Evaluation of Keratin-Cellulose Blend Fibers as Precursors for Carbon Fibers.

One main challenge to utilize cellulose-based fibers as the precursor for carbon fibers is their inherently low carbon yield. This study aims to evaluate the use of keratin in chicken feathers, a byproduct of the poultry industry generated in large quantities, as a natural charring agent to improve the yield of cellulose-derived carbon fibers. Keratin-cellulose composite fibers are prepared through direct dissolution of the pulp and feather keratin in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) and subsequent dry jet wet spinning (so-called Ioncell process). Thermogravimetric analysis reveals that there is an increase in the carbon yield by ∼53 wt % with 30 wt % keratin incorporation. This increase is comparable to the one observed for lignin-cellulose composite fibers, in which lignin acts as a carbon booster due to its higher carbon content. Keratin, however, reduces the mechanical properties of cellulose precursor fibers to a lesser extent than lignin. Keratin introduces nitrogen and induces the formation of pores in the precursor fibers and the resulting carbon fibers. Carbon materials derived from the keratin-cellulose composite fiber show potential for applications where nitrogen doping and pores or voids in the carbon are desirable, for example, for low-cost bio-based carbons for energy harvest or storage.

Fast and quantitative compositional analysis of hybrid cellulose-based regenerated fibers using thermogravimetric analysis and chemometrics.

Cellulose can be dissolved with another biopolymer in a protic ionic liquid and spun into a bicomponent hybrid cellulose fiber using the Ioncell® technology. Inside the hybrid fibers, the biopolymers are mixed at the nanoscale, and the second biopolymer provides the produced hybrid fiber new functional properties that can be fine-tuned by controlling its share in the fiber. In the present work, we present a fast and quantitative thermoanalytical method for the compositional analysis of man-made hybrid cellulose fibers by using thermogravimetric analysis (TGA) in combination with chemometrics. First, we incorporated 0-46 wt.% of lignin or chitosan in the hybrid fibers. Then, we analyzed their thermal decomposition behavior in a TGA device following a simple, one-hour thermal treatment protocol. With an analogy to spectroscopy, we show that the derivative thermogram can be used as a predictor in a multivariate regression model for determining the share of lignin or chitosan in the cellulose hybrid fibers. The method generated cross validation errors in the range 1.5-2.1 wt.% for lignin and chitosan. In addition, we discuss how the multivariate regression outperforms more common modeling methods such as those based on thermogram deconvolution or on linear superposition of reference thermograms. Moreover, we highlight the versatility of this thermoanalytical method-which could be applied to a wide range of composite materials, provided that their components can be thermally resolved-and illustrate it with an additional example on the measurement of polyester content in cellulose and polyester fiber blends. The method could predict the polyester content in the cellulose-polyester fiber blends with a cross validation error of 1.94 wt.% in the range of 0-100 wt.%. Finally, we give a list of recommendations on good experimental and modeling practices for the readers who want to extend the application of this thermoanalytical method to other composite materials. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10570-021-03923-6.

Close Packing of Cellulose and Chitosan in Regenerated Cellulose Fibers Improves Carbon Yield and Structural Properties of Respective Carbon Fibers.

A low carbon yield is a major limitation for the use of cellulose-based filaments as carbon fiber precursors. The present study aims to investigate the use of an abundant biopolymer chitosan as a natural charring agent particularly on enhancing the carbon yield of the cellulose-derived carbon fiber. The ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) was used for direct dissolution of cellulose and chitosan and to spin cellulose-chitosan composite fibers through a dry-jet wet spinning process (Ioncell). The homogenous distribution and tight packing of cellulose and chitosan revealed by X-ray scattering experiments enable a synergistic interaction between the two polymers during the pyrolysis reaction, resulting in a substantial increase of the carbon yield and preservation of mechanical properties of cellulose fiber compared to other cobiopolymers such as lignin and xylan.

Metal(loid) immobilization in soils with biochars pyrolyzed in N2 and CO2 environments.

Previous studies indicated that using CO2 as a reaction agent in the pyrolysis of biomass led to an enhanced generation of syngas via direct reaction between volatile organic carbons (VOCs) evolved from the thermal degradation of biomass and CO2. In addition, the physico-chemical properties of biochar in CO2 were modified. In this current study, biochars generated from red pepper stalks in N2 and CO2 (RPS-N and RPS-C, respectively) were tested for their effects on the immobilization of Pb, Cd, Zn, and As in contaminated soils. Soils were incubated for one month with 2.5% of RPS, and two biochars (i.e., RPS-N and RPS-C) at 25°C. After the incubation period soils were analyzed to determine the amendment effects on the behavior of metal(loid)s. The potential availability and mobility kinetics of metal(loid)s were assessed by single extraction of ammonium acetate and consecutive extraction of calcium chloride, respectively. Sequential extraction was used to further examine potential changes in geochemical fractions of metal(loid)s. The increased soil pH induced by application of the biochars reduced the potentially available Pb, Cd, and Zn, while RPS-C significantly reduced Pb due to the high surface area and aromaticity of RPS-C. However, RPS-C mobilized potentially available As compared to RPS-N due to the increased soil pH. Biochars reduced the mobility kinetics of Pb, Cd, and Zn, and RPS-N effectuated the greatest reduction of As mobility. The RPS-C increased the Fe and Mn oxides, hydroxide, and organically bound Pb, while both biochars and RPS-N increased residual Cd and Zn, and organically bound As, respectively. When considering the two biochars, RPS-C was highly effective for immobilization of Pb in soils, but it had no effect on Cd and Zn and a negative effect on As. In addition, RPS-C significantly increased the total exchangeable cations in soils.