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Recycled crumb rubber (RCR) is considered a reliable asphalt modifier and a solution to the problem of scrap tyre recycling. RCR-modified asphalt (RCRMA) typically has good low-temperature performance and storage stability. However, the pre-treatment of crumb rubber (CR) impairs its physical properties, resulting in poor high-temperature performance, which limits the industrial application of RCRMA. In this study, low-density polyethylene (LDPE) composite RCR was used to modify asphalt, and LDPE/RCR-composite-modified asphalt (L-RCRMA) was produced to compensate for the deficiencies in the high-temperature performance of RCRMA. The comprehensive physical properties of L-RCRMA were elucidated using tests such as the conventional properties, rotational viscosity, and rheological tests. The results showed that the incorporation of LDPE improved the high-temperature stability and rutting resistance of the asphalt, but an excessive amount of LDPE impaired the low-temperature performance and storage stability of L-RCRMA. Therefore, it is necessary to control the amount of LDPE to balance the performance of the asphalt. On this basis, we recommend a dosage of 20% for RCR and 1.5% for LDPE.
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Animals create high-performance fibers at natural ambient conditions via a unique spinning process. In contrast, the spinning technologies developed by human beings are usually clumsy and require sophisticated skills. Here, inspired by adhesion-based silkworm spinning, we report a microadhesion guided (MAG) spinning technology for instant and on-demand fabrication of micro/nanofibers. Enabled by the adhesion between the spinning fluids and the microneedles, the MAG spinning can generate micro/nanofibers with programmable morphology. By further mimicking the head movement of the silkworm spinning, the MAG technology is extended with three different modes: straight, vibratory, and twisted spinning, which generate oriented fibers, hierarchical cross-linked fibers, and all-in-one fibers, respectively. Due to the prevalence of microadhesion and its unprecedented flexibility in operation, equipment-free MAG spinning is finally realized for instant fiber fabrication by only polymeric foams. Finally, the MAG spinning is demonstrated as a promising instant technology for emergent applications, such as wound dressing.
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Bombyx , Nanofibras , Animais , Humanos , Biomimética , PolímerosRESUMO
Covalently crosslinked polymeric materials, known as thermosets, possess enhanced mechanical strength and thermal stability relative to the corresponding uncrosslinked thermoplastics. However, the presence of covalent inter-chain crosslinks that makes thermosets so attractive is precisely what makes them so difficult to reprocess and recycle. Here, we demonstrate the introduction of chemically cleavable groups into a bis-diazirine crosslinker. Application of this cleavable crosslinker reagent to commercial low-functionality polyolefins (or to a small-molecule model) results in the rapid, efficient introduction of molecular crosslinks that can be uncoupled by specific chemical inputs. These proof-of-concept findings provide one potential strategy for circularization of the thermoplastic/thermoset plastics economy, and may allow crosslinked polyolefins to be manufactured, used, reprocessed, and re-used without losing value. As an added benefit, the method allows the ready introduction of functionality into non-functionalized commodity polymers.
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Topochemical polymerizations hold the promise of producing high molecular weight and stereoregular single crystalline polymers by first aligning monomers before polymerization. However, monomer modifications often alter the crystal packing and result in non-reactive polymorphs. Here, we report a systematic study on the side chain functionalization of the bis(indandione) derivative system that can be polymerized under visible light. Precisely engineered side chains help organize the monomer crystals in a one-dimensional fashion to maintain the topochemical reactivity. By optimizing the side chain length and end group of monomers, the elastic modulus of the resulting polymer single crystals can also be greatly enhanced. Lastly, using ultrasonication, insoluble polymer single crystals can be processed into free-standing and robust polymer thin films. This work provides new insights on the molecular design of topochemical reactions and paves the way for future applications of this fascinating family of materials.
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Melt electrospun fibers, in general, have larger diameters than normally achieved with solution electrospinning. This study uses a modified nozzle to direct-write melt electrospun medical-grade poly(ε-caprolactone) onto a collector resulting in fibers with the smallest average diameter being 275 ± 86 nm under certain processing conditions. Within a flat-tipped nozzle is a small acupuncture needle positioned so that reduces the flow rate to ≈0.1 µL h-1 and has the sharp tip protruding beyond the nozzle, into the Taylor cone. The investigations indicate that 1-mm needle protrusion coupled with a heating temperature of 120 °C produce the most consistent, small diameter nanofibers. Using different protrusion distances for the acupuncture needle results in an unstable jet that deposited poor quality fibers that, in turn, affects the next adjacent path. The material quality is notably affected by the direct-writing speed, which became unstable above 10 mm min-1 . Coupled with a dual head printer, first melt electrospinning, then melt electrowriting could be performed in a single, automated process for the first time. Overall, the approach used here resulted in some of the smallest melt electrospun fibers reported to date and the smallest diameter fibers from a medical-grade degradable polymer using a melt processing technology.
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Device applications of shape memory polymers demand diverse shape changing geometries, which are currently limited to non-omnidirectional movement. This restriction originates from traditional thermomechanical programming methods such as uniaxial, biaxial stretching, bending, or compression. A solvent-modulated programming method is reported to achieve an omnidirectional shape memory behavior. The method utilizes freeze drying of hydrogels of polyethylene glycol networks with a melting transition temperature around 50 °C in their dry state. Such a process creates temporarily fixed macroporosity, which collapses upon heating, leading to significant omnidirectional shrinkage. These shrunken materials can swell in water to form hydrogels again and the omnidirectional programming and recovery can be repeated. The fixity ratio (R f ) and recovery ratio (R r ) can be maintained at 90% and 98% respectively upon shape memory multicycling. The maximum linear recoverable strain, as limited by the maximum swelling, is ≈90%. Amongst various application potentials, one can envision the fabrication of multiphase composites by taking advantages of the omnidirectional shrinkage from a porous polymer to a denser structure.
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Hidrogéis/química , Polietilenoglicóis/química , Liofilização , Tamanho da Partícula , Porosidade , Propriedades de SuperfícieRESUMO
Functional polymer composites have gained extensive interest due to their wide range of applications. Various functionalities are mainly provided by functional fillers and their networks in polymer matrix. Therefore, morphology control on filler network has important influence on the final functionalities. The confinement, assembly, and relaxation of inorganic functional fillers in polymers are thought as the basic issues related to such control. Processing as the means to achieve the desired shape and properties for materials often involves strong temperature and shear field, among other factors-not to mention the complex interaction between polymer and filler. These processing fields and interactions during processing are reported to have profound influence on the confinement, assembly, and relaxation of inorganic fillers in polymer matrix. Therefore, various functionalities could be significantly affected by processing. This paper is a review of recent developments in this area.
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Polímeros/química , Teste de Materiais , TemperaturaRESUMO
Flow-induced structure formation is investigated with in situ wide-angle X-ray diffraction with high acquisition rate (30 Hz) using isotactic polypropylene in a piston-driven slit flow with high wall shear rates (up to ≈900 s(-1) ). We focus on crystallization within the shear layers that form in the high shear rate regions near the walls. Remarkably, the kinetics of the crystallization process show no dependence on either flow rate or flow time; the crystallization progresses identically regardless. Stronger or longer flows only increase the thickness of the layers. A conceptual model is proposed to explain the phenomenon. Above a certain threshold, the number of shish-kebabs formed affects the rheology such that further structure formation is halted. The critical amount is reached already within 0.1 s under the current flow conditions. The change in rheology is hypothesized to be a consequence of the "hairy" nature of shish. Our results have large implications for process modelling, since they suggest that for injection molding type flows, crystallization kinetics can be considered independent of deformation history.
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Polipropilenos/química , Cristalização , Cinética , Polipropilenos/síntese química , Pressão , Reologia , Resistência ao Cisalhamento , Difração de Raios XRESUMO
This review summarizes the state-of-the-art knowledge of the usage of poly(hydroxy alkanoate)s in medical and sanitary applications. Depending on the monomers incorporated into the polymers and copolymers, this class of polymers exhibits a broad range of (thermo-)plastic properties, enabling their processing by, e.g., solution casting or melt extrusion. In this review, strategies for the polymer analogous modification of these materials and their surfaces are highlighted and correlated with the potential applications of the corresponding materials and blends. While the commercial availability of purified PHAs is addressed in brief, special focus is put on the (bio-)degradability of these polymers and ways to influence the degradation mechanism and/or the duration of degradation.
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Resource efficient processing of polymers is of paramount importance to minimize energy consumption, processing time, and material losses in the polymer industry. This study is concerned with polymer processing in planetary roller extruders. A three-dimensional numerical flow simulation was tailored to understand the polymer flow through the extruder in detail. Using the simulation software ANSYS Polyflow, we quantified both directly measurable process parameters, such as pressure build-up, and more intangible parameters, such as material shear. By varying operational and material parameters in a sensitivity analysis, we showed that the dynamics, material stress and pressure build-up are controlled primarily by the number of spindles and their rotational speed. Notably, this work provides the first successful validation of a 3D simulation of a polymer flow in a planetary roller extruder against actual experimental data. The simulation showed robust agreement between the simulated and experimental values, provided that a critical backpressure length is reached. This computational approach minimizes labor-intensive experimental testing in polymer processing.
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The helical arrangement of cardiac muscle fibres underpins the contractile properties of the heart chamber. Across the heart wall, the helical angle of the aligned fibres changes gradually across the range of 90-180°. It is essential to recreate this structural hierarchy in vitro for developing functional artificial tissue. Ice templating can achieve single-oriented pore alignment via unidirectional ice solidification with a flat base mould design. We hypothesise that the orientation of aligned pores can be controlled simply via base topography, and we propose a scalable base design to recapitulate the transmural fibre orientation. We have utilised finite element simulations for rapid testing of base designs, followed by experimental confirmation of the Bouligand-like orientation. X-ray microtomography of experimental samples showed a gradual shift of 106 ± 10°, with the flexibility to tailor pore size and spatial helical angle distribution for personalised medicine.
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Biobased plastics have the potential to be sustainable, but to explore their circularity further, current end-of-life options need to be broadened. Mechanical recycling is one of the most accepted methods to bring back plastics into the loop. Polyhydroxybutyrates (PHBs) are biobased and biodegradable in nature with promising properties and varied applications in the market. This study focuses on their potential for mechanical recycling by multiple extrusion cycles (E1-E5) and multi-faceted characterization of the virgin (V) and reprocessed materials from E1 to E5. The behavior is compared to polypropylene (PP) as a reference with a similar property profile, which has also been reprocessed five times. The thermal properties of both series showed a stable melting point and thermal decomposition temperature from thermal analyses (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)). However, a steady increase in the degree of crystallinity was observed which could counterbalance the decrease in molecular weight due to repeated extrusion measured by gel permeation chromatography and resulted in similar values of tensile strength across the cycles. The strain at break was impacted after the first extrusion, but no significant change was observed thereafter; the same was observed for impact strength. Even in scanning electron microscopy (SEM) images, virgin and E5 samples appeared similar, showing the stability of morphological characteristics. Fourier transform infrared spectroscopy (FTIR) results revealed that no new groups are being formed even on repeated processing. The deviation between the PHB and PP series was more predominant in the melt mass flow rate (MFR) and rheology studies. There was a drastic drop in the MFR values in PHB from virgin to E5, whereas not much difference was observed for PP throughout the cycles. This observation was corroborated by frequency sweeps conducted with the parallel plate method. The viscosity dropped from virgin to E1 and E2, but from E3 to E5 it presented similar values. This was in contrast to PP, where all the samples from virgin to E5 had the same values of viscosity. This paper highlights the possibilities of mechanical recycling of PHB and explains why future work with the addition of virgin material and other additives is an area to be explored.
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The development of Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) systems has provided significant advances in the processing and characterization of polymers. A fundamental understanding of ion-sample interactions is still missing despite FIB-SEM being routinely applied in microstructural analyses of polymers. This study applies Secondary Electron Hyperspectral Imaging to reveal oxygen and xenon plasma FIB interactions on the surface of a polymer (in this instance, polypropylene). Secondary Electron Hyperspectral Imaging (SEHI) is a technique housed within the SEM chamber that exhibits multiscale surface sensitivity with a high spatial resolution and the ability to identify carbon bonding present using low beam energies without requiring an Ultra High Vacuum (UHV). SEHI is made possible through the use of through-the-lens detectors (TLDs) to provide a low-pass SE collection of low primary electron beam energies and currents. SE images acquired over the same region of interest from different energy ranges are plotted to produce an SE spectrum. The data provided in this study provide evidence of SEHI's ability to be a valuable tool in the characterization of polymer surfaces post-PFIB etching, allowing for insights into both tailoring polymer processing FIB parameters and SEHI's ability to be used to monitor serial FIB polymer surfaces in situ.
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Expanded polytetrafluoroethylene (ePTFE) is promising in biomedical fields such as covered stents and plastic surgery owing to its excellent biocompatibility and mechanical properties. However, ePTFE material prepared by the traditional biaxial stretching process is with thicker middle and thinner sides due to the bowing effect, which poses a major problem in industrial-scale fabrication. To solve this problem, we design an olive-shaped winding roller to provide the middle part of the ePTFE tape with a greater longitudinal stretching amplitude than the two sides, so as to make up for the excessive longitudinal retraction tendency of the middle part when it is transversely stretched. The as-fabricated ePTFE membrane has, as designed, uniform thickness and node-fibril microstructure. In addition, we examine the effects of mass ratio of lubricant to PTFE powder, biaxial stretching ratio and sintering temperature on the performance of the resultant ePTFE membranes. Particularly, the relation between the internal microstructure of the ePTFE membrane and its mechanical properties is revealed. Besides stable mechanical properties, the sintered ePTFE membrane exhibits satisfactory biological properties. We make a series of biological assessments including in vitro hemolysis, coagulation, bacterial reverse mutation and in vivo thrombosis, intracutaneous reactivity test, pyrogen test and subchronic systemic toxicity test; all of the results meet the relevant international standards. The muscle implantation of the sintered ePTFE membrane into rabbits indicates acceptable inflammatory reactions of our sintered ePTFE membrane fabricated on industrial scale. Such a medical-grade raw material with the unique physical form and condensed-state microstructure is expected to afford an inert biomaterial potentially for stent-graft membrane.
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Polyhydroxybutyrate (PHB) is a promising biopolymer. However, processing PHB in pure form in thermoplastic processes is limited due to its rapid degradation, very low initial crystallization rate, strong post-crystallization, and its low final stretchability. In this article, we screened commercial PHBs for morphological characteristics, rheological properties, and "performance" in the meltblown process in order to reveal process-relevant properties and overcome the shortcoming of PHB in thermoplastic processes for fiber formation. An evaluation of degradation (extruded (meltblown) material vs. granules) was performed via rheological and SEC analysis. The study revealed large differences in the minimum melt temperature (175 up to 200 °C) and the grade-dependent limitation of accessible throughput on a 500 mm plant. The average fiber diameter could be lowered from around 10 µm to 2.4 µm in median, which are the finest reported values in the literature so far. It was found that the determination of the necessary process temperature can be predicted well from the complex shear viscosity. Different to expectations, it became apparent that a broader initial molar mass distribution (>8) is suitable to overcome the state-of-the art limitations of PHAs in order to stabilize fiber formation, increase the productivity, and obtain better resistance towards thermal degradation in process. Accordingly, longer polymer chain fractions could be more affected by degradation than medium and short polymer chains in the distribution. Further, a low initial narrow distributed molar mass resulted in too brittle fabrics.
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Polypropylene (PP) is one of the most abundant plastics used due to its low price, moldability, temperature and chemical resistance, and outstanding mechanical properties. Consequently, waste from plastic materials is anticipated to rapidly increase with continually increasing demand. When addressing the global problem of solid waste generation, post-consumer recycled materials are encouraged for use in new consumer and industrial products. As a result, the demand is projected to grow in the next several years. In this study, material recovery facility (MRF)-recovered post-consumer PP was utilized to determine its suitability for extrusion blow molded bottle food packaging. PP was sorted and removed from mixed-polymer MRF-recovered bales, ground, trommel-washed, then washed following the Association of Plastics Recyclers' protocols. The washed PCR-PP flake was pelletized then manually blended with virgin PP resin at 25%, 50%, 75, and 100% PCR-PP concentrations and fed into the extrusion blow molding (EBM) machine. The EBM bottles were then tested for physical performance and regulatory compliance (limits of TPCH: 100 µg/g). The results showed an increased crystallization temperature but no practical difference in crystallinity as a function of PCR-PP concentrations. Barrier properties (oxygen and water vapor) remained relatively constant except for 100% MRF-recovered PCR-PP, which was higher for both gas types. Stiffness significantly improved in bottles with PCR-PP (p-value < 0.05). In addition, a wider range of N/IAS was detected in PCR-PP due to plastic additives, food additives, and degradation byproducts. Lastly, targeted phthalates did not exceed the limits of TPCH, and trace levels of BPA were detected in the MRF PCR-PP. Furthermore, the study's results provide critical information on the use of MRF recovered in food packaging applications without compromising performance integrity.
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Herein, we reported the synthesis of TiO2 through different non-hydrolytic sol-gel (NHSG) routes in viscous polymer media. For the first time, the influence of the polymer nature (Polystyrene (PS) or Polypropylene (PP)) on the morphology of synthesized inorganic domains was investigated. The non-hydrolytic sol-gel reactions between titanium isopropoxide Ti(OiPr)4 and acetic anhydride in molten polypropylene lead to the formation of microfillers with a mean diameter of about 1 µm, while the same synthesis carried out in viscous polystyrene lead to the formation of nanofillers with diameter lower than 10 nm forming aggregates of approximately 200 nm. We have also investigated the influence of the oxygen donor nature on the morphology of synthesized fillers using aromatic oxygen donors in a polystyrene matrix. The use of benzoic anhydride or acetophenone as oxygen donors with Ti(OiPr)4 in viscous polystyrene lead to respectively platelet-like morphology or aggregated nanofillers. We demonstrated that the affinity between polymer, reactants, and/or by-products had an influence on the morphology and the size of in situ synthesized TiO2 fillers. These results evidenced for the first time the possibility to control and to tune the morphology of in situ grown inorganic objects through the NHSG process by the appropriate choice of solvent, here a viscous polymer medium, and reactants.
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The sustainable management of multilayer paper/plastic waste is a technological challenge due to its composite nature. In this paper, a mechanical recycling approach for multilayer cartons (MC) is reported, illustrating the realization of thermoplastic composites based on recycled polyethylene and an amount of milled MC ranging from 20 to 90 wt%. The effect of composition of the composites on the morphology and on thermal, mechanical, and water absorption behavior was investigated and rationalized, demonstrating that above 80 wt% of MC, the fibrous nature of the filler dominates the overall properties of the materials. A maleated polyethylene was also used as a coupling agent and its effectiveness in improving mechanical parameters of composites up to 60 wt% of MC was highlighted.
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A new member of low-dimensional structures with a high aspect ratio (LDHA) is introduced. For the first time, commodity polymer is processed into LDHA, which has long been stagnated by the lack of suitable processing techniques. The key to solve the current bottleneck is to overcome the trade-off between kinetic processability and thermodynamic stability. These two factors are both highly determined by intermolecular interaction level (IIL). Thus with a wide tuning range of IIL, ultrahigh molecular weight polyethylene (UHMWPE) is selected and investigated to break through the trade-off. Polymeric LDHA preparation needs both thinning and stiffening. By focusing on one then the other sequentially, they are realized simultaneously. Thus the over sixty-year-old material is finally thinned down by seven orders of magnitude into a 65.5 nm thick and 0.64 m2 large lamellar-thin framework (LTF). LTF exhibits a series of exceptional properties such as over-95% transparency, and seven times higher specific strength referred to steel. For the first time, cryogenic electron microscopy (Cryo-EM) is utilized to observe commodity polymers directly. This new LDHA material is promising to expand the scale boundaries of both fundamental research and practical applications, not only for UHMWPE, but also for more commodity polymers to come.
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Auditory sensors have shortcomings with respect to not only personalization with wearability and portability but also detecting a human voice clearly in a noisy environment or when a mask covers the mouth. In this work, an electret-powered and hole-patterned polymer diaphragm is exploited into a skin-attachable auditory sensor. The optimized charged electret diaphragm induces a voltage bias of >400 V against the counter electrode, which reduces the necessity of a bulky power source and enables the capacitive sensor to show high sensitivity (2.2 V Pa-1 ) with incorporation of an elastomer nanodroplet seismic mass. The sophisticated capacitive structure with low mechanical damping enables a flat frequency response (80-3000 Hz) and good linearity (50-80 dBSPL ). The hole-patterned electret diaphragms help the skin-attachable sensor detect only neck-skin vibration rather than dynamic air pressure, enabling a person's voice to be detected in a harsh acoustic environment. The sensor operates reliably even in the presence of surrounding noise and when the user is wearing a gas mask. Therefore, the sensor shows strong potential of a communication tool for disaster response and quarantine activities, and of diagnosis tool for vocal healthcare applications such as cough monitoring and voice dosimetry.