| 1. |
- Özeren, Hüsamettin Deniz, et al.
(author)
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Role of Hydrogen Bonding in Wheat Gluten Protein Systems Plasticized with Glycerol and Water
- 2021
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In: Polymer. - : Elsevier BV. - 0032-3861 .- 1873-2291. ; 232, s. 124149-
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Journal article (other academic/artistic)abstract
- Many biopolymers are stiff and brittle and require plasticizers. To optimize the choice and amount of plasticizer, the mechanisms behind plasticization need to be understood. For polar biopolymers, such as polysaccharides and proteins, plasticization depends to a large extent on the hydrogen bond network. In this study, glycerol-plasticized protein systems based on wheat gluten were investigated, in combination with the effects of water. The methodology was based on a combination of mechanical tests and molecular dynamics simulations (MD). The simulations accurately predicted the glycerol content where the experimental depression in glass transition temperature (Tg) occurred (between 20 and 30 wt.% plasticizer). They also predicted the strong water-induced depression in Tg. Detailed analysis revealed that in the dry system, the main effect of glycerol was to break protein-protein hydrogen bonds. In the moist system, glycerol was partly outcompeted by water in forming hydrogen bonds with the protein, making the glycerol plasticizer less effective than in dry conditions. These results show that MD can successfully predict the plasticizer concentration at which the onset of efficient plasticization occurs. MD can therefore be an important tool for understanding plasticizer mechanisms, even in a complex system, on a level of detail that is impossible with experiments.
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| 2. |
- Janewithayapun, Ratchawit, 1998, et al.
(author)
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Nanostructures of etherified arabinoxylans and the effect of arabinose content on material properties
- 2024
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In: Carbohydrate Polymers. - : Elsevier BV. - 0144-8617 .- 1879-1344. ; 331
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Journal article (peer-reviewed)abstract
- To further our understanding of a thermoplastic arabinoxylan (AX) material obtained through an oxidation-reduction-etherification pathway, the role of the initial arabinose:xylose ratio on the material properties was investigated. Compression molded films with one molar substitution of butyl glycidyl ether (BGE) showed markedly different tensile behaviors. Films made from low arabinose AX were less ductile, while those made from high arabinose AX exhibited elastomer-like behaviors. X-ray scattering confirmed the presence of nanostructure formation resulting in nano-domains rich in either AX or BGE, from side chain grafting. The scattering data showed variations in the presence of ordered structures, nano-domain sizes and their temperature response between AX with different arabinose contents. In dynamic mechanical testing, three transitions were observed at approximately −90 °C, −50 °C and 80 °C, with a correlation between samples with more structured nano-domains and those with higher onset transition temperatures and lower storage modulus decrease. The mechanical properties of the final thermoplastic AX material can therefore be tuned by controlling the composition of the starting material.
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| 3. |
- Nilsson, Fritjof, Docent, 1978-, et al.
(author)
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Nanocomposites and polyethylene blends: two potentially synergistic strategies for HVDC insulation materials with ultra-low electrical conductivity
- 2021
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In: Composites Part B: Engineering. - : Elsevier BV. - 1359-8368 .- 1879-1069. ; 204
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Journal article (peer-reviewed)abstract
- Among the various requirements that high voltage direct current (HVDC) insulation materials need to satisfy, sufficiently low electrical conductivity is one of the most important. The leading commercial HVDC insulation material is currently an exceptionally clean cross-linked low-density polyethylene (XLPE). Previous studies have reported that the DC-conductivity of low-density polyethylene (LDPE) can be markedly reduced either by including a fraction of high-density polyethylene (HDPE) or by adding a small amount of a well dispersed, semiconducting nanofiller such as Al2O3 coated with a silane. This study demonstrates that by combining these two strategies a synergistic effect can be achieved, resulting in an insulation material with an ultra-low electrical conductivity. The addition of both HDPE and C8–Al2O3 nanoparticles to LDPE resulted in ultra-insulating nanocomposites with a conductivity around 500 times lower than of the neat LDPE at an electric field of 32 kV/mm and 60–90 °C. The new nanocomposite is thus a promising material regarding the electrical conductivity and it can be further optimized since the polyethylene blend and the nanoparticles can be improved independently.
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| 4. |
- Nilsson, Robin, 1993, et al.
(author)
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Experimental and simulated distribution and interaction of water in cellulose esters with alkyl chain substitutions
- 2023
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In: Carbohydrate Polymers. - : Elsevier BV. - 0144-8617 .- 1879-1344. ; 306
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Journal article (peer-reviewed)abstract
- This study investigated the effect of the average length of substituted side chains in different cellulose esters on water sorption and the water association mechanism. For this purpose, a set of esters with a similar total degree of substitution was selected: cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. Dynamic vapor sorption was used to determine the effect of the side chain length on sorption, desorption, and the occurrence of water clustering. Since water association in the structure was of interest, molecular dynamics simulations were performed on cellulose acetate and cellulose acetate propionate. This study showed that cellulose acetate appears to be water-sensitive and experiences hysteresis upon water sorption, which was attributed to structural changes. The simulations also showed that water is screened out by the side chains and forms intermolecular hydrogen bonds, primarily to the carbonyl oxygen rather than the residual hydroxyl groups.
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| 5. |
- Hoogendoorn, Billy W.
(author)
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Exploring cellulose as a biomacromolecule for enhanced battery metal ion recovery/recycling
- 2023
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Doctoral thesis (other academic/artistic)abstract
- The research focused on the effects of integrating nanocellulose in the solidification of metal ions into metal oxide particles or metallic electrodeposits. Firstly, the cellulose was isolated as highly crystalline ca. 15-25 nm thick and 500 nm long fibers from bacterial cellulose using acid hydrolysis and had a negative surface charge. Positively charged nanocellulose was also explored using cationic functional groups substituted onto the nanofiber surface. The effect of the isolated nanocellulose when preparing metal oxides via enforced precipitation of zinc metal ions into zinc oxide particles was investigated at ultra-low nanocellulose content ≤0.01 %. The result indicated that increased reaction yields of ~15 % and a reduction of particle sizes by up to 50 % could occur at nanocellulose concentrations of 0.01 %. The kinetics was studied and showed that the presence of cellulose consistently increased the consumption rates of zinc ions. If the reaction consumed a large fraction of the zinc-ions (>80%) within the first 15 min, continued growth of ZnO was also suppressed by the presence of nanocellulose. This was observed during the synthesis of sheet-like ZnO-particles, where an increase in reaction yield from 81 to 95 % hindered the growth of additional nanorods, which otherwise had formed after 15 min of the reaction. Further, nanocellulose was then evaluated for metal recovery reactions of Zn, Cd, and Ni using electrodeposition. Zinc and cadmium, which generally form separate, faceted metal particles during electrodeposition, grew large dendrites when nanocellulose was present in the electrolyte. In the case of cadmium, the formation of dendrites was correlated with increases in yield by up to 15 %. For nickel, which always deposited as uniform and non-faceted layers, the presence of nanocellulose did not result in dendritic deposits. While the presence of 0.05 % of nanocellulose did not affect the yield for negatively charged nanocellulose, positively charged nanocellulose decreased the deposited amount by up to ca. 20 %. The temperature was also used to tune the dendritic formation during the zinc deposition. The major finding was that while the zinc electrodeposition in the presence of nanocellulose at 20 or 40°C induced dendritic growth, a similar deposition at 60 °C did not, reverting the deposition towards promoting dense and faceted zinc particles. The research on integrating nanocellulose in metal oxide particle solidification and metal recovery using electrodeposition aligns with the United Nations' Sustainable Development Goals (SDGs), particularly Goal 12: Responsible Consumption and Production, and Goal 1: End poverty in all its forms everywhere, but also Goal 13: Climate Action. The use of nanocellulose as an additive can contribute to sustainable consumption and production practices, reducing waste and conserving natural resources. This approach can help to address the challenge of meeting growing demands for metals used in various industrial applications, particularly those associated with battery manufacturing. Recycling valuable metals using nanocellulose can reduce the environmental impact of mining and processing ores, contributing to sustainable resource management and contribute to poverty reduction for creating job opportunities. Furthermore, the use of nanocellulose in electrodeposition reactions will help to combat climate change by promoting more efficient and environmentally friendly metal recovery methods, potentially reducing the carbon footprint associated with traditional metal recovery and mitigate the environmental impacts of metal extraction and mining. Overall, the research on integrating nanocellulose in metal oxide particle solidification and metal recovery using electrodeposition demonstrates innovative and sustainable solutions for resource management, contributing to the UN's SDGs.
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| 6. |
- Newson, William, et al.
(author)
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Effect of Additives on the Tensile Performance and Protein Solubility of Industrial Oilseed Residual Based Plastics
- 2014
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In: Journal of Agricultural and Food Chemistry. - : American Chemical Society (ACS). - 0021-8561 .- 1520-5118. ; 62:28, s. 6707-6715
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Journal article (peer-reviewed)abstract
- Ten chemical additives were selected from the literature for their proposed modifying activity in protein-protein interactions. These consisted of acids, bases, reducing agents, and denaturants and were added to residual deoiled meals of Crambe abyssinica (crambe) and Brassica carinata (carinata) to modify the properties of plastics produced through hot compression molding at 130 degrees C. The films produced were examined for tensile properties, protein solubility, molecular weight distribution, and water absorption. Of the additives tested, NaOH had the greatest positive effect on tensile properties, with increases of 105% in maximum stress and 200% in strain at maximum stress for crambe and a 70% increase in strain at maximum stress for carinata. Stiffness was not increased by any of the applied additives. Changes in tensile strength and elongation for crambe and elongation for carinata were related to changes in protein solubility. Increased pH was the most successful in improving the protein aggregation and mechanical properties within the complex chemistry of residual oilseed meals.
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| 7. |
- Perroud, Théo, et al.
(author)
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Testing bioplastic containing functionalised biochar
- 2022
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In: Polymer testing. - : Elsevier. - 0142-9418 .- 1873-2348. ; 113
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Journal article (peer-reviewed)abstract
- Although flame retardants are very effective in reducing the fire hazard of polymeric materials, their presence may be detrimental to mechanical strength. Hence, in order to have a holistic improvement of performance properties, a new approach has been developed wherein biochar is used to host a naturally-occurring flame retardant (lanosol). The issue of loss in mechanical strength of a polymer host is alleviated by the use of biochar. Three different doping procedures were investigated, namely, dry mixing, and chemical and thermal-based doping, to integrate lanosol into the biochar pores. The doped biochar was used to develop wheat gluten-based blends. The mechanical and flammability properties of the blends were assessed. It was found that thermal doping was the most effective in introducing significant amounts of lanosol particles inside the biochar pores. The bioplastic containing chemically, and thermally doped biochar had equal tensile strength (5.2 MPa), which was comparable to that of the unmodified material (5.4 MPa). The thermally doped biochar displayed the lowest cone calorimeter peak heat release rate (636 kW m−2) for combustion and the highest apparent activation energy (32.4 kJ mol−1) for decomposition. Thus, for flame retarding protein-based matrices, the use of additives thermally doped into biochar is recommended to both simultaneously improve fire-resistance and conserve mechanical strength.
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| 8. |
- Özeren, Hüsamettin Deniz
(author)
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Plasticization of Biobased Polymers: A Combined Experimental and Simulation Approach
- 2021
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Doctoral thesis (other academic/artistic)abstract
- The field of bio-based plastics has developed significantly in recent decades and there is an increasing demand for industries to shift from petrochemical to biobased polymers. Biobased polymers offer competitive properties, and in many cases have advantages in terms of cost. Thermoplastic starch is already commercially available, while wheat-gluten protein-based materials are considered to be promising candidates for commercial use.Biobased materials can, however, have several drawbacks that have to be handled. Starch-based materials are, in general, brittle due to the stiff glucose-based molecular chain and hydrogen bond network. This is the case also for proteins (due to the stiff peptide bond, bulky side groups and hydrogen bond network), like for example gluten. These issues can, however, be resolved with effective compatible plasticizers. But in order to be able to optimize the choice of the right plasticizer for a specific polymer, there is a need for an increased understanding of the plasticizer mechanisms. Besides, a methodology for prediction of the plasticizer amount needed, as well as to be able to rank possible plasticizer candidates, based on their effectiveness. As a part of the development of a methodology (based on the combination of experimental and molecular-dynamics simulations) for prediction of plasticization and to investigate and understand plasticizer mechanisms, the main material investigated was starch, but also wheat gluten, both plasticized with glycerol. The main plasticizer used to date for biobased polymer materials is glycerol, because of its effectiveness, stability and low cost. In addition, it is also a large byproduct of biodiesel production. A number of other plasticizer candidates were also studied for the starch system to see if the developed methodology could be used to rank plasticizers. Diols were tested in the starch system as plasticizers, but they had no or little plasticization effect. Nevertheless, they gave rise to unexpected structures and properties. Several techniques were used to determine the experimental properties of the bio-based films, including calorimetry, gravimetry, dynamic mechanical analysis, and tensile testing.The results (based on mechanical and thermal properties) showed that the methodology could be used to rank plasticizers in terms of their effectiveness. It was also possible to predict the amount of plasticizer needed for effective softening. With the help of the simulations, the emollient effect could be studied in detail and largely explained by hydrogen bonding effects. The methodology was also developed to be able to predict from simulation not only trends in mechanical properties but also absolute values in stiffness and strength at elongation rates corresponding to experimental measurements.
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| 9. |
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| 10. |
- Karlsson, Mattias E., et al.
(author)
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Lamellae-controlled electrical properties of polyethylene - morphology, oxidation and effects of antioxidant on the DC conductivity
- 2020
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In: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 10:8, s. 4698-4709
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Journal article (peer-reviewed)abstract
- Destruction of the spherulite structure in low-density polyethylene (LDPE) is shown to result in a more insulating material at low temperatures, while the reverse effect is observed at high temperatures. On average, the change in morphology reduced the conductivity by a factor of 4, but this morphology-related decrease in conductivity was relatively small compared with the conductivity drop of more than 2 decades that was observed after slight oxidation of the LDPE (at 25 degrees C and 30 kV mm(-1)). The conductivity of LDPE was measured at different temperatures (25-60 degrees C) and at different electrical field strengths (3.3-30 kV mm(-1)) for multiple samples with a total crystalline content of 51 wt%. The transformation from a 5 mu m coherent structure of spherulites in the LDPE to an evenly dispersed random lamellar phase (with retained crystallinity) was achieved by extrusion melt processing. The addition of 50 ppm commercial phenolic antioxidant to the LDPE matrix (e.g. for the long-term use of polyethylene in high voltage direct current (HVDC) cables) gave a conductivity ca. 3 times higher than that of the same material without antioxidants at 60 degrees C (the operating temperature for the cables). For larger amounts of antioxidant up to 1000 ppm, the DC conductivity remained stable at ca. 1 x 10(-14) S m(-1). Finite element modeling (FEM) simulations were carried out to model the phenomena observed, and the results suggested that the higher conductivity of the spherulite-containing LDPE stems from the displacement and increased presence of polymeric irregularities (formed during crystallization) in the border regions of the spherulite structures.
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