Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

The synthesis and processing of most thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization is an attractive, scalable alternative due to its exploitation of polymerization heat that is generally wasted and unutilized. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully cured thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat- or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Numerous applications of frontally generated materials exist, ranging from porous substrate reinforcement to fabrication of patterned composites. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications

Investigation of the levels of PBDEs and PCNs in the surface water and sediments from selected waterbodies in the Eastern Cape Province, South Africa

Studies have revealed that persistent organic pollutants (POPs) are omnipresent in our environment; almost all human beings have definite levels of POPs in their bodies. Even fetus and embryos are not spared; they have been found to bear certain levels of POPs. So far, there are about 28 chemicals listed as POPs among which are polybrominated diphenyl ethers (PBDEs) and polychlorinated naphthalenes (PCNs). PCN and PBDE distributions have been reported from different sources around the world, but studies relating to PCNs occurrence and distribution in Africa, especially South Africa is still minimal. PBDEs have been reported to cause diabetes, cancer, damage to reproductive system, thyroid, liver and other vital organs in the body, while PCNs have been linked to chloracne (severe skin reactions/lesions) and liver disease (yellow atrophy) in humans, chicken oedema and X-disease in cattle. Hence, this study evaluates PCN levels in water and sediment samples from three waterbodies: North End Lake (NEL), Chatty River (CHA) and Makman Canal (MMC), while PBDE levels was reported in NEL and CHA samples. The three sites are located in Port Elizabeth, Eastern Cape Province (ECP) of South Africa. The lake serves as a recreational resort while the latter two waterbodies are tributaries discharging into the Swartkop Estuary, an important estuary in ECP. Water samples were extracted with C18 cartridges (solid phase), while soxhlet was employed for the extraction of sediments. Water and sediment extricates were purified and quantified with gas chromatography-micro electron capture detector (GC-μECD). Forty-seven (47) water samples and 44 sediment samples were collected in August until December 2020 from six sampling points in NEL, five points in each of CHA and MMC. All the samples were evaluated for physicochemical properties, PBDEs and PCNs using validated standard methods. The sampling period covered three South Africa seasons: August (winter), October (spring) and December (summer). The physicochemical parameters (PP) of NEL water samples for the three seasons generally varied as follows: temperature (15.3–23°C), pH (7.9–10.3), oxidation-reduction potential, ORP (23.4-110 mV), atmospheric pressure, AP (14.52-15.56 PSI), turbidity (15.1–167 NTU), electrical conductivity, EC (114–1291 μS/cm), total dissolved solids, TDS (55-645 mg/L), total suspended solids, TSS (20–107 mg/L) and salinity (0.05–0.65 PSU). All the PPs except for turbidity and TSS are within acceptable limits. NEL sediments had moisture content (MC), organic matter (OM) and organic carbon (OC) in the range of 0.04–8.0percent, 0.08–2.2percent and 0.05–1.8percent, respectively. The sum of eight PCN congeners Σ8PCNs and six PBDE congeners Σ6PBDEs in NEL water samples ranged from 0.164–2.934 μg/L and 0.009-1.025 μg/L individually. The values for Σ8PCNs and Σ6PBDEs in NEL sediment samples varied from 0.991–237 μg/kg and 0.354-28.850 μg/kg, respectively. The calculated hazard quotient (HQ) corresponding to the non-carcinogenic health risk associated with PBDEs in NEL water samples was 2.0×10-3-1.4×10-1, while the TEQ values due to PCNs varied from 6.10×10-7- 3.12×10-3 μg/L in NEL water samples and 3.70×10-5-1.96×10-2 μg/kg dw in sediments. The PP values for CHA water samples include temperature (15.4–22.9°C), pH (7.7–10.5), TDS (991–1771 mg/L), TSS (6–41 mg/L), turbidity (1.0–198 NTU), EC (1981–3542 μS/cm), AP (14.60–14.80 PSI), ORP (-339.1-51.3 mV), and salinity (1.02–1.87 PSU). The EC, TDS and salinity exceeded acceptable values at certain points. The sediments of CHA have MC, OM and OC contents ranging from 0.01-10.2percent, 0.2-1.3percent and 0.1-0.8percent in that order. Sum of Σ8PCNs, Σ6PBDEs in CHA water and sediment samples ranged from 0.026–1.054 μg/L, 0.007-0.079 μg/L and 0.429–1888.468 μg/kg, 0.347-6.468 μg/kg individually. The HQ in CHA water samples was 1.6×10-3-7.7×10-3 and the estimated TEQ was 1.0×10-7-6.62×10-5 μg/L and 1.10×10−5-6.40×10−2 μg/kg in water and sediments, respectively. The temperatures for MMC water samples ranged from 15.6-24.5°C, while other PPs recorded were as follows: pH (8.4-10.2), TDS (943–4002 mg/L), TSS (7-491 mg/L), turbidity (2.9-154.2 NTU), EC (1885-8004 μS/cm), AP (14.53–14.82 PSI), ORP (7.8-130 mV) and salinity (0.96-4.47 PSU). MMC’s sediments recorded MC, OM and OC varying as 0.4- 18.9percent, 0.2-4.5percent and 0.1-2.6percent, respectively across the three seasons. The Σ8PCNs for MMC water and sediment samples were 0.035–0.699 μg/L and 0.260–6744 μg/kg. The TEQ values in MMC water and sediment samples were 1.19×10-7-1.47×10-4 μg/L and 4.43×10−5- 4.19×10−1 μg/kg, respectively. The results are all less than one, and this suggests that the selected water is safe. Results showed that NEL water had highest TEQ, PCN and PBDE concentrations, while MMC sediments recorded maximum TEQ and PCN levels in this study. PBDE concentrations in NEL sediments were above the other site. In conclusion, NEL water was most polluted with both pollutants (PCNs and PBDEs), but MMC sediments contained more PCNs. There is need for the immediate remediation of these selected waterbodies.Thesis (PhD) -- Faculty of Science and Agriculture, 202

Investigation of the levels of PBDEs and PCNs in the surface water and sediments from selected waterbodies in the Eastern Cape Province, South Africa

Studies have revealed that persistent organic pollutants (POPs) are omnipresent in our environment; almost all human beings have definite levels of POPs in their bodies. Even fetus and embryos are not spared; they have been found to bear certain levels of POPs. So far, there are about 28 chemicals listed as POPs among which are polybrominated diphenyl ethers (PBDEs) and polychlorinated naphthalenes (PCNs). PCN and PBDE distributions have been reported from different sources around the world, but studies relating to PCNs occurrence and distribution in Africa, especially South Africa is still minimal. PBDEs have been reported to cause diabetes, cancer, damage to reproductive system, thyroid, liver and other vital organs in the body, while PCNs have been linked to chloracne (severe skin reactions/lesions) and liver disease (yellow atrophy) in humans, chicken oedema and X-disease in cattle. Hence, this study evaluates PCN levels in water and sediment samples from three waterbodies: North End Lake (NEL), Chatty River (CHA) and Makman Canal (MMC), while PBDE levels was reported in NEL and CHA samples. The three sites are located in Port Elizabeth, Eastern Cape Province (ECP) of South Africa. The lake serves as a recreational resort while the latter two waterbodies are tributaries discharging into the Swartkop Estuary, an important estuary in ECP. Water samples were extracted with C18 cartridges (solid phase), while soxhlet was employed for the extraction of sediments. Water and sediment extricates were purified and quantified with gas chromatography-micro electron capture detector (GC-μECD). Forty-seven (47) water samples and 44 sediment samples were collected in August until December 2020 from six sampling points in NEL, five points in each of CHA and MMC. All the samples were evaluated for physicochemical properties, PBDEs and PCNs using validated standard methods. The sampling period covered three South Africa seasons: August (winter), October (spring) and December (summer). The physicochemical parameters (PP) of NEL water samples for the three seasons generally varied as follows: temperature (15.3–23°C), pH (7.9–10.3), oxidation-reduction potential, ORP (23.4-110 mV), atmospheric pressure, AP (14.52-15.56 PSI), turbidity (15.1–167 NTU), electrical conductivity, EC (114–1291 μS/cm), total dissolved solids, TDS (55-645 mg/L), total suspended solids, TSS (20–107 mg/L) and salinity (0.05–0.65 PSU). All the PPs except for turbidity and TSS are within acceptable limits. NEL sediments had moisture content (MC), organic matter (OM) and organic carbon (OC) in the range of 0.04–8.0percent, 0.08–2.2percent and 0.05–1.8percent, respectively. The sum of eight PCN congeners Σ8PCNs and six PBDE congeners Σ6PBDEs in NEL water samples ranged from 0.164–2.934 μg/L and 0.009-1.025 μg/L individually. The values for Σ8PCNs and Σ6PBDEs in NEL sediment samples varied from 0.991–237 μg/kg and 0.354-28.850 μg/kg, respectively. The calculated hazard quotient (HQ) corresponding to the non-carcinogenic health risk associated with PBDEs in NEL water samples was 2.0×10-3-1.4×10-1, while the TEQ values due to PCNs varied from 6.10×10-7- 3.12×10-3 μg/L in NEL water samples and 3.70×10-5-1.96×10-2 μg/kg dw in sediments. The PP values for CHA water samples include temperature (15.4–22.9°C), pH (7.7–10.5), TDS (991–1771 mg/L), TSS (6–41 mg/L), turbidity (1.0–198 NTU), EC (1981–3542 μS/cm), AP (14.60–14.80 PSI), ORP (-339.1-51.3 mV), and salinity (1.02–1.87 PSU). The EC, TDS and salinity exceeded acceptable values at certain points. The sediments of CHA have MC, OM and OC contents ranging from 0.01-10.2percent, 0.2-1.3percent and 0.1-0.8percent in that order. Sum of Σ8PCNs, Σ6PBDEs in CHA water and sediment samples ranged from 0.026–1.054 μg/L, 0.007-0.079 μg/L and 0.429–1888.468 μg/kg, 0.347-6.468 μg/kg individually. The HQ in CHA water samples was 1.6×10-3-7.7×10-3 and the estimated TEQ was 1.0×10-7-6.62×10-5 μg/L and 1.10×10−5-6.40×10−2 μg/kg in water and sediments, respectively. The temperatures for MMC water samples ranged from 15.6-24.5°C, while other PPs recorded were as follows: pH (8.4-10.2), TDS (943–4002 mg/L), TSS (7-491 mg/L), turbidity (2.9-154.2 NTU), EC (1885-8004 μS/cm), AP (14.53–14.82 PSI), ORP (7.8-130 mV) and salinity (0.96-4.47 PSU). MMC’s sediments recorded MC, OM and OC varying as 0.4- 18.9percent, 0.2-4.5percent and 0.1-2.6percent, respectively across the three seasons. The Σ8PCNs for MMC water and sediment samples were 0.035–0.699 μg/L and 0.260–6744 μg/kg. The TEQ values in MMC water and sediment samples were 1.19×10-7-1.47×10-4 μg/L and 4.43×10−5- 4.19×10−1 μg/kg, respectively. The results are all less than one, and this suggests that the selected water is safe. Results showed that NEL water had highest TEQ, PCN and PBDE concentrations, while MMC sediments recorded maximum TEQ and PCN levels in this study. PBDE concentrations in NEL sediments were above the other site. In conclusion, NEL water was most polluted with both pollutants (PCNs and PBDEs), but MMC sediments contained more PCNs. There is need for the immediate remediation of these selected waterbodies.Thesis (PhD) -- Faculty of Science and Agriculture, 202

An experimental feasibility study on fast pyrolysis of MSW-derived trommel fines for energy recovery and waste management

Trommel fines are solid wastes with particle sizes of 30 wt.%) and along with the volatile matter and higher heating values (HHV), varied in relation to particle sizes. By careful pre-treatment process design, the size fraction 0.5 mm – 2 mm, which was suitable for fast pyrolysis, had an experimental energy content of 13.8 MJ kg -1. The energy contents of the AW and AWS feedstocks increased with a reduction in ash contents after the respective washing procedures. A 300 g h-1 bubbling fluidised bed fast pyrolysis rig was used to investigate the effect of temperature and moisture content on product yields and process conversion efficiency of dry physically pre-treated trommel fines (PT) to determine their optimum processing conditions. Investigations were also undertaken to study the effect of feedstock pre-treatment method; dry (PT) and wet (AW and AWS) on both the pyrolysis products and process conversion efficiency. Using PT feedstock, the highest organic liquid yield and highest conversion efficiency was obtained between 500 °C and 550 ºC with <3 wt% feedstock moisture content. The organic liquid yield and the process conversion efficiencies increased with AW and AWS feedstocks, with AW feedstock giving the best results. The HHV of primary condensate from all feedstocks was greater than 30 MJ kg-1 and the washing procedure was found to reduce the nitrogen contents of the liquid products especially in the secondary condensate liquids.The fast pyrolysis results were used to determine the economic feasibility of the fast pyrolysis technology at PT optimum processing conditions for energy recovery and management of trommel fines at different processing capacities. The PT fast pyrolysis was found to be economically feasible from 2000 kg h-1 processing capacity, with a capital investment payback period of 8.6 years at 20% interest rate. The net present value (NPV) increased with the AW and AWS feedstocks and further analysis showed that processing these feedstocks could still be economically feasible at capacities of approximately 1000 kg h-1. 3 Overall, the results of this study suggest that the laboratory-scale fast pyrolysis rig used in this study and the developed economic model can form the basis for future research and process development for treatment of MSW