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At least 541 records · Page 30

Rapid discrimination of plastic packaging materials using MIR spectroscopy coupled with independent components analysis (ICA)

Highlights: • An innovative technique, MIR-ICA, was applied to plastic packaging separation. • This study was carried out on PE, PP, PS, PET and PLA plastic packaging materials. • ICA was applied to discriminate plastics and 100% separation rates were obtained. • Analyses performed on two spectrometers proved the reproducibility of the method. • MIR-ICA is a simple and fast technique allowing plastic identification/classification. - Abstract: Plastic packaging wastes increased considerably in recent decades, raising a major and serious public concern on political, economical and environmental levels. Dealing with this kind of problems is generally done by landfilling and energy recovery. However, these two methods are becoming more and more expensive, hazardous to the public health and the environment. Therefore, recycling is gaining worldwide consideration as a solution to decrease the growing volume of plastic packaging wastes and simultaneously reduce the consumption of oil required to produce virgin resin. Nevertheless, a major shortage is encountered in recycling which is related to the sorting of plastic wastes. In this paper, a feasibility study was performed in order to test the potential of an innovative approach combining mid infrared (MIR) spectroscopy with independent components analysis (ICA), as a simple and fast approach which could achieve high separation rates. This approach (MIR-ICA) gave 100% discrimination rates in the separation of all studied plastics: polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polylactide (PLA). In addition, some more specific discriminations were obtained separating plastic materials belonging to the same polymer family e.g. high density polyethylene (HDPE) from low density polyethylene (LDPE). High discrimination rates were obtained despite the heterogeneity among samples especially differences in colors, thicknesses and surface textures. The reproducibility of the proposed approach was also tested using two spectrometers with considerable differences in their sensitivities. Discrimination rates were not affected proving that the developed approach could be extrapolated to different spectrometers. MIR combined with ICA is a promising tool for plastic waste separation that can help improve performance in this field; however further technological improvements and developments are required before it can be applied at an industrial level given that all tests presented here were performed under laboratory conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis of branched, nano channeled, ultrafine and nano carbon tubes from PET wastes using the arc discharge method

Highlights: • Polymer wastes are converted into ultrafine and nano carbon tubes and spheres. • Simple process with a minimal processing time. • It is a catalyst free and solvent free approach. • This process forms branched ultrafine carbon tubules with nano channels. - Abstract: Upcycling polymer wastes into useful, and valuable carbon based materials, is a challenging process. We report a novel catalyst-free and solvent-free technique for the formation of nano channeled ultrafine carbon tubes (NCUFCTs) and multiwalled carbon nanotubes (MWCNTs) from polyethylene terephthalate (PET) wastes, using rotating cathode arc discharge technique. The soot obtain from the anode contains ultrafine and nano-sized solid carbon spheres (SCS) with a mean diameter of 221 nm and 100 nm, respectively, formed at the lower temperature region of the anode where the temperature is approximately 1700 °C. The carbon spheres are converted into long “Y” type branched and non-branched NCUFCTs and MWCNTs at higher temperature regions where the temperature is approximately 2600 °C, with mean diameters of 364 nm and 95 nm, respectively. Soot deposited on the cathode is composed of MWCNTs with a mean diameter of 20 nm and other nanoparticles. The tubular structures present in the anode are longer, bent and often coiled with lesser graphitization compared to the nanotubes in the soot on the cathode.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Separation of polyethylene terephthalate from municipal waste plastics by froth flotation for recycling industry

Highlights: • Factors of NaOH treatment were studied by orthogonal and single factor experiments. • Mechanism of alkaline treatment for facilitating flotation was manifested. • Flotation separation of PET was achieved with high purity and efficiency. • A flow sheet of purification PET from MWP was designed. - Abstract: Recycling is an effective way to manage plastic wastes and receives considerable attention. Since plastic mixtures are difficult to recycle because of their intrinsic characteristics, separation of mixed plastics is the key problem for recycling. Separation of polyethylene terephthalate (PET) from municipal waste plastics (MWP) by froth flotation combined with alkaline pretreatment was investigated for recycling industry. The effect of process variables was estimated by L{sub 9} (3{sup 4}) orthogonal array of experiments and single factor experiments. The optimum conditions of alkaline pretreatment are 10 wt% sodium hydroxide, 20 min and 70 °C. After alkaline pretreatment under optimum conditions, flotation separation PET from acrylonitrile–butadiene–styrene, polystyrene, polycarbonate or polyvinyl chloride was achieved with high purity and efficiency. The purity of PET is up to 98.46% and the recovery is above 92.47%. A flow sheet of separation PET from MWP by a combination of froth flotation and sink float separation was designed. This study facilitates industrial application of plastics flotation and provides technical insights into recycling of waste plastics.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Combating oil spill problem using plastic waste

Highlights: • Up-cycling one type of pollution i.e. plastic waste and successfully using it to combat the other type of pollution i.e. oil spill. • Synthesized oil sorbent that has extremely high oil uptake of 90 g/g after prolonged dripping of 1 h. • Synthesized porous oil sorbent film which not only facilitates in oil sorption but also increases the affinity between sorbent and oil by means of adhesion. - Abstract: Thermoplastic polymers (such as polypropylene, polyethylene, polyethylene terephthalate (PET) and high density polyethylene (HDPE)) constitute 5–15% of municipal solid waste produced across the world. A huge quantity of plastic waste is disposed of each year and is mostly either discarded in landfills or incinerated. On the other hand, the usage of synthetic polymers as oil sorbents, in particular, polyolefins, including polypropylene (PP), and polyethylene (PE) are the most commonly used oil sorbent materials mainly due to their low cost. However, they possess relatively low oil absorption capacities. In this work, we provide an innovative way to produce a value-added product such as oil-sorbent film with high practical oil uptake values in terms of g/g from waste HDPE bottles for rapid oil spill remedy.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Alveolocapillary model system to study alveolar re-epithelialization

In the present study an in vitro bilayer model system of the pulmonary alveolocapillary barrier was established to investigate the role of the microvascular endothelium on re-epithelialization. The model system, confluent monolayer cultures on opposing sides of a porous membrane, consisted of a human microvascular endothelial cell line (HPMEC-ST1.6R) and an alveolar type II like cell line (A549), stably expressing EGFP and mCherry, respectively. These fluorescent proteins allowed the real time assessment of the integrity of the monolayers and the automated analysis of the wound healing process after a scratch injury. The HPMECs significantly attenuated the speed of re-epithelialization, which was associated with the proximity to the A549 layer. Examination of cross-sectional transmission electron micrographs of the model system revealed protrusions through the membrane pores and close contact between the A549 cells and the HPMECs. Immunohistochemical analysis showed that these close contacts consisted of heterocellular gap-, tight- and adherens-junctions. Additional analysis, using a fluorescent probe to assess gap-junctional communication, revealed that the HPMECs and A549 cells were able to exchange the fluorophore, which could be abrogated by disrupting the gap junctions using connexin mimetic peptides. These data suggest that the pulmonary microvascular endothelium may impact the re-epithelialization process. -- Highlights: ► Model system for vital imaging and high throughput screening. ► Microvascular endothelium influences re-epithelialization. ► A549 cells form protrusions through membrane to contact HPMEC. ► A549 cells and HPMECs form heterocellular tight-, gap- and adherens-junctions.

60 APPLIED LIFE SCIENCES↗

Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition

The grafting-through copolymerization of two distinct macromonomers via ring-opening metathesis polymerization is normally used to form statistical or diblock bottlebrush polymers with large total backbone degrees of polymerization (N BB ) relative to that of the side-chains (N SC ). Here, we demonstrate that Grubbs-type chemistry in the opposite limit, namely N BB << N SC , produces well-defined materials with excellent control over ensemble-averaged properties, including molar mass, dispersity, composition, and number of branch points. The dependence of self-assembly on these molecular design parameters was systematically probed using small angle X-ray scattering and self-consistent field theoretic simulations. Moreover, our analysis supports the notion that two-component bottlebrush copolymers with small N BB behave like miktoarm star polymers. The star-to-bottlebrush transition is quantifiable for both statistical and diblock sequences by unique signatures in the experimental scaling of domain spacing and simulated distribution of backbone/side-chain density within lamellar unit cells. These findings represent a conceptual framework that simplifies the synthesis of miktoarm star polymers when dispersity in the number of arms and composition can be tolerated. The analytical approach introduced to distinguish chain conformations in complex macromolecules also complements previous methods, for example form factor scattering and rheology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Friction- and Wear-Reducing Properties of Multifunctional Small Molecules

Nitrogen- and oxygen-containing compounds were designed and synthesized, and their tribological performance as multifunctional base oils (MFBOs) for internal combustion engine applications was evaluated. Two of the compounds displayed good rheology without the addition of polymeric viscosity modifiers, with a high viscosity index (VI) above 200.Additionally, all three MFBOs had lower coefficients of friction when compared to well established and accepted benchmarks, and demonstrated wear improvement by a factor of 5.5 to 70 compared to either of the benchmarks. Moreover, the compounds were easily synthesized in one step from commercial intermediates or starting materials. This work demonstrates that careful design of a single molecule might provide the functions of base oil, viscosity modifiers (or viscosity index improvers), anti-wear and friction reducing additives.

Cosimbescu, Lelia↗

Poly(lactic acid) Toughening through Chain End Engineering

The intrinsic brittleness of poly(lactic acid) (PLA) has hindered its widespread use in many structural applications. Various strategies have been developed to toughen PLA; however, most of the methods lead to a trade-off in strength or modulus. In this study, a chain end engineering strategy was developed to toughen PLA via an industry-friendly melt processing method. Green acids with multifunctional groups, such as 1,2,3,4-butanetetracarboxylic acid (BTCA), were used to modify PLA chain ends/tails via a melt reaction. We report a remarkable improvement in toughness (16×) was achieved by the addition of a minimal amount of BTCA (0.5%). At the same time, the toughened PLA samples maintained the tensile strength and Young’s modulus of neat PLA, suggesting a unique toughening mechanism that is different from the plasticizing effect. Other acid–based modifiers with different numbers of functional groups were also studied in this work. To understand the toughening, we propose a chain end engineering picture that can improve the toughness via a reduction in the number density of chain ends or defects of entanglement and the formation of long-branch topological structures. This study demonstrates a unique and cost-effective strategy for toughening PLA via scalable melt reaction without sacrificing other mechanical properties of PLA, potentially broadening the applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbonylative Co- and Terpolymerizations of 10-Undecen-1-ol: A Route to Polyketoesters with Tunable Compositions

A strategy to synthesize branched polyketoesters from the carbonylative polymerization of bifunctional α,ω-alkenols such as 10-undecen-1-ol is presented. This strategy hinges on the competitive application of two related catalytic manifolds, alternating alkene/CO copolymerization, and alkene hydroesterification, which share a common metal acyl intermediate. Small molecule model studies of cationic Pd-catalyzed alkene carbonylation in the presence of alcohols demonstrate that the relative rates of ketone formation (through alternating alkene/CO insertion) and ester formation (through metal acyl alcoholysis) can be tuned across a wide range through judicious bis(phosphine) ligand design. Carbonylative polymerization of 10-undecen-1-ol with a (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 catalyst (dppp(3,5-CF 3 ) 4 = 1,3-bis[bis[3,5-bis(trifluoromethyl)phenyl]-phosphino]propane) led to the formation of high molecular weight polyketoesters with intermediate dispersity (M n > 20,000 g/mol, D- = 2.6) and a ketone/ester microstructure ratio of approximately 1:2. In these polymerization reactions, deploying electron-deficient bis(phosphines) to suppress deleterious alkene isomerization was the key to accessing the high molecular weight polymer. Further, terpolymerization reactions of 1-hexene/10-undecen-1-ol/CO or 1-fluoro-10-undecene/10-undecen-1-ol/CO by (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 were also successful. Furthermore, this proof of concept polymerization unlocks access to tunable polymer microstructures without extensive postpolymerization treatment.

10-undecen-1-ol↗

Counterintuitive Compatibilization of Poly(-Valerolactone) and Poly(L-Lactic Acid) by Statistical Copolymers toward Compostable and Recyclable Packaging

Poly(δ-valerolactone) (PVL) and poly(l-lactic acid) (PLLA) are bioderivable, compostable, and chemically recyclable plastics with synergistic properties for addressing plastic waste accumulation in receiving environments. Though recyclable-by-design polymers often fall short of competing with incumbent materials, blending affords a means to leverage individual component strengths toward ideal tunable properties. Polymer blends are often immiscible, but a range of methodologies are available to promote mixing. Here, we report on the compatibilization of 9 immiscible PVL and PLLA blends with three different compatibilization agents: thermoplastic starch, synthesized PVL-co-PLLA statistical copolymers (SCPs), and synthesized PVL-b-PLLA block-type copolymers. Resulting degrees of compatibilization are observed through scanning electron microscopy, corroborated by thermal and mechanical analyses monitoring performance as a function of microdomain size. Small-angle and wide-angle X-ray scattering experiments are conducted to observe the influence of compatibilizers on individual crystalline phases to further elucidate material behavior. Molecular dynamics simulations provide key insights into the interfacial interactions between homopolymers and compatibilizers. Finally, a suite of end-of-life avenues is established by biodegradation in industrial composting conditions, chemical recycling by deconstruction to hydroxymethyl esters, and direct chemical depolymerization to lactone precursors in mixed feed. Overall, we highlight several promising blends and the counterintuitive SCP compatibilization phenomenon toward high-performance, sustainable materials.

Compatibilization, copolymer compatibilizer, bio-b↗

Synthesis and magnetic reversal of bi-conical Ni nanostructures

Template synthesis in polyethylene terephthalate (PET) membranes has been used to grow hour glass shaped nickel nanowires with a constriction in the range of tens of nanometers at the center. Anisotropic magnetoresistance measurements have been performed on a single nanowire to follow magnetization reversal of the structure. The results are explained via 3D micromagnetic simulations showing the appearance of a complex vortex state close to the constriction whose propagation depends on the angle between the cone axis and the applied field. The interest of this original growth process for spintronics is discussed.

36 MATERIALS SCIENCE↗

Mechanically tunable magnetic properties of Fe{sub 81}Ga{sub 19} films grown on flexible substrates

We investigated on magnetic properties of magnetostrictive Fe{sub 81}Ga{sub 19} films grown on flexible polyethylene terephthalate (PET) substrates under various mechanical strains. The unstrained Fe{sub 81}Ga{sub 19} films exhibit a significant uniaxial magnetic anisotropy due to a residual stress in PET substrates. It was found that the squareness of hysteresis loops can be tuned by an application of strains, inward/compressive or outward/tensile bending of the films. A modified Stoner-Wohlfarth model with considering a distribution of easy axes in polycrystalline films was developed to account for the mechanically tunable magnetic properties in flexible Fe{sub 81}Ga{sub 19} films. These results provide an alternative way to tune mechanically magnetic properties, which is particularly important for developing flexible magnetoelectronic devices.

36 MATERIALS SCIENCE↗

120 MeV Ni Ion beam induced modifications in poly (ethylene terephthalate) used in commercial bottled water

We report the effects of heavy ion irradiation on the optical, structural, and chemical properties of polyethylene terephthalate (PET) film used in commercial bottled water. PET bottles were exposed with 120 MeV Ni ions at fluences varying from 3 x 10{sup 10} to 3 x 10{sup 12} ion/cm{sup 2}. The modifications so induced were analyzed by using UV-Vis, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. Substantial decrease in optical band gap is observed with the increase in ion fluence. In the FTIR spectra, most of bands are decreased due the degradation of the molecular structure. XRD measurements show the decrease in peak intensity, which reflects the loss of crystallinity after irradiation.

36 MATERIALS SCIENCE↗

Tensile and fatigue behaviors of printed Ag thin films on flexible substrates

Flexible electronics using nanoparticle (NP) printing has been highlighted as a key technology enabling eco-friendly, low-cost, and large-area fabrication. For NP-based printing to be used as a successive alternative to photolithography and vacuum deposition, stretchability and long term reliability must be considered. This paper reports the stretchability and fatigue behavior of 100 nm thick NP-based silver thin films printed on polyethylene-terephthalate substrate and compares it to films deposited by electron-beam evaporation. NP-based films show stretchability and fatigue life comparable to evaporated films with intergranular fracture as the dominant failure mechanism.

36 MATERIALS SCIENCE↗

Flexible cobalt-phthalocyanine thin films with high charge carrier mobility

The structural and charge transport characteristics of cobalt phthalocyanine (CoPc) films deposited on flexible bi-axially oriented polyethylene terephthalate (BOPET) substrates are investigated. CoPc films exhibited a preferential (200) orientation with charge carrier mobility of {approx}118 cm{sup 2} V{sup -1} s{sup -1} (at 300 K). These films exhibited a reversible resistance changes upon bending them to different radius of curvature. The charge transport in CoPc films is governed by a bias dependent crossover from ohmic (J-V) to trap-free space-charge limited conduction (J-V{sup 2}). These results demonstrate that CoPc films on flexible BOPET having high mobility and high mechanical flexibility are a potential candidate for flexible electronic devices.

36 MATERIALS SCIENCE↗

An XPS study on the chemical bond structure at the interface between SiO{sub x}N{sub y} and N doped polyethylene terephthalate

The super-thin silicon oxynitride (SiO{sub x}N{sub y}) films were deposited onto the N doped polyethylene terephthalate (PET) surface. Varying the N doping parameters, the different chemical bond structures were obtained at the interface between the SiO{sub x}N{sub y} film and the PET surface. X-ray photoelectron spectra results showed that at the initial stage of SiO{sub x}N{sub y} film growth, the C=N bonds could be broken and C-N-Si crosslink bonds could be formed at the interface of SiO{sub x}N{sub y}/PET, which C=N bonds could be formed onto the PET surface during the N doping process. At these positions, the SiO{sub x}N{sub y} film could be crosslinked well onto the PET surface. Meanwhile, the doped N could crosslink the [SiO{sub 4}] and [SiN{sub 4}] tetrahedrons, which could easily form the dense layer structure at the initial stage of SiO{sub x}N{sub y} film growth, instead of the ring and/or chain structures of [SiO{sub 4}] tetrahedrons crosslinked by O. Finally, from the point of applying SiO{sub x}N{sub y}/PET complex as the substrate, the present work reveals a simple way to crosslink them, as well as the crosslink model and physicochemical mechanism happened at the interface of complex.

36 MATERIALS SCIENCE↗

Optical emission spectroscopic diagnostics of a non-thermal atmospheric pressure helium-oxygen plasma jet for biomedical applications

In this work, we have applied optical emission spectroscopy diagnostics to investigate the characteristics of a non-thermal atmospheric pressure helium plasma jet. The discharge characteristics in the active and afterglow region of the plasma jet, that are critical for biomedical applications, have been investigated. The voltage-current characteristics of the plasma discharge were analyzed and the average plasma power was measured to be around 18 W. The effect of addition of small fractions of oxygen at 0.1%-0.5% on the plasma jet characteristics was studied. The addition of oxygen resulted in a decrease in plasma plume length due to the electronegativity property of oxygen. Atomic and molecular lines of selected reactive plasma species that are considered to be useful to induce biochemical reactions such as OH transitions A{sup 2}{Sigma}{sup +}({nu}=0,1){yields}X{sup 2}{Pi}({Delta}{nu}=0) at 308 nm and A{sup 2}{Sigma}{sup +}({nu}=0,1){yields}X{sup 2}{Pi}({Delta}{nu}=1) at 287 nm, O I transitions 3p{sup 5}P{yields}3s{sup 5}S{sup 0} at 777.41 nm, and 3p{sup 3}P{yields}3s{sup 3}S{sup 0} at 844.6 nm, N{sub 2}(C-B) second positive system with electronic transition C{sup 3}{Pi}{sub u}{sup {yields}}B{sup 3}{Pi}{sub g}'' in the range of 300-450 nm and N{sub 2}{sup +}(B-X) first negative system with electronic transition B{sup 2}{Sigma}{sub u}{sup +}{yields}X{sup 2}{Sigma}{sub g}{sup +}({Delta}{nu}=0) at 391.4 nm have been studied. The atomic emission lines of helium were identified, including the He I transitions 3p{sup 3}P{sup 0}{yields}2s{sup 3}S at 388.8 nm, 3p{sup 1}P{sup 0}{yields} 2s{sup 1}S at 501.6 nm, 3d{sup 3}D{yields}2p{sup 3}P{sup 0} at 587.6 nm, 3d{sup 1}D{yields}2p{sup 1}P{sup 0} at 667.8 nm, 3s{sup 3}S{sup 1}{yields}2p{sup 3}P{sup 0} at 706.5 nm, 3s{sup 1}S{sup 0}{yields}2p{sup 1}P{sup 0} at 728.1 nm, and H{sub {alpha}} transition 2p-3d at 656.3 nm. Using a spectral fitting method, the OH radicals at 306-312 nm, the rotational and vibrational temperatures equivalent to gas temperatures of the discharge was measured and the effective non-equilibrium nature of the plasma jet was demonstrated. Our results show that, in the entire active plasma region, the gas temperature remains at 310 {+-} 25 K and 340 {+-} 25 K and it increases to 320 {+-} 25 K and 360 {+-} 25 K in the afterglow region of the plasma jet for pure helium and helium/oxygen (0.1%) mixture, respectively. Additionally, the vibrational temperatures range from 2200 {+-} 100 K and 2500 {+-} 100 K for pure helium and helium/oxygen (0.1%) mixture, respectively. The plasma jet was tested on heat sensitive polymer films used in biomedical applications such as polyethylene terephthalate and poly-L-lactide samples continuously for several minutes without causing any physical or thermal damage to the films. The plasma jet produces significant reactive species of interest while the gas temperatures remain very low demonstrating its potential for a range of biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗