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.
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 6 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 5 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.
Multiple pH-sensitive composites have been prepared through non-covalently functionalizing chemically converted graphene (CCG) with chitosan. Chtiosan exhibits as polybases and CCG shows characteristics of polyacids. Owing to the synergistic effects of chitosan and CCG, chitosan decorated graphene (CS-G) presents a multiple pH-responsive behavior that it can be dispersed well whether in acidic or in basic solution but aggregated in near-neutral solution. After CS-G was modified through a controlled deposition and cross-linking process of chitosan, the resultant cross-linked chitosan decorated graphene (CLCS-G) can be converted to a different pH-sensitive material that disperses only in acidic solution. Both CS-G and CLCS-G present a reversible switching between dispersed and aggregated states with pH as a stimulus. The unique pH response mechanisms of CS-G and CLCS-G have been further investigated by zeta potential analysis. Based on the unique pH-responsive property of CS-G, a stable and repeatable pH-driven switch was developed for monitoring pH change.
The technology used in the manufacturing of televisions and monitors has been changing in recent years. Monitors with liquid crystal displays (LCD) emerged in the market with the aim of replacing cathode ray tube monitors. As a result, the disposal of this type of product, which is already very high, will increase. Thus, without accurate knowledge of the components and materials present in an LCD monitor, the recycling of materials, such as mercury, thermoplastic polymers, glasses, metals and precious metals amongst others, is not only performed, but allows contamination of soil, water and air with the liberation of toxic compounds present in this type of waste when disposed of improperly. Therefore, the objective of this study was to disassemble and characterize the materials in this type of waste, identify the composition, amount and form to enable, in further work, the development of recycling routes. After various tests and analyses, it was observed that an LCD display can be recycled, provided that precautions are taken. Levels of lead, fluoride and copper are above those permitted by the Brazilian law, characterizing this residue as having a high pollution potential. The materials present in printed circuit boards (base and precious metals)-thermoplastics, such as polyethylene terephthalate, acrylic, acrylonitrile butadiene styrene and polycarbonate and metals, such as steel and aluminum, and a layer of indium (in the internal face of the glass)-are components that make a point in terms of their potential for recycling.