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At least 523 records · Page 29

Developing a Roadmap for Bio-Derivable and Recyclable Composites: Re-Design and Scale-Up Considerations

Composites, often in the form of fiber reinforced plastics, are used in multiple facets of modern life from snowboards to vehicles, to wind turbines and beyond. Despite their prolific, and often renewable energy related uses, they are currently subject to a linear material economy from emission intensive precursors; thus, there is an opportunity to re-design these materials to be both bio-derivable and recyclable. In the present work, we provide a roadmap of what application considerations must be considered for vacuum assisted resin transfer molding (VARTM) processes for large composites materials at scale (e.g. infusible viscosities, moderate cure times, proper fiber adhesion, low cost, and maximum peak exotherm) when implementing bio-derivable and recyclable materials. We also provide illustrative concepts utilizing polyester covalently adaptable networks, from epoxy-anhydride chemistry, to achieve these goals. We further provide considerations when developing recycling process (e.g. maintenance of fiber sizing and orientation) and demonstrate these practices using low temperature methanolysis. Accompanying technoeconomic and life cycle analysis further illustrate the decarbonization benefits to bio-derivable and recyclable thermosets while informing future research and recycling processes. Finally, we provide a brief introduction to synergistic work within our team exploring how to further decarbonize the manufacturing of these materials.

BIOMASS FUELS,ENERGY CONSERVATION, CONSUMPTION, AN↗

Streamlined Loads Analysis of Floating Wind Turbines With Fiber Rope Mooring Lines: Preprint

This paper presents an approach for more accurate yet relatively streamlined accounting for the nonlinear characteristics of synthetic fiber rope mooring lines for floating wind turbines. First, we select a minimal set of parameters that can efficiently approximate a mooring line material's quasi-static and dynamic stiffness characteristics. We also develop a set of baseline coefficients for different rope materials based on published product information and research papers. We then expand a quasi-static mooring model to include dynamic mooring line stiffness terms in a way that allows the nonlinear stiffness behavior of fiber ropes to be considered even in quasi-static analyses. For dynamic analysis, we have updated the model MoorDyn, coupled with OpenFAST, to work with the new dynamic mooring line stiffness terms. This includes the implementation of a new viscoelastic approach that allows the tension-strain relation of each mooring line segment to vary between two stiffness values depending on the strain rate. After presenting the formulation of the approaches for modeling synthetic ropes, they are demonstrated on a floating wind turbine mooring system with taut polyester rope mooring lines. The results are compared with those of other approaches of similar fidelity including the static-dynamic method and separate simulations with static and dynamic stiffness values. Comparing the results shows the ability of the new method to match the results of the previous methods in a more streamlined manner.

elasticity↗

Converting Poly(ethylene terephthalate) to Rigid Thermosets: Performance and Recycling Considerations

Poly(ethylene terephthalate) (PET) is one of today's most ubiquitous plastics finding predominant uses in textiles and food applications. Due to its prolific implementation, PET already possesses a robust mechanical recycling infrastructure; however, current requirements for mechanical recycling still leads to an underutilization of PET. Thus, to keep carbon in the economy and further encourage decarbonization efforts it is paramount to find other applications for PET. In the present work, PET is converted to thermoset applications, specifically those relevant to fiber reinforced plastics. In one case, bioderived monomers are utilized to convert glycolyzed PET into unsaturated polyesters resins which can possess better thermomechanical performance than their petrochemical counterpart while also emitting less GHG emissions in their manufacture. In the second case, the constituent monomers from PET are converted into epoxies and reacted with either amines or anhydrides to form thermoset networks. When anhydrides are implemented alongside carboxylate-based epoxies, 100% monomer recyclability is obtainable. Meanwhile, when amines are used, performance of the materials can be enhanced at the sacrifice of some recyclability. Overall, this work demonstrates the potential to further incentivize the reclamation of materials through multiple second life applications in pursuance of maintaining carbon in today's material economy.

BIOMASS FUELS,ENVIRONMENTAL SCIENCES↗

Synthesis and characterization of biobased copolyesters based on pentanediol: (1) Poly(pentylene dodecanoate–co–furandicarboxylate)

A series of biobased aliphatic-aromatic copolyesters, poly(pentylene dodecanoate-co-furandicarboxylates) (PPeDFs) were synthesized via an esterification and polycondensation melt process. The copolyesters were characterized using gel permeation chromatography, Fourier transform infrared spectroscopy, 1 H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, wide angle x-ray scattering, and tensile testing. The thermal transition behavior was strongly dependent on composition, with the melting and glass transition temperatures reaching a minimum at approximately equimolar ratio of D to F. All copolyesters were stable below 300°C with their R 600 (the weight of material remaining at 600°C) values increasing with F fraction. PPeD to PPeDF30 (e.g., mole ratio D/F = 7:3) show sharp PPeD crystalline reflections only while broad PPeF reflections are shown in PPeF and PPeDF90. PPeDF40 to PPeDF80 showed both crystal structures. The fractional crystallinity for the PPeD was much higher than PPeF and the fractional crystallinity of the copolymers showed a minimum at D/F ratios closer to the latter. Here, the stress at break and modulus both exhibited maxima at D/F ratios that were either high or low, but somewhat surprisingly a strong maximum in percent elongation at break of over 600% occurs at PPeDF40. For this composition, a typical plastic behavior curve was found including a yield point, high elongation at break, and strain hardening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

End-Of-Life Textiles as Reinforcements in Biocomposites

A number of attempts have been made to recycle cotton/polyester blend woven fabrics after use; however, most of these fabrics are disposed of in landfills. Major part of these blend fabrics are not recycled due to complexity of the fibre arrangement and cannot be separated economically. This study shows that these discarded woven fabrics could be directly used as reinforcements in composites without fibre separation. Uniform alignment in the woven fabric provided consistent properties to the composites. The fabrics were reinforced by soybean-based-bioresins to produce biocomposites. The composites were analysed for mechanical, thermal, viscoelastic and morphological properties. Porosity and wettability of the composites were also evaluated. Results demonstrate that the tensile strength and modulus of over 100 and 10 MPa, respectively, can be obtained without any fibre treatment. Furthermore, impact strength over 70 kJ/m{sup 2} was obtained without any chemical treatment on fibres. The porosity of the composites produced was less than 9 vol%. Additionally, the fabrics were treated with alkali in order to improve the fibre–matrix interface and the composite properties were studied. From the economical perspective, these composites can be produced at a low cost as the major component is available for free or low cost.

36 MATERIALS SCIENCE↗

Aerobic Biodegradation of Aromatic Aliphatic Copolyester Induced by Bacteria Obtained from Different Environments

In this study the biodegradation characteristics of aromatic aliphatic copolyester Ecoflex was assayed with five different bacterial strains isolated from different kinds of environments and living at diverse optimum of temperature. The biodegradation properties of selected strains (Brevibacterium luteolum, Bacillus thuringiensis, Aeromonas media, Geobacillus kaustophilus and Serratia sp.) were assessed through several plate assays oriented to their proteolytic, lipolytic, esterolytic and cellulolytic abilities; catalase activities were measured too. In addition the bacterial hydrolytic abilities for polyhydroxybutyrate, polylactic acid and polybutyrate adipate terephthalate were obtained using specific culture media including also a specific Ecoflex agar. The biodegradation dynamics of selected strains were evaluated mainly by the incubation of Ecoflex foils with a specific bacterium during a period from 3 days until 16 weeks and the change of the degradability of the Ecoflex surface in nitrogen has been assessed by nonisothermal chemiluminescence measurements from 40 to 250 °C. Scanning electron microscope observation of inoculated foils was applied too. The comparison of the results showed the complexity of biodegradation phenomena. The concentration of oxygenated products measured by reached the maximum after 2 weeks of cultivation for strains G. kaustophilus and B. thurigiensis, after 4 weeks of cultivation for strain B. luteolum, and 8 weeks of cultivation for strains Serratia sp. and A. media. Each strain evidenced its own hydrolytic optimum at different periods, but almost all tested strains demonstrated a decline of hydrolysis up to 16 weeks of incubation. This study demonstrated that nonisothermal chemiluminescence examining momentaneous oxidation state of the polymer surface is a valuable technique to follow the biodegradation dynamics on polymeric film, while the Ecoflex agar is able to select useful polymer-degrading bacteria.

36 MATERIALS SCIENCE↗

Dissimilar Tendencies of Innovative Green Clay Organo-Modifier on the Final Properties of Poly(ε-caprolactone) Based Nanocomposites

Composites based on poly(ε-caprolactone) (PCL) were prepared by melt blending the polymer with natural and modified bentonite. Soy lecithin (SL), a natural and nontoxic biosurfactant, was used as modifier agent. Three organoclays with different SL contents were employed as fillers and composites containing 1 and 2 wt% of each clay, were prepared. Thermal (by thermogravimetric analysis, and differential scanning calorimetry), morphological (by X-ray diffraction (XRD) and melt rheology), mechanical (by tensile tests) and barrier properties (by means of water vapor permeability tests) of matrix and composites were studied as a function of clay type and content. Morphological analysis by XRD showed nanocomposites with intercalated-exfoliated structures while melt rheology suggests thermal degradation of PCL matrix catalyzed by SL bentonite modifier. Thermal and mechanical properties were consistent with this assumption, due to the slight increment in crystallinity percentage and detriment in the Young’s modulus of the nanocomposites in comparison with the neat matrix. On the other hand, water vapor permeability of PCL significantly decreased in composites, as is expected for polymer/clay nanocomposites, favoring its potential application as food packaging. Thus, dissimilar tendencies were found in the final properties of the nanocomposites that were attributed to the matrix molecular weight degradation catalyzed by the novel green clay organo-modifier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ageing and Its Influence on Vibration Characteristics of Jute/Polyester Composites

In this work, the influence of ageing on vibration characteristics of jute/polyester composite was investigated by varying the fiber length and weight percent. The ageing of composite was carried out under normal and seawater in room temperature. From the result, it is observed that the composite with the fiber length of 5 mm and 25-weight percentage has least moisture absorption and permeability than other types in both normal and seawater due to better fiber-matrix adhesion and closed pack arrangement of fibers. In addition, the above said combination shows better stability and vibration properties are least effected. Further, due to aging, the bonding between fiber and matrix is significantly affected to a larger degree with increase in the fiber content and length, which in turn decreases the natural frequency and damping properties of the composites.

36 MATERIALS SCIENCE↗

Abiotic Hydrolysis and Compostability of Blends Based on Cassava Starch and Biodegradable Polymers

When associated with polymer blends, starch may improve the biodegradability and compostability of other materials. The objectives of this work were to evaluate the abiotic hydrolysis and the composting process of films obtained from polymer blends between thermoplastic starch (TPS) and three other biodegradable polymers: poly[(butylene adipate)- co -(terephthalate)] (PBAT), poly(lactic acid) (PLA) and polyvinyl alcohol (PVA). PVA/TPS stood out as the most homogeneous blend and the one that showed the highest weight loss, with 46.21% of its initial weight remaining after abiotic hydrolysis tests. On the other hand, PBAT/TPS and PLA/TPS underwent more drastic and rapid degradation during composting in contrast to PVA/TPS. They became very fragmented after 21 days of composting, while the PVA/TPS was visually modified but remained unbroken until day 70. No blend sample exerted negative effects on the quality of the compost.

36 MATERIALS SCIENCE↗

Electrical Transport Properties of Carbon Nanotube/Polyester Polymer Composites

The electrical properties of polyester/carbon nanotube composites have been investigated within the frequency range of 10{sup 2} and 10{sup 6} Hz and temperature from 200 to 360 K. This paper reports the electrical conductivity behavior as a function of filler content, frequency, and temperature. The electrical conductivity of the composites obeys the universal Jonschers’ power law and leads to the parameter ss with values as 0.12< s < 0.93. The impedance data is found to fit well with Mott conditions of variable range hopping conduction. The values of Mott’s temperature, density of states at the Fermi energy, range of hopping, and hopping energy are also presented in this work.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The role of binding modules in enzymatic poly(ethylene terephthalate) hydrolysis at high-solids loadings

In nature, enzymes that deconstruct biological polymers, such as cellulose and chitin, often exhibit multi-domain architectures, comprising a catalytic domain and a non-catalytic binding module; the latter serves to increase the enzyme concentration at the substrate surface. This multi-domain architecture has been shown to improve the hydrolysis of poly(ethylene terephthalate) (PET) using engineered cutinase enzymes. Here, we examine the role of accessory binding modules at industrially relevant PET solids loadings necessary for cost-effective enzymatic recycling. Using a thermostable variant of leaf compost cutinase (LCC), we produced synthetic fusion constructs of LCC with five type A carbohydrate-binding modules (CBMs). At solids loadings below 10 wt%, the CBMs improve aromatic monomer yield from PET, but above this threshold, conversion extents up to 97% are reached with no added benefits from the presence of CBM fusions. This suggests that fusion constructs with the herein studied CBMs are not necessary for industrial enzymatic PET recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal oxide-promoted calcium cuprate catalysts for diol oxidative dehydrocyclization to lactones

Here, this work investigates structure-function relationships in electronically tunable, redox-active, basic Cu-Ca mixed metal oxide catalysts for oxidative dehydrocyclization of liquid diols to lactones. Compositional screening identified Ni 2+ and Zn 2+ as effective promoters that increase the surface Cu 2+ population by ∼1.7× and Cu-normalized activity for liquid 1,4-butanediol conversion to γ-butyrolactone by ∼3–4×. In situ Raman spectroscopy, in situ X-ray absorption spectroscopy (XAS), in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS), ex situ X-ray diffraction (XRD), and H 2 -temperature-programmed reduction (H 2 -TPR) show that Ni 2+ or Zn 2+ incorporation promotes the formation of Ca 0.82 Cu 1.00 O 2 nanoparticles under mild calcination conditions. This cuprate phase features stronger and shorter Cu–O bonds (1.90 Å) than inactive bulk CuO (1.95 Å) and square-planar Cu 2+ O 4 sites with enhanced d z2 electrophilicity, strengthening alkoxy adsorption. Pyridine-DRIFTS confirms the purely basic nature of the catalyst surface, while methanol-DRIFTS indicates Cu 2+ surface enrichment with Ni or Zn promotion, where Cu–O(Ca)–Cu sites can exist as amorphous domains or a truncation layer on crystalline nanoparticles.

09 BIOMASS FUELS↗

Layered double hydroxide/polyethylene terephthalate nanocomposites. Influence of the intercalated LDH anion and the type of polymerization heating method

Conventional and microwave heating routes have been used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate had been previously intercalated in the LDH. PXRD and TEM were used to detect the degree of dispersion of the filler and the type of the polymeric composites obtained, and FTIR spectroscopy confirmed that the polymerization process had taken place. The thermal stability of these composites, as studied by thermogravimetric analysis, was enhanced when the microwave heating method was applied. Dodecyl sulphate was more effective than terephthalate to exfoliate the samples, which only occurred for the terephthalate ones under microwave irradiation. - Graphical abstract: Conventional and microwave heating routes were used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate was previously intercalated into the LDH. The microwave process improves the dispersion and the thermal stability of nanocomposites due to the interaction of the microwave radiation and the dipolar properties of EG and the homogeneous heating. Highlights: > LDH-PET compatibility is enhanced by preintercalation of organic anions. > Dodecylsulphate performance is much better than that of terephthalate. > Microwave heating improves the thermal stability of the composites. > Microwave heating improves as well the dispersion of the inorganic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transfer of microstructure pattern of CNTs onto flexible substrate using hot press technique for sensing applications

Graphical abstract: - Highlights: • Successfully transfer of microstructure patterned CNTs on PET substrate. • Demonstrate as resistor-based NH{sub 3} gas sensor in the sub-ppm range. • Excellent photodetector having instantaneous response and recovery characteristics. • An effective technique to grow and produce flexible electronic device. - Abstract: In this work, we report the successful and efficient transfer process of two- dimensional (2-D) vertically aligned carbon nanotubes (CNTs) onto polyethylene terephthalate (PET) substrate by hot pressing method with an aim to develop flexible sensor devices. Carbon nanotubes are synthesized by cold wall thermal chemical vapor deposition using patterned SiO{sub 2} substrate under low pressure. The height of the pattern of CNTs is controlled by reaction time. The entire growth and transfer process is carried out within 30 min. Strong adhesion between the nanotube and polyethylene terephthalate substrate was observed in the post-transferred case. Raman spectroscopy and scanning electron microscope (SEM) studies are used to analyze the microstructure of carbon nanotube film before and after hot pressing. This technique shows great potential for the fabrication of flexible sensing devices. We report for the first time, the application of patterned microstructure developed by this technique in the development of gas sensor and optoelectronic device. Surface resistive mode is used for detection of ammonia (NH{sub 3}) gas in the sub-ppm range. An impressive photoconducting response is also observed in the visible wavelength. The reproducibility of the sample was checked and the results indicate the possibility of use of carbon nanotube as gas sensor, photodetector, CCDs etc.

36 MATERIALS SCIENCE↗

Electrical and optical properties of nitrogen doped SnO{sub 2} thin films deposited on flexible substrates by magnetron sputtering

Graphical abstract: The best SnO{sub 2}:N TCO film: about 80% transmittance and 9.1 × 10{sup −4} Ω cm. - Highlights: • Nitrogen-doped tin oxide film was deposited on PET by RF-magnetron sputtering. • Effects of oxygen partial pressure on the properties of thin films were investigated. • For SnO{sub 2}:N film, visible light transmittance was 80% and electrical resistivity was 9.1 × 10{sup −4} Ω cm. - Abstract: Nitrogen-doped tin oxide (SnO{sub 2}:N) thin films were deposited on flexible polyethylene terephthalate (PET) substrates at room temperature by RF-magnetron sputtering. Effects of oxygen partial pressure (0–4%) on electrical and optical properties of thin films were investigated. Experimental results showed that SnO{sub 2}:N films were amorphous state, and O/Sn ratios of SnO{sub 2}:N films were deviated from the standard stoichiometry 2:1. Optical band gap of SnO{sub 2}:N films increased from approximately 3.10 eV to 3.42 eV as oxygen partial pressure increased from 0% to 4%. For SnO{sub 2}:N thin films deposited on PET, transmittance was about 80% in the visible light region. The best transparent conductive oxide (TCO) deposited on flexible PET substrates was SnO{sub 2}:N thin films preparing at 2% oxygen partial pressure, the transmittance was about 80% and electrical conductivity was about 9.1 × 10{sup −4} Ω cm.

36 MATERIALS SCIENCE↗

Alternative polymer separation technology by centrifugal force in a melted state

Highlights: • Waste separation should take place at high purity. • Developed a novel, alternative separation method, where the separation occurred in a melted state by centrifugal forces. • Possibility of separation two different plastics into neat fractions. • High purity fractions were established at granulates and also at prefabricated blend. • Results were verified by DSC, optical microscopy and Raman spectroscopy. - Abstract: In order to upgrade polymer waste during recycling, separation should take place at high purity. The present research was aimed to develop a novel, alternative separation opportunity, where the polymer fractions were separated by centrifugal force in melted state. The efficiency of the constructed separation equipment was verified by two immiscible plastics (polyethylene terephthalate, PET; low density polyethylene, LDPE), which have a high difference of density, and of which large quantities can also be found in the municipal solid waste. The results show that the developed equipment is suitable not only for separating dry blended mixtures of PET/LDPE into pure components again, but also for separating prefabricated polymer blends. By this process it becomes possible to recover pure polymer substances from multi-component products during the recycling process. The adequacy of results was verified by differential scanning calorimetry (DSC) measurement as well as optical microscopy and Raman spectroscopy.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗