Lignin by-products from biorefineries has the potential to provide a low-cost alternative to petroleum-based precursors to manufacture carbon fiber, which can be combined with a binding matrix to produce a structural material with much greater specific strength and specific stiffness than conventional materials such as steel and aluminum. The market for carbon fiber is universally projected to grow exponentially to fill the needs of clean energy technologies such as wind turbines and to improve the fuel economies in vehicles through lightweighting. In addition to cellulosic biofuel production, lignin-based carbon fiber production coupled with biorefineries may provide $2,400 to $3,600 added value dry Mg-1 of biomass for vehicle applications. Compared to producing ethanol alone, the addition of lignin-derived carbon fiber could increase biorefinery gross revenue by 30% to 300%. Using lignin-derived carbon fiber in 15 million vehicles per year in the US could reduce fossil fuel consumption by 2-5 billion liters year(-1), reduce CO2 emissions by about 6.7 million Mg year(-1), and realize fuel savings through vehicle lightweighting of $700 to $ 1,600 per Mg biomass processed. The value of fuel savings from vehicle lightweighting becomes economical at carbon fiber price of $6.60 kg(-1) under current fuel prices, or $13.20 kg(-1) under fuel prices of about $1.16 l(-1).

The structural changes occurring to hardwood Alcell™ lignin as a result of fiber devolatilization/extrusion, oxidative thermo-stabilization and carbonization are investigated in this study by solid-state and solution nuclear magnetic resonance (NMR) spectroscopy techniques. Solution based 1H–13C correlation NMR of the un-spun Alcell™ lignin powder and extruded lignin fiber detected modest changes occurring due to fiber devolatilization/extrusion in the type and proportion of aliphatic side-chain carbons or monolignol inter-unit linkages. Molecular weight analysis by gel permeation chromatography (GPC), along with an additional 31P NMR method used to indicate changes in terminal hydroxyl functionality, suggest fiber devolatilization/extrusion causes both chain scission and condensation reactions. 1H CRAMPS (combined rotation and multiple-pulse spectroscopy) and 13C cross-polarization/magic angle spinning (CP/MAS) spectra of extruded and stabilized lignin fibers indicate stabilization severely reduces the proportion of methoxy groups present, while also increasing the relative proportion of carbonyl and carboxyl-related structures, typically associated with cross-linking chemistries. 13C direct-polarization/magic angle spinning (DP/MAS) analysis of stabilized and carbonized fibers shows an increased relative amount of carbon–carbon bonds on aryl structures and a relative decrease of aryl ethers. DP/MAS dipolar dephasing experiments suggest that a majority of non-protonated carbons convert from carbonyl to aryl and condensed aryl structures during carbonization.

Productive uses of lignin, the third most abundant natural polymer, have been sought for decades. One especially attractive possibility is that of developing value-added products including thermoplastics based on lignin. This possibility warrants special attention due to growth of the modern biofuel industries. However, the polydisperse molecular weight and hyper-branched structure of lignin has hindered the creation of high-performance biopolymers. Here, we report the preparation and characterization of novel lignin-based, partially carbon-neutral thermoplastics. We first altered the molecular weight of lignin, either by fractionation with methanol, or by formaldehyde crosslinking. Crosslinking of lignin increases the molecular weight, exhibiting Mn = 31000 g mol−1, whereas that of as-received lignin is 1840 g mol−1. Tuning the molecular weight of lignin enabled successful preparation of novel lignin-derived thermoplastics, when coupled with telechelic polybutadiene soft-segments at proper feed ratios. Characteristic to thermoplastic rubbers, free-standing films of the resulting copolymers exhibit two-phase morphology and associated relaxations in the dynamic mechanical loss spectrum. To the best of our knowledge this article is the first report to demonstrate phase immiscibility, melt-processibility, and biphasic morphology of soft and hard segments in a lignin-based copolymer for all feed ratios of two macromolecular components. The use of higher molecular weight lignin enhanced the resulting shear modulus due to efficient network formation of telechelic polybutadiene bridges. The storage modulus in the rubbery plateau region increased with increasing lignin content. The successful synthesis of novel lignin-based thermoplastics will open a new pathway to biomass utilization and will help conserve petrochemicals.

ABSTRACT: A Kraft hardwood lignin (HWL) and an organic-purified hardwood lignin (HWL-OP) were evaluated as potential precursors for the production of lowcost carbon fibers. It was found that the unpurified HWL exhibited poor spinnability while the HWL-OP exhibited excellent spinnability characteristics. Fibers of various diameters were obtained from the HWL-OP. Thermostabilization studies showed that oxidative stabilization can only be used to convert HWL-OP-based fibers into carbon fibers if extremely low heating rates are applied. Carbonized lignin-based fibers had tensile strength of 0.51 GPa and tensile modulus of 28.6 GPa. VC

Hydrogen adsorption on ultramicroporous carbon was investigated at near-ambient temperatures using volumetric and gravimetric methods. The results showed that the main process, physisorption, is accompanied by a slow process of different nature, that causes slow uptake at high pressures and hysteresis on desorption. The combined result is unusually high levels of hydrogen uptake at near-ambient temperatures and pressures (e.g. up to 0.8wt.% at 25°C and 2MPa). The heat of adsorption corresponding to the slow process leading to high uptake (17–20kJ/mol) is higher than usually reported for carbon materials; the adsorption kinetics is slow, and the isotherms exhibit pronounced hysteresis. These unusual properties were attributed to contributions from polarization-enhanced physisorption induced by traces of alkali metals residual from chemical activation. The results support the hypothesis that polarization-induced physisorption in high surface area carbons modified with traces of alkali metal ions is an alternate route for increasing the hydrogen storage capacity of carbon adsorbents.

The DOE Vehicle Technologies-funded work at ORNL is directed to the development of processes for the low cost production of carbon fibers. The objective of the project is to develop more energy-efficient, cost-effective processes for production of carbon fibers for use in composite materials for vehicles, which would substantially reduce vehicle weight, increase vehicle fuel economy, and result in lower CO2 emissions. Carbon fibers have the potential for substantial weight saving in vehicles because of their remarkable high strength, high modulus, and low density. However, carbon fibers are currently too expensive for large scale automotive use, which necessitates a large reduction in the cost of commercial grade fiber from about $20/lb to $5-7/lb. Lignin, a renewable resource material, has significant potential as a precursor material for low cost carbon fiber production. In this paper we report on progress to demonstrate the melt-spinning of precursor fibers from various lignin sources, the subsequent processing of the lignin precursor fibers into carbon fibers, and carbon fiber properties.

In pursuit of the goal to produce ultra-lightweight fuel efficient vehicles, there has been great excitement during the last few years about the potential for using carbon fiber reinforced composites in high volume applications. Currently, the greatest hill-die that inhibits wider implementation of carbon fiber composites in transportation is the high cost of the fiber when compared to other candidate materials. As part of the United States Department of Energy FreedomCAR initiative, significant research is being conducted to develop lower cost, high volume technologies for producing carbon fiber This paper will highlight the ongoing research in this area.Through Department of Energy (DOE) sponsorship, Oak Ridge National Laboratoty (ORNL) and its partners have been working with the Automotive Composites Consortium (A CC) to develop technologies that would enable the production of carbon fiber at 11.00-15.40 dollars per kilogram (5-7 dollars per pound). Achievement of this cost goal, would allow the introduction of carbon fiber based composites into a greater number of applications for future vehicles. The goal of lower cost carbon fiber has necessitated the development of both alternative precursors and more efficient production methods.Alternative precursors under investigation include textile grade polyacrylonitrile (PAN) fibers and fibers from lignin-based feedstocks. Previously as part of the research program, Hexcel Corporation developed the science necessary to allow textile grade PAN to be used as a precursor rather than typical carbon fiber grade precursors. Efforts are also underway to develop carbon fiber precursors from lignin-based feedstocks. ORNL and its partners are working on this effort with domestic pulp and paper producers and with current and future ethanol fuel producers. In terms of alternative production methods, ORNL has developed a microwave-based carbonization unit that can process pre-oxidized fiber at over 200 inches per minute. ORNL has also developed a new method of high speed oxidation and a new method for precursor stabilization. Additionally novel methods of activating carbon fiber surfaces are under development which allow atomic oxygen concentrations as high as 25-30% to be achieved rather than the more typical 4-8% achieved by the standard industrial ozone treatment.

Lignin, a sustainable, renewable resource material, is being evaluated for the low cost production of carbon fiber for automotive and other applications. We previously reported the successful production of carbon fiber from a solvent extracted lignin [1] and from other lignins [2]. However, it was found that the lignin fiber, produced by the melt spinning of the solvent extracted lignin, was difficult to stabilize (i.e., render infusible) and thus carbonize. The long stabilization time, due to the fiber s low Tg, led to the conclusion that thermal engineering of a lignin feedstock could ultimately raise the Tg of the lignin and thereby of the spun fiber. This would permit a higher temperature of stabilization, which would reduce stabilization time as well as overall processing times. The thermally-engineered lignins were evaluated in terms of their rheological properties, melt spinning ability, morphology, stabilization and carbonization properties, and ultimately mechanical properties of the carbon fibers obtained.

Lignin is a renewable resource material that is being evaluated for the low cost production of carbon fiber for automotive and other applications. Solvent extraction of a commercial hardwood lignin product yielded a purified lignin free of the contaminants typical of lignins derived from the Kraft chemical pulping of wood. The purified lignin was highly melt-spinnable into fibers, from which carbon fiber was subsequently produced. The lignin has been evaluated in terms of its rheological properties, fiber melt spinning ability, and potential for manufacture of low cost carbon fiber without the need for plasticizing agents or chemical modifications.

In continuation of the development of composite materials for air separation based on molecular sieving properties and magnetic fields effects, several molecular sieve materials were tested in a flow system, and the effects of temperature, flow conditions, and magnetic fields were investigated. New carbon materials adsorbents, with and without pre-loaded super-paramagnetic nanoparticles of Fe3O4 were synthesized; all materials were packed in chromatographic type columns which were placed between the poles of a high intensity, water-cooled, magnet (1.5 Tesla). In order to verify the existence of magnetodesorption effect, separation tests were conducted by injecting controlled volumes of air in a flow of inert gas, while the magnetic field was switched on and off. Gas composition downstream the column was analyzed by gas chromatography and by mass spectrometry. Under the conditions employed, the tests confirmed that N2 - O2 separation occurred at various degrees, depending on material's intrinsic properties, temperature and flow rate. The effect of magnetic fields, reported previously for static conditions, was not confirmed in the flow system. The best separation was obtained for zeolite 13X at sub-ambient temperatures. Future directions for the project include evaluation of a combined system, comprising carbon and zeolite molecular sieves, and testing the effect of stronger magnetic fields produced by cryogenic magnets.

The efforts for designing a meaningful and acceptable standard test method for characterization of kinetic parameters of air oxidation of graphite helped identify several practical issues that must be considered for the development of such a test. Using standard size (and shape) specimens, large enough in size to accommodate the inherent local microstructure differences between graphite samples, resulted in non-uniform oxidation profiles and preferential binder oxidation; this was not expected based on the linearity of Arrhenius plots and the (large) values of activation energy. It was found that the transition between the regimes 1 and 2 of graphite oxidation occurs gradually, depending both on the oxidation temperature and rate of oxygen supply. Nevertheless, measuring oxidation rates obtained on standard size samples provides a basis for a meaningful comparison among materials, which may serve as much needed information for predictive models.

Palladium-doped activated carbon fibers are being evaluated as candidate materials for enhanced hydrogen storage at near ambient conditions. Pd-doped fibers were spun using a Pd salt mixed with an isotropic pitch precursor. Experimental techniques such as in situ X-ray analysis, thermogravimetric studies, scanning transmission electron microscopy and gas adsorption were employed to understand how processing conditions for the production of Pd-doped activated carbon fibers affect the microstructure, pore development, and dispersion of metal particles throughout the fibers. The results showed that PdO phase is present in the stabilized fibers and that this oxide phase is stable up to about 250°C. The oxide phase transforms into Pd metal with increasing heat treatment temperature, going through the formation of an intermediate carbide phase. Sintering of Pd particles was observed with heat treatment at temperatures over 750°C. It was also found that pore development during physical activation with CO2 was not significantly affected by the presence of Pd particles within the fibers.