regimes for spinning stronger fibers could be predicted by using the spinning-solution rheological characteristics and correlation coefficients obtained in a viscometer.

Anisotropic Conjugated Polymer Chain Conformation Tailors the Energy Migration in Nanofibers.

Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. Although the packing of the conjugated chains in the solid state is known to be a key factor to tailor the electronic energy transfer and the resulting optical properties, most of the current solution-based processing methods do not allow for effectively controlling the molecular order, thus making the full unveiling of energy transfer mechanisms very complex. Here we report on conjugated polymer fibers with tailored internal molecular order, leading to a significant enhancement of the emission quantum yield. Steady state and femtosecond time-resolved polarized spectroscopies evidence that excitation is directed toward those chromophores oriented along the fiber axis, on a typical time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties.

Orientation of Graphene Nanoplatelets in Thermosetting Matrices

A simple procedure for the alignment of graphene nanoplatelets (GNPs) in a thermosetting matrix is presented. First, the alignment of GNPs in thermoplastic fibers of amorphous polyetylene terephthalate (aPET) is achieved by a fiber spinning process. The nanocomposite fibers, obtained with a very high filler content (10 wt%), are then transferred into a reactive epoxy resin. After dissolution of aPET, the nanofillers remained oriented in the thermosetting matrix. The characterization of the obtained nanocomposites has been carried by means of different experimental techniques which provided complementary results. The proposed method has the potential to be used in the manufacturing of hierarchical composites, by introducing nanofilled microfibers into continuous fibers reinforced composites.

High Modulus Regenerated Cellulose Fibers Spun from a Low Molecular Weight Microcrystalline Cellulose Solution

We have developed a novel process to convert low molecular weight microcrystalline cellulose into stiff regenerated cellulose fibers using a dry-jet wet fiber spinning process. Highly aligned cellulose fibers were spun from optically anisotropic microcrystalline cellulose/1-ethyl-3-methylimidazolium diethyl phosphate (EMImDEP) solutions. As the cellulose concentration increased from 7.6 to 12.4 wt %, the solution texture changed from completely isotropic to weakly nematic. Higher concentration solutions (>15 wt %) showed strongly optically anisotropic patterns, with clearing temperatures ranging from 80 to 90 °C. Cellulose fibers were spun from 12.4, 15.2, and 18.0 wt % cellulose solutions. The physical properties of these fibers were studied by scanning electron microscopy (SEM), wide angle X-ray diffraction (WAXD), and tensile testing. The 18.0 wt % cellulose fibers, with an average diameter of ∼20 μm, possessed a high Young’s modulus up to ∼22 GPa, moderately high tensile strength of ∼305 MPa, as well ...

Mesoporous Titanium Dioxide Nanofibers with a Significantly Enhanced Photocatalytic Activity

AbstractMesoporous TiO2 nanofibers with controlled diameter, crystal size, and anatase versus rutile crystal structures are produced by calcination at 500–700 °C of precursor nanofibers of polyvinylpyrrolidone and titanium isopropoxide, obtained from a scalable gas jet fiber spinning process. These TiO2 nanofibers are used in the photocatalytic oxidation of gas‐phase ethanol at room temperature on exposure to UV irradiation. The experimental trends are analyzed using electron–hole (e‐h) charge recombination inferred from high‐intensity photoluminescence emission spectra, specific surface area, crystallinity, and the proportions of anatase and rutile phases. The nanofibers show a photocatalytic activity that is up to an order of magnitude higher than that of commercial‐grade P25 TiO2 nanoparticles because of slower e‐h recombination phenomena in the former. The results show that ethanol undergoes complete oxidation into CO2 and H2O on the nanofibers without the accumulation of the intermediate products acetaldehyde and formic acid.

Asymptotics and numerics for the upper-convected Maxwell model describing transient curved viscoelastic jets

This work deals with the modeling and simulation of non-Newtonian jet dynamics as it occurs in fiber spinning processes. Proceeding from a three-dimensional instationary boundary value problem of upper-convected Maxwell equations, we present a strict systematic derivation of a one-dimensional viscoelastic string model by using asymptotic analysis in the slenderness ratio of the jet. The model allows for the unrestricted motion and shape of the jet’s curve, and its deduction extends the hitherto existing uniaxial asymptotic approaches. However, the system of partial differential equations with algebraic constraint has a varying character (hyperbolic, hyperbolic–elliptic, parabolic deficiency). Its applicability range turns out to be limited depending on the physical parameters and the boundary conditions (i.e. singular perturbation). Numerical results are discussed for the hyperbolic regime of gravitational inflow–outflow set-ups which become relevant in drawing and extrusion processes. The simulations are performed with a normal form total upwind scheme in space and an implicit time-integration ensuring convergence of first order.

Towards the Knittability of Graphene Oxide Fibres.

Recent developments in graphene oxide fibre (GO) processing include exciting demonstrations of hand woven textile structures. However, it is uncertain whether the fibres produced can meet the processing requirements of conventional textile manufacturing. This work reports for the first time the production of highly flexible and tough GO fibres that can be knitted using textile machinery. The GO fibres are made by using a dry-jet wet-spinning method, which allows drawing of the spinning solution (the GO dispersion) in several stages of the fibre spinning process. The coagulation composition and spinning conditions are evaluated in detail, which led to the production of densely packed fibres with near-circular cross-sections and highly ordered GO domains. The results are knittable GO fibres with Young’s modulus of ~7.9 GPa, tensile strength of ~135.8 MPa, breaking strain of ~5.9%, and toughness of ~5.7 MJ m−3. The combination of suitable spinning method, coagulation composition, and spinning conditions led to GO fibres with remarkable toughness; the key factor in their successful knitting. This work highlights important progress in realising the full potential of GO fibres as a new class of textile.

Role of humidity on the structures and properties of regenerated silk fibers

Silk fiber was processed from highly concentrated spinning dope to solid fibers along with water removal. To understand the mechanism of water removal during silk fiber spinning process, a microfluidic chip was designed and applied to investigate the structures and mechanical properties of two kinds of regenerated silk fibroin fibers dry-spun at different relative humidity. The experimental results showed that the diameters of the fibers spun at 40% RH are always larger than the fibers spun at 50% RH due to different removal rates of water. The fibers spun at low humidity contain more β-sheet structure and lower degree of chain orientation and crystalline orientation. These results indicate that the fast phase transition of silk fibroin from sol–gel to silk fiber undergoes with rapid water removal and higher fiber orientation relates to more residue water and drawing force.