Muhammed Hajee

This work reports the use of cross-linkers in bio-based blends from hydroxypropyl-modified lignin (TcC) and a bio-based polyamide (PA1010) for possible use as carbon fibre precursors, which, while minimising their effects on melt processing into filaments, assist in cross-linking components during the subsequent thermal stabilisation stage. Cross-linkers included a highly sterically hindered aliphatic hydrocarbon (Perkadox 30, PdX), a mono-functional organic peroxide (Triganox 311, TnX), and two different hydroxyalkylamides (Primid® XL-552 (PmD 552) and Primid® QM-1260 (PmD 1260)). The characterisation of melt-compounded samples of TcC/PA1010 containing PdX and TnX indicated considerable cross-linking via FTIR, DSC, DMA and rheology measurements. While both Primids showed some evidence of cross-linking, it was less than with PdX and TnX. This was corroborated via melt spinning of the melt-compounded chips or pellet-coated TcC/PA1010, each with cross-linker via a continuous, sub-pilot scale, melt-spinning process, where both Primids showed better processability. With the latter technique, while filaments could be produced, they were very brittle. To overcome this, melt-spun TcC/PA1010 filaments were immersed in aqueous solutions of PmD 552 and PmD 1260 at 80 °C. The resultant filaments could be easily thermally stabilised and showed evidence of cross-linking, producing higher char residues than the control filaments in the TGA experiments.

Biobased blends from hydroxypropyl modified lignin (TcC) and a biobased polyamide (PA1010) were produced by continuous sub-pilot scale melt spinning process. A reactive compatibilization was employed with the help of two different compatibilizers (ethylene-acrylic ester-maleic anhydride (MA) and ethylene-methyl acrylate-glycidyl methacrylate (GMA)) to enhance the compatibility between the TcC and PA1010. The enhanced compatibility between the TcC and PA1010 achieved by reaction between hydroxyl groups with maleic anhydride groups in the MA compatibilizer or epoxy groups in the GMA compatibilizer via nucleophilic substitution, was confirmed by chemical (Fourier infrared measurements), physical (glass transition, melting and crystallization behaviour), rheological, morphological and tensile properties of the filaments from compatibilized blends. MA compatibilizer required a higher concentration (2 phr) than GMA (1 phr) to achieve an optimal performance because of the difference in the reactive group's concentration within the each compatibilizer. The MA compatibilizer though was more effective than GMA. The precursor blended filaments were successfully carbonized in a lab scale experiment to yield coherent carbon fibres with tensile stress values of 192 ± 77 and 159 ± 95 MPa; and moduli of 16.2 and 13.9 GPa respectively for uncompatibilised and 2% MA compatibilized blends. That the compatibilized carbon fibre properties are slightly inferior may be attributed to the need to accurately control and optimise applied stress during the thermostabilisation and carbonization stages. Notwithstanding, these differences, the results indicate the potential benefit of using compatibilized TcC/PA1010 blend filaments as carbon fibre precursors.

The compatability of hardwood lignin (TcA)/bio-polyamide (PA) blends, prepared by melt compounding TcA with three different biobased polyamides, PA 1012, PA 1010 and PA 11 in a twin screw extruder have been studied. FTIR studies indicated the existence of physicochemical interactions between the TcA and polyamide. The melting temperatures of the blends were significantly reduced compared to the respective neat polyamides, which was attributed to the enhanced compatibility between the two components. The compatibility was also attributed to the increased glass transition (Tg) of the polyamide. Thermogravimetric studies, while not indicating any interaction during the processing stage, suggested that there was some during the thermal degradation stage, which assisted formation of carbonaceous residue. The addition of each polyamide to TcA considerably reduced its viscosity and enhanced its processability even at high lignin contents. Morphological analysis showed that heterogeneity for all the blends was quite uniform, although TcA domain sizes were considerably smaller (~ 0.5 μm) in the PA11 matrix compared to those in PA1010 and PA1012, suggesting better compatibility in the TcA/PA11 blends. This observation was consistent with the thermodynamic Gibbs’ free enery values of the respective blends. Overall, the order of blend compatibility was TcA/PA11 > TcA/PA1010 > TcA/PA1012.