Nanofibers with several hundred of nanometers were successfully fabricated using electrospinning process and a mixture of two types of polymers which are: polydimethylsiloxane and polyacrylonitrile as precursors. After stabilization and carbonization at 1000 °C, three phases which are: silicon carbide (SiC), carbon, and oxy‐SiC were presented. Spectroscopic and microscopic techniques had confirmed the presence of nanocrystalline SiC and turbostratic carbons. These phases formed an intertwined network at the nanometric scale. In addition, the resulted fibers showed a core‐skin effect with skin richer in carbon and a core mainly dominated by silicon‐based phases in the form SiC or SiOC ceramics. A significant improvement was observed in both tensile strength and elastic modulus in these hybrid fibers. In term of crystallography, these nanofibers seem to exhibit similar microstructure that was observed in Nicalon fiber. However, it was difficult to determine the ratio of these phases and their influence on the physical properties of these hybrid fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45967.
Lignin macromolecules are potential precursor materials for producing electrospun nanofibers for composite applications. However, little is known about the effect of lignin type and blend ratios with synthetic polymers. This study analyzed blends of poly(acrylonitrile-co-methyl acrylate) (PAN-MA) with two types of commercially available lignin, low sulfonate (LSL) and alkali, kraft lignin (AL), in DMF solvent. The electrospinning and polymer blend solution conditions were optimized to produce thermally stable, smooth lignin-based nanofibers with total polymer content of up to 20 wt % in solution and a 50/50 blend weight ratio. Microscopy studies revealed that AL blends possess good solubility, miscibility, and dispersibility compared to LSL blends. Despite the lignin content or type, rheological studies demonstrated that PAN-MA concentration in solution dictated the blend’s viscosity. Smooth electrospun nanofibers were fabricated using AL depending upon the total polymer content and blend ratio. AL’s addition to PAN-MA did not affect the glass transition or degradation temperatures of the nanofibers compared to neat PAN-MA. We confirmed the presence of each lignin type within PAN-MA nanofibers through infrared spectroscopy. PAN-MA/AL nanofibers possessed similar morphological and thermal properties as PAN-MA; thus, these lignin-based nanofibers can replace PAN in future applications, including production of carbon fibers and supercapacitors.
Investigation of three preceramic polymer formulations for potential use in additive manufacturing technologies.
A novel route to fabricating hybrid ceramic matrix composites has been developed. The fabrication is based on the unique combination of additive manufacturing (AM), a preceramic polymer, and a chopped carbon fiber precursor. After introducing the photoinitiator to the preceramic polymer formulation, a photosensitive resin was introduced. The resulting resin was loaded with distinct weight percentages of stabilized polyacrylonitrile nanofiber-the carbon fiber precursor. These formulations were 3D printed, cured, and converted to ceramic phases using a pyrolysis cycle. The end objective of the pyrolysis cycle is the conversion of the polycarbosilane resin into a silicon carbide matrix and the transformation of the PAN polymer into reinforcing carbon nanofibers within one cycle. The results of this work showed that ceramic matrix composite components can be successfully fabricated using a suitable combination of 3D printing, resin formulation, and processing cycle. The pyrolyzed ceramic hybrid composite was fully dense with nearly linear shrinkage and a shiny, smooth surface.Approximately 60% retained weight after pyrolysis to 1350 • C was confirmed by thermogravimetric analysis. In terms of crystallography, the ceramic matrix composite displayed three coexisting phases including silicon carbide, silicon oxycarbide, and turbostratic carbon. The results showed this combination of material and processes has a high potential for fabricating hybrid composites with hightemperature performance and improved mechanical properties combined with complex geometries.
The properties of ceramic materials are dependent on crystal sizes and their distribution. These parameters can be controlled using electrospinning of the two-phase mixed system. The preceramic solution consists of silicon nanoparticles and polyacrylonitrile (PAN) polymer mixture. Particle distribution during the electrospinning technique was characterized using transmission electron microscopy and modeled using the finite element method. The experimental and numerical results were in agreement. Large silicon particles were located in the skin and the smaller ones were located at the core. This was illustrated by the migration rate from the core, which was the fastest for large particles and diminished as the particles become smaller in size. The threshold for Stokes number was found to be around 2.2 × 10 with a critical particle size of 1.0 × 10 m in diameter. The current results are very promising, as it demonstrated a novel way for the fabrication of PAN/Si ceramic nanofibers with a gradient of particle size and properties from the skin to the core.
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