Global warming, market and production capacity are being the key drivers for selecting the main players for the next decades in the market of bio-based plastics. The drop-in bio-based polymers such as the bio-based polyethylene terephtalate (PET) or polyethylene (PE), chemically identical to their petrochemical counterparts but having a component of biological origin, are in the top of the list. They are followed by new polymers such as PHA and PLA with a significant market growth rate since 2014 with projections to 2020. Research will provide improved strains designed through synthetic and systems biology approaches; furthermore, the use of low-cost substrates will contribute to the widespread application of these bio- based polymers. The durability of plastics is not considered anymore as a virtue, and interesting bioprospecting strategies to isolate microorganisms for assimilating the recalcitrant plastics will pave the way for in vivo strategies for plastic mineralization. In this context, waste management of bio-based plastic will be one of the most important issues in the near future in terms of the circular economy. There is a clear need for standardized labelling and sorting instructions, which should be regulated in a coordinated way by policymakers and material producers.
Nitrogen-based thermoset polymers have many industrial applications (for example, in composites), but are difficult to recycle or rework. We report a simple one-pot, low-temperature polycondensation between paraformaldehyde and 4,4'-oxydianiline (ODA) that forms hemiaminal dynamic covalent networks (HDCNs), which can further cyclize at high temperatures, producing poly(hexahydrotriazine)s (PHTs). Both materials are strong thermosetting polymers, and the PHTs exhibited very high Young’s moduli (up to ~14.0 gigapascals and up to 20 gigapascals when reinforced with surface-treated carbon nanotubes), excellent solvent resistance, and resistance to environmental stress cracking. However, both HDCNs and PHTs could be digested at low pH (<2) to recover the bisaniline monomers. By simply using different diamine monomers, the HDCN- and PHT-forming reactions afford extremely versatile materials platforms. For example, when poly(ethylene glycol) (PEG) diamine monomers were used to form HDCNs, elastic organogels formed that exhibited self-healing properties.
Concerns regarding marine plastic pollution and its affinity for chemical pollutants led us to quantify relationships between different types of mass-produced plastic and organic contaminants in an urban bay. At five locations in San Diego Bay, CA we measured sorption of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) throughout a 12-month period to the five most common types of mass-produced plastic: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP). During this long-term field experiment, sorption rates and concentrations of PCBs and PAHs varied significantly among plastic types and among locations. Our data suggest that for PAHs and PCBs, PET and PVC reach equilibrium in the marine environment much faster than HDPE, LDPE and PP. Most importantly, concentrations of PAHs and PCBs sorbed to HDPE, LDPE and PP were consistently much greater than concentrations sorbed to PET and PVC. These data imply that products made from HDPE, LDPE and PP pose a greater risk than products made from PET and PVC of concentrating these hazardous chemicals onto fragmented plastic debris ingested by marine animals.
Triclosan (TCS), a broad-spectrum antimicrobial, is used in commercial toothpastes with reported dental benefits. Our studies on 22 popular manual toothbrushes in the U.S. showed that common toothbrush head components can accumulate substantial amounts of TCS after brushing with TCS-formulated toothpastes (TCS-TPs). After simulated 3-month brushing with a commercial best-selling TCS-TP, over one third of the adults' toothbrushes showed a cumulative TCS uptake of 21-37.5 mg, equivalent to 7-12.5 doses of the TCS used per brushing. Similar results were observed on children’s toothbrushes with small pea-size heads. Elastomer components were found to be the main contributor while both nylon bristles and elastomers could act as absorptive sinks for TCS during brushing. Studies on six different TCS-TPs containing 0.3 wt% TCS showed similar profiles of TCS accumulation. The absorbed TCS was gradually released into toothpaste slurries after switching to TCS-free alternatives. Release of TCS, which typically measured at a fraction (<75%) of the standard dose using the TCS-TPs, continued for over 2 weeks and occurred most rapidly in peroxide-containing "whitening" toothpastes, followed by alkaline and surfactant-rich toothpastes. The accumulating effect was not exclusive to TCS but was commonly observed on several chemicals identified in TCS-TPs and a range of regular toothpastes.
Materials often exhibit a trade-off between stiffness and extensibility; for example, strengthening elastomers by increasing their cross-link density leads to embrittlement and decreased toughness. Inspired by cuticles of marine mussel byssi, we circumvent this inherent trade-off by incorporating sacrificial, reversible iron-catechol cross-links into a dry, loosely cross-linked epoxy network. The iron-containing network exhibits two to three orders of magnitude increases in stiffness, tensile strength, and tensile toughness compared to its iron-free precursor while gaining recoverable hysteretic energy dissipation and maintaining its original extensibility. Compared to previous realizations of this chemistry in hydrogels, the dry nature of the network enables larger property enhancement owing to the cooperative effects of both the increased cross-link density given by the reversible iron-catecholate complexes and the chain-restricting ionomeric nanodomains that they form.
The Mediterranean Sea has been recently proposed as one of the most impacted regions of the world with regards to microplastics, however the polymeric composition of these floating particles is still largely unknown. Here we present the results of a large-scale survey of neustonic micro- and meso-plastics floating in Mediterranean waters, providing the first extensive characterization of their chemical identity as well as detailed information on their abundance and geographical distribution. All particles >700 μm collected in our samples were identified through FT-IR analysis (n = 4050 particles), shedding for the first time light on the polymeric diversity of this emerging pollutant. Sixteen different classes of synthetic materials were identified. Low-density polymers such as polyethylene and polypropylene were the most abundant compounds, followed by polyamides, plastic-based paints, polyvinyl chloride, polystyrene and polyvinyl alcohol. Less frequent polymers included polyethylene terephthalate, polyisoprene, poly(vinyl stearate), ethylene-vinyl acetate, polyepoxide, paraffin wax and polycaprolactone, a biodegradable polyester reported for the first time floating in off-shore waters. Geographical differences in sample composition were also observed, demonstrating sub-basin scale heterogeneity in plastics distribution and likely reflecting a complex interplay between pollution sources, sinks and residence times of different polymers at sea.
Flexural properties and shock-absorbing capabilities of new face guard materials reinforced with fiberglass cloth
- Dental traumatology : official publication of International Association for Dental Traumatology
- Published over 7 years ago
Abstract - Aim: Experimental materials incorporating fiberglass cloth were used to develop a thin and lightweight face guard (FG). This study aims to evaluate the effect of fiberglass reinforcement on the flexural and shock absorption properties compared with conventional thermoplastic materials. Material and Method: Four commercial 3.2-mm and 1.6-mm medical splint materials (Aquaplast, Polyform, Co-polymer, and Erkodur) and two experimental materials were examined for use in FGs. The experimental materials were prepared by embedding two or four sheets of a plain woven fiberglass cloth on both surfaces of 1.5-mm Aquaplast. The flexural strength and flexural modulus were determined using a three-point bending test. The shock absorption properties were evaluated for a 5200-N impact load using the first peak intensity with a load cell system and the maximum stress with a film sensor system. Results and Conclusions: The flexural strength (74.6 MPa) and flexural modulus (6.3 GPa) of the experimental material with four sheets were significantly greater than those of the 3.2-mm commercial specimens, except for the flexural strength of one product. The first peak intensity (515 N) and maximum stress (2.2 MPa) of the experimental material with four sheets were significantly lower than those of the commercial 3.2-mm specimens, except for one product for each property. These results suggest that the thickness and weight of the FG can be reduced using the experimental fiber-reinforced material.
- Proceedings of the National Academy of Sciences of the United States of America
- Published almost 6 years ago
In this paper we explore the direct transfer via lamination of chemical vapor deposition graphene onto different flexible substrates. The transfer method investigated here is fast, simple, and does not require an intermediate transfer membrane, such as polymethylmethacrylate, which needs to be removed afterward. Various substrates of general interest in research and industry were studied in this work, including polytetrafluoroethylene filter membranes, PVC, cellulose nitrate/cellulose acetate filter membranes, polycarbonate, paraffin, polyethylene terephthalate, paper, and cloth. By comparing the properties of these substrates, two critical factors to ensure a successful transfer on bare substrates were identified: the substrate’s hydrophobicity and good contact between the substrate and graphene. For substrates that do not satisfy those requirements, polymethylmethacrylate can be used as a surface modifier or glue to ensure successful transfer. Our results can be applied to facilitate current processes and open up directions for applications of chemical vapor deposition graphene on flexible substrates. A broad range of applications can be envisioned, including fabrication of graphene devices for opto/organic electronics, graphene membranes for gas/liquid separation, and ubiquitous electronics with graphene.
We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid and chitosan were incorporated with AIT and used to coat one side of the film. The films were subjected to different storage conditions (storage time, storage temperature, and packed or unpacked) and handling conditions (washing, abrasion, and air blowing), and the antimicrobial activity of the films against Salmonella Stanley in tryptic soy broth was determined. The films (8.16 μl of AIT per cm(2) of surface area) significantly (P < 0.05) inhibited the growth of Salmonella during 24 h of incubation at 22°C, while the populations of Salmonella in controls increased from ca. 4 to over 8 log CFU/ml, indicating a minimum inactivation of 4 log CFU/ml on films in comparison to the growth on controls. Statistical analyses indicated that storage time, storage temperature, and surface abrasion affected the antimicrobial activity of the films significantly (P < 0.05). However, the differences in microbial reduction between those conditions were less than 0.5 log cycle. The results suggest that the films' antimicrobial properties are stable under practical storage and handling conditions and that these antimicrobial films have potential applications in food packaging.
Although biodegradable polymers have found extensive applications in medical areas, there are limited reports that show elastomeric behavior. In this work, a biodegradable, elastomeric polymer is demonstrated from a four-armed star copolymer. With a fixed middle core composition, comprising caprolactone (CL) and L-lactide (LA), an elastomer is obtained by increasing the polylactide (PLA) end block lengths to obtain sufficient end block crystallinity. This increase suppressed the middle core’s crystallinity yet ensured cocrystallization of the PLA ends of individual star copolymer chains to form a three-dimensional network via physical crosslinking. Cyclic and creep test of the star copolymers showed that at least 75% of recovery was achieved. Degradation study of the copolymer showed that degradation first occurred in the caprolactone-co-lactide (CLLA) core, followed by degradation in the PLA ends. Chain scission in the middle core resulted in immediate formation of CL crystals within the core and increased crystallinity over time, in both CLLA core and PLA ends. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 100A:3436-3445, 2012.