skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Rheology of Polyacrylonitrile/Lignin Blends in Ionic Liquids under Melt Spinning Conditions
Lignin, while economically and environmentally beneficial, has had limited success in use in reinforcing carbon fibers due to harmful chemicals used in biomass pretreatment along with the limited physical interactions between lignin and polyacrylonitrile (PAN) during the spinning process. The focus of this study is to use lignin obtained from chemical-free oxidative biomass pretreatment (WEx) for blending with PAN at melt spinning conditions to produce carbon fiber precursors. In this study, the dynamic rheology of blending PAN with biorefinery lignin obtained from the WEx process is investigated with the addition of 1-butyl-3-methylimidazolium chloride as a plasticizer to address the current barriers of developing PAN/lignin carbon fiber precursors in the melt-spinning process. Lignin was esterified using butyric anhydride to reduce its hydrophilicity and to enhance its interactions with PAN. The studies indicate that butyration of the lignin (BL) increased non-Newtonian behavior and decreased thermo-reversibility of blends. The slope of the Han plot was found to be around 1.47 for PAN at 150 °C and decreased with increasing lignin concentrations as well as temperature. However, these blends were found to have higher elasticity and solution yield stress (47.6 Pa at 20%wt BL and 190 °C) when compared to pure PAN (5.8 Pa at 190 °C). The results from this study are significant for understanding lignin–PAN interactions during melt spinning for lower-cost carbon fibers.  more » « less
Award ID(s):
1738669
PAR ID:
10174441
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Molecules
Volume:
24
Issue:
14
ISSN:
1420-3049
Page Range / eLocation ID:
2650
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Biomass conversion to alcohols using supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHO) with CuMgAl mixed metal oxide is a promising process for biofuel production. We demonstrate how maple wood can be converted at high weight loadings and product concentrations in a batch and a semi-continuous reactor to a mixture of C 2 –C 10 linear and cyclic alcohols. Maple wood was solubilized semi-continuously in supercritical methanol and then converted to a mixture of C 2 –C 9 alcohols and aromatics over a packed bed of CuMgAlO x catalyst. Up to 95 wt% of maple wood can be solubilized in the methanol by using four temperature holds at 190, 230, 300, and 330 °C. Lignin was solubilized at 190 and 230 °C to a mixture of monomers, dimers, and trimers while hemicellulose and cellulose solubilized at 300 and 330 °C to a mixture of oligomeric sugars and liquefaction products. The hemicellulose, cellulose, and lignin were converted to C 2 –C 10 alcohol fuel precursors over a packed bed of CuMgAlO x catalyst with 70–80% carbon yield of the entire maple wood. The methanol reforming activity of the catalyst decreased by 25% over four beds of biomass, which corresponds to 5 turnovers for the catalyst, but was regenerable after calcination and reduction. In batch reactions, maple wood was converted at 10 wt% in methanol with 93% carbon yield to liquid products. The product concentration can be increased to 20 wt% by partially replacing the methanol with liquid products. The yield of alcohols in the semi-continuous reactor was approximately 30% lower than in batch reactions likely due to degradation of lignin and cellulose during solubilization. These results show that solubilization of whole biomass can be separated from catalytic conversion of the intermediates while still achieving a high yield of products. However, close contact of the catalyst and the biomass during solubilization is critical to achieve the highest yields and concentration of products. 
    more » « less
  2. The research investigates the thermal behavior of mixed systems based on natural and artificial cellulose fibers used as precursors for carbon nonwoven materials. Flax and hemp fibers were employed as natural components; they were first chemically treated to remove impurities and enriched with alpha-cellulose. The structure, chemical composition, and mechanical properties of both natural and viscose fibers were studied. It was shown that fiber properties depend on the fiber production process history; natural fibers are characterized by a high content of impurities and exhibit high strength characteristics, whereas viscose fibers have greater deformation properties. The thermal behavior of blended compositions was investigated using TGA and DSC methods across a wide range of component ratios. Carbon yield values at 1000 °C were found to be lower for blended systems containing 10–40% by weight of bast fibers, with carbon yield increasing as the quantity of natural fibers increased. Thus, the composition of the cellulose composite affects carbon yield and thermal processes in the system. Using the Kissinger method, data were obtained on the value of the activation energy of thermal decomposition for various cellulose and composite systems. It was found that natural fiber systems have three-times higher activation energy than viscose fiber systems, indicating their greater thermal stability. Blends of natural and artificial fibers combine the benefits of both precursors, enabling the deliberate regulation of thermal behavior and carbon material yield. This approach opens up prospects for the creation of functional carbon materials used in various high-tech areas, including thermal insulation. 
    more » « less
  3. null (Ed.)
    Carbon nanotube (CNT)‐reinforced polymer fibers have broad applications in electrical, thermal, optical, and smart applications. The key for mechanically robust fibers is the precise microstructural control of these CNTs, including their location, dispersion, and orientation. A new methodology is presented here that combines dry‐jet‐wet spinning and forced assembly for scalable fabrication of fiber composites, consisting of alternating layers of polyacrylonitrile (PAN) and CNT/PAN. The thickness of each layer is controlled during the multiplication process, with resolutions down to the nanometer scale. The introduction of alternating layers facilitates the quality of CNT dispersion due to nanoscale confinement, and at the same time, enhances their orientation due to shear stress generated at each layer interface. In a demonstration example, with 0.5 wt% CNTs loading and the inclusion of 170 nm thick layers, a composite fiber shows a significant mechanical enhancement, namely, a 46.4% increase in modulus and a 39.5% increase in strength compared to a pure PAN fiber. Beyond mechanical reinforcement, the presented fabrication method is expected to have enormous potential for scalable fabrication of polymer nanocomposites with complex structural features for versatile applications. 
    more » « less
  4. Carbon fibers (CFs) are an important engineering material due to their superior mechanical, electrical, and thermal properties. Majority of them are produced from the thermal conversion of polyacrylonitrile (PAN)-based fibers. In order to promote the CF manufacturing speed and offer the possibility to control the microstructure of the fibers, an alternative technology for carbonization of stabilized PAN fiber are explored by laser processing technology. In this work, we investigated the relationship between the laser process and the properties of fibers. Laser irradiation introduces the structural changes in the stabilized PAN fibers. The appearance of D band and G band in Raman spectrum verifies the existence of graphite structures in the laser scanned fibers. The characteristic peaks in FTIR disappear when the high laser energy condition is engaged, which indicates diminishing of non-carbon bonds. Laser treatment also introduces an obvious shrinkage in fiber diameter. The condition of laser irradiation could influence the electrical and mechanical properties of fibers. A new approach to convert stabilized PAN fiber into carbon fiber was demonstrated. 
    more » « less
  5. High performance carbon fibers are widely used as fiber reinforcements in composite material systems for aerospace, automotive, and defense applications. Longitudinal tensile failure of such composite systems is a result of clustering of single fiber tensile failures occurring at the microscale, on the order of a few microns to a few hundred microns. Since fiber tensile strength at the microscale has a first order effect on composite strength, it is important to characterize the strength of single fibers at microscale gage lengths which is extremely challenging. An experimental technique based on a combination of transverse loading of single fibers under SEM with DIC is a potential approach to access microscale gage lengths. The SEM-DIC technique requires creation of uniform, random, and contrastive sub-microscale speckle pattern on the curved fiber surface for accurate strain measurements. In this paper, we investigate the formation of such sub-microscale speckle patterns on individual sized IM7 carbon fibers of nominal diameter 5.2 µm via sputter coating. Various process conditions such as working pressure, sputtering current, and coating duration are investigated for pattern creation on fiber surface using a gold-palladium (Au-Pd) target. A nanocluster type sub-microscale pattern is obtained on the fiber surface for different coating conditions. Numerical translation experiments are performed using the obtained patterns to study image correlation and identify a suitable pattern for SEM-DIC experiments. The pattern obtained at a working pressure of 120–140 mTorr with 50 mA current for a duration of 10 min is found to have an average speckle size of 53 nm and good contrast for image correlation. Rigid body translation SEM experiments for drift/distortion correction using a sized IM7 carbon fiber coated with the best patterning conditions showed that Stereo-SEM-DIC is needed for accurately characterizing fiber strain fields due to its curved surface. The effect of sputter coating on fiber tensile strength and strain is investigated via single fiber tensile tests. Results showed that there is no significant difference in the mean tensile strength and failure strain between uncoated and coated fibers (average increment in fiber diameter of ∼221 nm due to coating) at 5% significance level. SEM images of failure surfaces for uncoated and coated fibers also confirmed a tensile failure of fibers as observed for polyacrylonitrile PAN-based fibers in literature. 
    more » « less