ABSTRACT
In the present paper, a scalable, economically feasible, and continuous process for making cellulose-based carbon fibers (CFs) is described encompassing precursor spinning, precursor additivation, thermal stabilization, and carbonization. By the use of boric acid (BA) as an additive, the main drawback of cellulose-based CFs, i.e., the low carbon yield, is overcome while maintaining a high level of mechanical properties. This is demonstrated by a systematic comparison between CFs obtained from a BA-doped and an un-doped cellulose precursor within a temperature range for carbonization between 1000 and 2000 °C. The changes in chemical composition (via elemental analysis) and physical structure (via X-ray scattering) as well as the mechanical and electrical properties of the resulting CFs were investigated. It turned out that, in contrast to current opinion, the catalytic effect of boron in the formation of graphite-like structures sets in already at 1000 °C. It becomes more and more effective with increasing temperature. The catalytic effect of boron significantly affects crystallite sizes (La, Lc), lattice plane spacings (d002), and orientation of the crystallites. Using BA, the carbon yield increased by 71%, Young's modulus by 27%, and conductivity by 168%, reaching 135,000 S/m. At the same time, a moderate decrease in tensile strength by 25% and an increase in density of 14% are observed.
ABSTRACT
The still-rising global demand for plastics warrants the substitution of non-renewable mineral oil-based resources with natural products as a decisive step towards sustainability. Lignin is one of the most abundant natural polymers and represents an ideal but hitherto highly underutilized raw material to replace petroleum-based resources. In particular, the use of lignin composites, especially polyolefin-lignin blends, is currently on the rise. In addition to specific mechanical property requirements, a challenge of implementing these alternative polymers is their heavy odor load. This is especially relevant for lignin, which exhibits an intrinsic odor that limits its use as an ingredient in blends intended for high quality applications. The present study addressed this issue by undertaking a systematic evaluation of the odor properties and constituent odorants of commercially available lignins and related high-density polyethylene (HDPE) blends. The potent odors of the investigated samples could be attributed to the presence of 71 individual odorous constituents that originated primarily from the structurally complex lignin. The majority of them was assignable to six main substance classes: carboxylic acids, aldehydes, phenols, furan compounds, alkylated 2-cyclopenten-1-ones, and sulfur compounds. The odors were strongly related to both the lignin raw materials and the different processes of their extraction, while the production of the blends had a lower but also significant influence. Especially the investigated soda lignin with hay- and honey-like odors was highly different in its odorant composition compared to lignins resulting from the sulfurous kraft process predominantly characterized by smoky and burnt odors. These observations highlight the importance of sufficient purification of the lignin raw material and the need for odor abatement procedures during the compounding process. The molecular elucidation of the odorants causing the strong odor represents an important procedure to develop odor reduction strategies.
ABSTRACT
Presented study deals with the pre-treatment of cellulose fibres with the aim to activate their surface and to enlarge their pore system, leading to an enhancement of fibres' affinity for subsequent functionalization processes. Swelling of fibres in aqueous solutions of sodium hydroxide opens their fibrillar structure, while freezing and freeze-drying retain this enlargement of the pore system, in contrast with conventional air or elevated temperature drying. Effect of different pre-treatment procedures on fibres' supramolecular structure, enlargement of their pore system, surface topography, zeta potential and mechanical properties was investigated. Degree of enhancement of the pore system depends on the concentration of sodium hydroxide and type of freezing; higher alkali concentrations are more effective, but at the cost of extensive deterioration of mechanical properties. Swelling of fibres in lower concentrations of NaOH, in combination with freeze drying, offers an acceptable compromise between enhancement of the fibres' pore system, changes in surface potential and tensile properties of treated fibres. Design of a suitable regime of swelling and drying of cellulose fibres results in an effective procedure for controlled tuning of their surface topography in combination with an increase of the available internal surface area and pore volume.
