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Interesting facts about plastics and rubber

We come across plastics and rubber everywhere in our daily lives. Discover fascinating stories, surprising facts and interesting background information – from historical developments and well-known products to key figures and innovations in the industry.

Results (423)

  • From biopaste to bioplastic

    The biopaste used to print this cylinder consists of 50 percent lignin and 50 percent cellulose. Image: Lisa Ebers A viscous biopaste that is easy to process, solidifies quickly and is suitable for producing even complex structures using the 3D printing process has been developed by a research team headed by Prof. Dr. Marie-Pierre Laborie from the Chair of Forest Biomaterials at the University of Freiburg. The wood-based biodegradable synthetic could potentially be used in lightweight construction, amongst other things. The scientists have published their initial results in the journals Applied Bio Materials and Biomacromolecules. Lignin strengthens the cell walls of plants and causes them to turn woody (lignify) - a mechanism that helps plants to protect themselves against wind or pests. It is a waste product from paper manufacture and largely incinerated to produce bioenergy. "This is why we're researching into alternative possibilities for making better use of this raw material in future," says Laborie. As a result the team started to reexamine a combination of materials which was already investigated in the 1980s by an American research team. In this system, liquid crystals based on cellulose, the main component of plant cell walls, ensure not only the strength but also the good flow properties of the biopaste. The other component, lignin, can 'stick together' the microstructure in the process of creating the biosynthetic, as Robert Gleuwitz discovered in his doctoral thesis. Its orientation subsequently determines the characteristics of the biosynthetic: for instance, it can respond more rigidly or more flexibly, depending on the direction from which the force comes. Further research work will however be necessary until industrial application is possible, for example as a composite in lightweight construction. Until now the team has used exceptionally pure lignin which is produced in a pilot biorefinery at the Fraunhofer Center for Chemical-Biotechnological Processes (CBP) in Leuna - whether the waste product from the paper industry can also be directly processed still has to be researched. As Lisa Ebers shows in her doctoral thesis, the characteristics of the biosynthetic can also be varied in many ways, for instance by chemically processing or varying the components: Trials to date have used lignin from beech trees - if it is obtained from other plants it will have slightly different material characteristics such as different liquid crystals, even though they are all based on cellulose. The optimal quantity ratios also differ depending on the planned application. In addition, the researchers will soon be testing an entirely different possible use: the quality of soil can be analyzed with the help of the bio-based material. This takes place by studying the degradability of lignin and cellulose in various types of soil. The results arose from a research project by the Sustainability Center Freiburg and the Fraunhofer Society. The research and 3D printing trials took place in cooperation with Prof. Dr. Dr. Christian Friedrich and Dr. Gopakumar Sivasankarapillai at the Freiburg Materials Research Center (FMF) of the University of Freiburg and with Dr. Gilberto Siqueira in the Swiss Federal Laboratories for Materials Testing and Research (EMPA) in Dübendorf, Switzerland. References Gleuwitz, F.R./ Sivasankarapillai, G./ Siqueira, G./Friedrich, C./ Laborie, M.-P. G. (2020): Lignin in Bio-Based Liquid Crystalline Network Material with Potential for Direct Ink Writing. In: Applied Bio Materials. https://doi.org/10.1021/acsabm.0c00661 Gleuwitz, F.R./ Sivasankarapillai, G./Chen, Y./Friedrich, C./ Laborie, M.-P. G. (2020): Lignin-Assisted Stabilization of an Oriented Liquid Crystalline Cellulosic Mesophase, Part B: Toward the Molecular Origin and Mechanism. In: Biomacromolecules 21/6, p. 2276?2284. https://dx.doi.org/10.1021/acs.biomac.0c00220 Gleuwitz, F.R./Friedrich, C./Laborie, M.-P. G. (2020): Lignin-Assisted Stabilization of an Oriented Liquid Crystalline Cellulosic Mesophase, Part A: Observation of Microstructural and Mechanical Behavior. In: Biomacromolecules 21/3, p. 1069?1077. https://dx.doi.org/10.1021/acs.biomac.9b01352

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  • Surface deep: Light-responsive top layer of plastic film induces movement

    The film (l.) is mostly composed of a non-photoresponsive polymer (200-400 nm), and a photoresponsive polymer layer exists only at the surface (some nm thick). Photograph of the films and surface shape after UV radiation through a photomask (r-). Image: I. Kitamura/Springer Nature Scientists show that only a thin, topmost layer of the light-dependent azobenzene-containing plastic film needs to be light-sensitive, rather than the entire film, opening up new ways to potentially reduce production costs and revolutionize its use. Azobenzene-containing plastic film is a peculiar material; its surface can change shape when exposed to light, making it a valuable component in modern technologies/devices like TV screens and solar cells. Scientists now show that only a thin, topmost layer of the light-dependent azobenzene-containing plastic film needs to be light-sensitive, rather than the entire film, opening up new ways to potentially reduce production costs and revolutionize its use. So far, it had been widely accepted that the light-sensitive nature of this material extends throughout the whole film, but scientists did not understand what was causing the shape-shifting movement. A group of scientists led by Dr Takahiro Seki of Nagoya University, Japan, set out to figure out exactly how this happens; they have published their findings in the journal Scientific Reports. They cite a well-studied phenomenon called Marangoni flow as their inspiration: owing to this phenomenon, differences in "surface tension" (the property by which the particles in the outermost layer of liquids are always attracted inwards, creating a boundary for the liquid) cause many soft, plastic films to move in a peculiar pattern. The most famous example of this phenomenon is the formation of "wine legs" or droplets of liquid evaporating and streaking down the surfaces of wine glasses. They decided to test whether ultraviolet light triggered changes in the surface tension of azobenzene plastic film, and whether those changes resulted in the film moving. They chose to first cover azobenzene film with a very thin top layer that was light-sensitive, then exposed this film to UV radiation. Next, they did the same with film that was covered in a top layer unresponsive to light. To their excitement, the scientists found surface structural changes in the film with a light-sensitive top layer, but not in the film with a "light-insensitive" top layer. "This is the first time anyone has demonstrated that only the light responsiveness of a very thin 'nanometer' level layer is needed for azobenzene-containing film to alter its surface morphology under UV," said Dr Seki. An important observation of this study is that the movement of the material isn't dependent on "light polarization," or the direction in which light waves travel. If it were, that would suggest that there is another force on the molecular level affecting the whole film. Instead, Dr Seki concludes that it is probably the changes in chemical structure at the surface induced by the UV radiation that changes surface tension, inducing movement to the top of the film. Describing the wider ramifications of their results, Dr Seki states: "We are only at the cusp of developing this discovery onto an industrial scale, but you can imagine how needing only a very small amount of light-sensitive material can reduce costs. Many optical devices like photocopiers, printers, and monitors depend on the light-based surface change in azobenzene polymer film. Based on our findings, azobenzene film can also act as an "actuator" (that part in a device that moves other parts) in nanomachinery." These newly discovered properties have vast implications, from improving the economics of production and lowering material prices, to advancing the field of nanotechnology itself. Reference Kitamura et al., Photo-triggered large mass transport driven only by a photoresponsive surface skin layer, Scientific Reports 10 (2020), http://dx.doi.org/10.1038/s41598-020-69605-8

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  • Scientists develop "biorubber" glue for faster surgical recovery and pain relief

    Liquid CaproGlu gel applied to meat bought from the supermarket. When cured by UV light it turns into biorubber. Credit: NTU Singapore Materials scientists from Nanyang Technological University, Singapore (NTU Singapore) have invented a new type of surgical glue that can help join blood vessels and close wounds faster and may also serve as a platform to deliver pain relief drugs. In a paper published in Elsevier's Biomaterials in July jointly with clinicians from Singapore General Hospital (SGH), the NTU researchers showed that their glue can bond soft tissues including muscle and blood vessels, even when their surfaces are wet. Named CaproGlu, it is activated by a low dose of ultraviolet (UV) light that cures it in seconds, turning it from a liquid glue into a solid but flexible biorubber - a biocompatible material that can be resorbed by the tissue after a few weeks. The team showed in animal experiments that blood vessels can be rejoined with just four stitches and a mesh wrapper dipped in CaproGlu, compared to the usual eight stitches that are required for a reliable and unobstructed join. The authors estimate that this will reduce surgery time by 25 per cent, as surgeons spend less time and effort stitching up blood vessels and tissues. As demonstrated in animal experiments, CaproGlu can also be used to deliver local anaesthetics or pain relief medication to tissues in the body, which may be useful both during and after an operation and would reduce the need for pain relief medication to be administered afterwards. Unlike current bio-adhesives - which need two chemicals to be mixed prior to use - the CaproGlu is a one-pot liquid gel solution that comes ready-to-use. Lead authors of the paper, Associate Professor Terry W.J. Steele and Senior Research Fellow Dr Ivan Djordjevic, emphasised that most surgical adhesives available on the market do not work in water or wet environments as found in the human body. "To make our light-activated glue work on wet tissues, we engineered our glue to first remove water from the surface and thus allow adhesion to the dehydrated surfaces," said Assoc Prof Steele. "This unique advantage of being able to bond with high strength in a wet environment, as well as being biocompatible, is what makes CaproGlu so suitable to be used in surgery and medical applications." The adhesion strength of CaproGlu was compared to other commercial bioadhesives on the market and was found to be three to seven times stronger, and is on a par with the shear strength of collagen and muscle tissue found in the human body. Benefits of CaproGlu Invented by Assoc Prof Steele and Dr Djordjevic from the NTU School of Materials Science and Engineering, CaproGlu combines two ingredients into a single-component formulation that does not require additives. The first is polycaprolactone - a biodegradable polymer which has been approved by the United States Food and Drug Administration for specific applications used in the human body - and the second: diazirine, a light-sensitive molecule that can form strong bonds when activated. In their research paper which was published in the scientific journal Biomaterials, the scientists demonstrated how CaproGlu could be used as part of a new surgical method, where sutures are used in combination with a glue. Instead of the conventional eight stitches needed to join the two ends of a blood vessel in a rabbit, they used four stitches and wrapped the vessel ends with a biodegradable mesh dipped in CaproGlu and cured with a small dose of UV light which crosslinked the amino acids on the tissue's surface As a result, the bleeding from the artery immediately after the procedure was comparable to what is observed from conventional stitches. When harvested seven days later, the artery was shown to have completely healed. In a separate experiment, the surgeons inserted CaproGlu loaded with anaesthetics within rats' calves and cured them with UV light before the wound was closed with conventional stitches. The scientists compared the activity of these rats with two other controls: rats who had received anaesthetics alone and rats who had received CaproGlu without anaesthetics. They found no discernible impediment of movement for the rats which had anaesthetics and CaproGlu loaded with anaesthetics, suggesting that CaproGlu is successful in delivering local anaesthetics over time and could be a useful way to extend local anaesthesia beyond its current limits and also to act as a drug delivery platform for medication such as anticoagulants to prevent excessive blood clotting. The team also observed that there were no discernible side effects to the animals which had CaproGlu implanted in their skin, which suggested that it is safe and biocompatible as expected. Since the bioadhesive dissolves and resorbs within weeks, no follow up clinical visits would be required for its removal. Stable shelf life after sterilisation A big challenge for bioadhesives on the market today is to cope with the standard method by which surgical grade equipment and disposables are sterilised using gamma irradiation. The gamma sterilisation process destroys proteins and activates bonding in both acrylate and epoxy adhesives. Unlike other surgical adhesives available on the market, CaproGlu's protein-free formulation exploits new crosslinking chemistry unaffected by gamma sterilisation. The light-activated bonding mechanism forms chain links to amino acids at the nanoscale level, even after several months of storage and gamma sterilisation, thus making CaproGlu's production and commercialisation potentially less costly than those based on proteins and acrylates. Their biorubber glue innovation took the research team five years to develop and is the subject of a provisional patent filed through NTUitive, the university's innovation and enterprise company. Funding and support for the project include the NTU-Surgery Academic Clinical Programme Strategic Joint Research Fund, Singapore General Hospital Research Grant, NTU-Northwestern Institute for Nanomedicine Grant, NTUitive Proof of Concept (Gap) Fund, A*Star industry Alignment Fund (Pre-Positioning) and the Ministry of Education Tier 1 & 2 research fund. Moving forward, the joint team will be looking to conduct further animal experiments and to assess the performance of CaproGlu in other applications, such as on bone and other organic surfaces. Reference Djordjevic et al., CaproGlu: Multifunctional tissue adhesive platform, Biomaterials (2020), https://doi.org/10.1016/j.biomaterials.2020.120215

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  • Aerogel - the micro structural material of the future

    To demonstrate that fine aerogel structures can be produced in 3D printing, the researchers printed a lotus flower made of aerogel. Credit: EMPA Aerogel is an excellent thermal insulator. So far, however, it has mainly been used on a large scale, for example in environmental technology, in physical experiments or in industrial catalysis. Empa researchers have now succeeded in making aerogels accessible to microelectronics and precision engineering: An article in the latest issue of the scientific journal "Nature" shows how 3D-printed parts made of silica aerogels and silica composite materials can be manufactured with high precision. Behind the simple headline "Additive manufacturing of silica aerogels" - the article was published on July 20th in the renowned scientific journal Nature - a groundbreaking development is hidden. Silica aerogels are light, porous foams that provide excellent thermal insulation. In practice, they are also known for their brittle behaviour, which is why they are usually reinforced with fibres or with organic or biopolymers for large-scale applications. Due to their brittle fracture behaviour, it is also not possible to saw or mill small pieces out of a larger aerogel block. Directly solidifying the gel in miniaturised moulds is also not reliably - which results in high scrap rates. This is why aerogels have hardly been usable for small-scale applications. Stable, well-formed microstructures To demonstrate that fine aerogel structures can be produced in 3D printing, the researchers printed a lotus flower made of aerogel. Credit: EMPA The Empa team led by Shanyu Zhao, Gilberto Siqueira, Wim Malfait and Matthias Koebel have now succeeded in producing stable, well-shaped microstructures from silica aerogel by using a 3D printer. The printed structures can be as thin as a tenth of a millimeter. The thermal conductivity of the silica aerogel is just under 16 mW/(m*K) - only half that of polystyrene and even significantly less than that of a non-moving layer of air, 26 mW/(m*K). At the same time, the novel printed silica aerogel has even better mechanical properties and can even be drilled and milled. This opens up completely new possibilities for the post-processing of 3D printed aerogel mouldings. With the method, for which a patent application has now been filed, it is possible to precisely adjust the flow and solidification properties of the silica ink from which the aerogel is later produced, so that both self-supporting structures and wafer-thin membranes can be printed. As an example of overhanging structures, the researchers printed leaves and blossoms of a lotus flower. The test object floats on the water surface due to the hydrophobic properties and low density of the silica aerogel - just like its natural model. The new technology also makes it possible for the first time to print complex 3D multi-material microstructures. Insulation materials for microtechnology and medicine With such structures it is now comparatively trivial to thermally insulate even the smallest electronic components from each other. The researchers were able to demonstrate the thermal shielding of a temperature-sensitive component and the thermal management of a local "hot spot" in an impressive way. Another possible application is the shielding of heat sources inside medical implants, which should not exceed a surface temperature of 37 degrees in order to protect body tissue. A functional aerogel membrane 3D printing allows multilayer/multi-material combinations to be produced much more reliably and reproducibly. Novel aerogel fine structures become feasible and open up new technical solutions, as a second application example shows: Using a printed aerogel membrane, the researchers constructed a "thermos-molecular" gas pump. This permeation pump manages without any moving parts at all and is also known to the technical community as a Knudsen pump, named after the Danish physicist Martin Knudsen. The principle of operation is based on the restricted gas transport in a network of nanoscale pores or one-dimensional channels of which the walls are hot at one end and cold at the other. The team built such a pump from aerogel, which was doped on one side with black manganese oxide nanoparticles. When this pump is placed under a light source, it becomes warm on the dark side and starts to pump gases or solvent vapours. Air purification without moving parts These applications show the possibilities of 3D printing in an impressive way: 3D printing turns the high-performance material aerogel into a construction material for functional membranes that can be quickly modified to suit a wide range of applications. The Knudsen pump, which is driven solely by sunlight, can do more than just pump: If the air is contaminated with a pollutant or an environmental toxin such as the solvent toluene, the air can circulate through the membrane several times and the pollutant is chemically broken down by a reaction catalyzed by the manganese oxide nanoparticles. Such sun-powered, autocatalytic solutions are particularly appealing in the field of air analysis and purification on a very small scale because of their simplicity and durability. Empa researchers are now looking for industrial partners who want to integrate 3D-printed aerogel structures into new high-tech applications. Reference Zhao et al., Additive manufacturing of silica aerogels, Nature 584 (2020) 387-392, http://dx.doi.org/10.1038/s41586-020-2594-0

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  • No more playing with fire: Study offers insight into 'safer' rechargeable batteries

    Lithium dendrites deposited on the surface of carbon electrode are detected using nuclear magnetic resonance (NMR) analysis. The amount of lithium dendrite deposited is quantitively estimated from the 7Li NMR signal intensity. Credit: J. Mater. Chem. A 29 (2020) / The Royal Society of Chemistry Lithium-ion batteries are used in various electronic devices. But, they also come with potential hazards, particularly if the battery is damaged or overcharged. This usually occurs because, in its overcharged state, spiky structures called 'lithium dendrites' get deposited in the battery. Now, scientists at Okayama University use a technique called 'operando nuclear magnetic resonance' to track the precise mechanism of dendrite formation. They also extend their experiments to sodium-ion batteries, making their practical application easier. Lithium-ion batteries (LIBs) are a common type of rechargeable batteries. Their versatile nature and numerous applications in all sorts of electronic devices--from mobile phones to cars--makes them seem too good to be true. And perhaps they are: recently, there has been an increase in the number of fire-related incidents associated with LIBs, especially during charging, causing serious concerns over their safety. Scientists now know that these incidents can be due to the use of a broken or unauthorized charger. Often, improper use of these chargers and overcharging can lead to the formation of spiky structures on the negative electrode of the battery, called "lithium (Li) dendrites," which penetrate through the barrier between the negative and positive electrodes and cause a short circuit. Thus, looking at exactly how dendrite formation occurs is crucial to improving the safety of LIBs. Scientists at Okayama University, led by Associate Professor Kazuma Gotoh, recently took a step in this direction, in a new study published in Journal of Materials Chemistry A. They delved into finding the precise mechanism of dendrite formation in LIBs, in an effort to overcome their limitations and make their practical application easier. Dr Gotoh explains, "We wanted to analyze the formation of metal dendrites in secondary (rechargeable) batteries and contribute to improve the safety of batteries." Previous studies that tried to understand the process of Li dendrite formation were successful to some extent: they revealed that when the battery is in an overcharged state, dendrite formation occurs in the "overlithiation" phase of the battery cycle. But, these experiments were performed ex situ (outside the actual electrochemical environment), and thus the exact time of onset of dendrite formation was not found. In their new study, Dr Gotoh and his team decided to overcome this limitation. They figured that by applying "operando" methods (which replicate the electrochemical environment) to an analytical technique called "nuclear magnetic resonance" (NMR), they can accurately track the Li atoms in the inner structure of materials, which is not possible when using ex situ methods. Using this technique, the team had previously succeeded in observing the overcharged states of two types of negative electrodes--graphite and hard carbon electrodes--in the overlithiation phase of an LIB. In the new study, they took this to the next level by observing the state of these electrodes during the lithiation and delithiation process (the "charge and discharge" cycle of the battery). Their NMR analysis helped them to track the precise onset time of dendrite formation and Li deposition in the overcharged battery, for both the graphite and hard carbon electrodes. In graphite, they found the Li dendrites form soon after the "fully lithiated" phase of the electrode occurs. In the hard carbon electrode--in contrast--they observed that dendrites form only after "quasimetallic" Li clusters occur in the pores of hard carbon. Thus, the scientists deduced that when the battery is overcharged, the quasimetallic Li cluster formation acts as a buffer for the formation of Li dendrites in hard carbon electrodes. They even applied the same analysis to another type of rechargeable battery, called sodium-ion battery (NIB), and found similar results. Dr Gotoh explains, "We found that some carbon materials having inner pores (such as amorphous carbon) have a buffer effect for the deposition of Li and Na dendrites during overcharging of batteries. This knowledge will play an important role in ensuring the safety of LIBs and NIBs." By revealing the intricacies of the dendrite formation mechanisms in LIBs and NIBs, Dr Gotoh and his team provide useful insight into their safety. In fact, the scientists are optimistic that their findings can be applied to other types of rechargeable batteries in the future. Dr Gotoh concludes, "Our findings can be applied not only to LIBs and NIBs but also to next-generation secondary batteries such as all solid-state batteries. This is an important step in making their practical application easier." With the findings of this new study, we can hope that we possibly are one step closer to realizing our dream of truly sustainable energy resources. Reference Gotoh et al., Mechanisms for overcharging of carbon electrodes in lithium-ion/sodium-ion batteries analysed by operando solid-state NMR, Journal of Materials Chemistry A 29 (2020), http://dx.doi.org/10.1039/D0TA04005C

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  • A new two-dimensional carbon allotrope - semiconducting diamane film synthesized

    We demonstrate the realization of a pristine diamane through diamondization of mechanically exfoliated few-layer graphene via compression. Compared to gapless graphene, semiconducting h-diamane offers exciting possibilities for carbon-based electronic devices. Credit: Feng Ke Atomically thin diamond, also called diamane, is a two-dimensional carbon allotrope and has attracted considerable scientific interest due to its potential physical properties. However, previous studies suggest that atomically thin diamond films are not achievable in a pristine state because diamonds possess a three-dimensional crystalline structure and would lack chemical stability when thinned down to the thickness of diamond's unit cell due to the dangling sp3 bonds. Chemical functionalization of the surface carbons with specific chemical groups was considered necessary to stabilize the two-dimensional structure, such as surface hydrogenation or fluorination, and various substrates have also been used in these synthesizing attempts. But all of these attempts change the composition of diamond films, that is to say, the successful synthesis of a pristine diamane has up until now not been achieved. Regulating the phase transition process of carbon materials under high pressure and high temperature is always a straightforward method for achieving diamondization. Here, a team of scientists led by Drs. Feng Ke and Bin Chen from HPSTAR (the Center for High Pressure Science and Technology Advanced Research) used this direct approach, diamondization of mechanically exfoliated few-layer graphene via compression, to synthesize the long-sought-after diamane film. The study is published in Nano Letters. The diamondization process is usually accompanied by an opening of an energy gap and a dramatic resistance increase due to the sp2-sp3 rehybridization between carbon atoms. "The in-situ electrical transport measurements of few-layer graphene are difficult to carry out under high pressure," said Feng Ke. "However, using our recently developed photolithography-based microwiring technique to prepare film electrodes on a diamond surface for resistance measurements, we are able to study the pressure-induced sp2-sp3 diamondization transition of mechanically exfoliated graphene with layer thickness ranging from 12- to bilayer at room temperature." Their studies demonstrate that pristine h-diamane could be synthesized by compressing trilayer and thicker graphene to above 20 GPa at room temperature, which once synthesized could be preserved to about 1.0 GPa upon decompression. "The optical absorption reveals that h-diamane has an energy gap of 2.8 ± 0.3 eV, and further band structure calculations confirm an indirect band gap of 2.7-2.9 eV," explained the co-frist-author Lingkong Zhang, a PhD student at HPSTAR. "Compared to gapless graphene, semiconducting h-diamane offers exciting possibilities for carbon-based electronic devices." The XRD measurements have shown that the few-layer graphene to h-diamane transition is a gradual structural transition, which helps to understand the continuous resistance increase and absorbance decrease in trilayer and thicker graphene with pressure above the transition pressure. Theoretical calculations indicate that a (−2110)-oriented h-diamane is energetically stable and has a lower enthalpy than its few-layer graphene precursor above the transition pressure. "Like the discovery of graphene, carbon nanotubes, fullerenes, and other novel carbon allotropes, the realization of a pristine diamane represents another exciting achievement in materials science," added Dr. Bin Chen, "Thermal treatment at high pressure may be helpful to preserve a pristine h-diamane to ambient pressure, as suggested from the high-temperature and high-pressure method to synthesize a pressure quenchable h-diamond. The challenges still remain to achieve the preservation and industrial applications of diamane." Reference Ke et al., Synthesis of Atomically Thin Hexagonal Diamond with Compression, Nano Letters 20 (2020) 5916-5921, http://dx.doi.org/10.1021/acs.nanolett.0c01872

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  • Army researchers explore self-healing materials

    Army researchers expect to embed materials they developed with Texas A&M University collaborators in intelligent systems, allowing the material to autonomously adapt to its environment without external control. Credit: ourtesy Texas A&M University Army and Texas A&M University researchers developed a new material that can autonomously heal in air and underwater. The first-of-its-kind, 3-D printable and stimuli-responsive polymeric materials are expected to enable massive reconfigurability in future military platforms, which opens new opportunities for morphing unmanned air vehicles and robotic platforms, said Dr. Frank Gardea, an aerospace engineer and principal investigator of this work for the U.S. Army's Combat Capabilities Development Command's Army Research Laboratory. Army researchers envision a future platform, suitable for air and ground missions, with the reconfiguration characteristics of the T-1000 character in the Hollywood film, Terminator 2, he said. As the research matures, the epoxy material is expected to have the ability for massive reconfigurability and have embedded intelligence allowing it to autonomously adapt to its environment without any external control. "We want a system of materials to simultaneously provide structure, sensing and response," Gardea said. Currently, the stimulus this material responds to is temperature, which researchers first selected because of its ease of use during laboratory testing. In the real world, applying a temperature stimulus is not as easy or practical so they introduced light-responsiveness because of its easier to control and apply remotely, Gardea said. Polymers are made up of repeating units, like links on a chain. For softer polymers, these chains are only lightly connected to each other through crosslinks. The more crosslinks between chains, the more rigid the material becomes. "Most cross-linked materials, especially those that are 3-D printed, tend to have a fixed form, meaning that once you manufacture your part the material cannot be reprocessed or melted," he said. This new material has a dynamic bond that allows it to go from liquid to solid multiple times, which allows it to be 3-D printed and recycled. In addition, the dynamic bonds introduce a unique shape memory behavior, in which the material can be programmed and triggered to return to a remembered shape. The flexibility introduced to the polymer chain allows it to be fine-tuned, in unprecedented ways, to get either the softness of rubber or the strength of load-bearing plastics. Dr. Bryan Glaz, associate chief scientist for the lab's Vehicle Technology Directorate, said much of the previous work on adaptive materials were for materials systems that are either too soft for structural applications or otherwise not suitable for platform development so turning to epoxies, in some ways, is groundbreaking. Glaz said the research team's scientific advancement marks "a first step along a very long path toward realizing the scientific possibility for deep future platforms." This research is part of an exploratory research program led by the corporate laboratory to look at new scientific developments that may disrupt current scientific and technological paradigms 30 to 50 years from now. Glaz said exploratory research, like this, has current significant scientific risk and seeks to address numerous open scientific questions about material performance and durability. The researchers recently published their findings in a peer-reviewed journal, Advanced Functional Materials, in the paper, A Tailorable Family of Elastomeric-to-Rigid, 3D Printable, Interbonding Polymer Networks. The research is still in the discovery phase. The team started off trying to develop a 3-D printable material for structural applications that could be used to print components of UAVs or even rotorcraft. During this exploratory research, they noticed that after failure the surfaces became active and "would easily adhere to one another," Gardea said. This is when they decided to investigate the self-healing capabilities. Gardea said the immediate next steps are to enhance the actuation behavior and healing. The researchers also want to introduce multi-responsiveness and have the material respond to stimuli beyond temperature and light. This research supports challenges highlighted in the U.S. Army Functional Concept for Movement and Maneuver publication related to multi-domain operations and the Army Modernization Priority for Future Vertical Lift by improving knowledge of material behaviors that may be capable of introducing multi-functionality into far-future Army platforms. Reference Zhou et al., A Tailorable Family of Elastomeric‐to‐Rigid, 3D Printable, Interbonding Polymer Networks, Advanced Functional Materials 30 (2020), https://doi.org/10.1002/adfm.202002374

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  • Pothole repair made eco-friendly using grit from wastewater treatment

    Researchers are turning grit from wastewater (left) into a ceramic mortar that can be used as pothole filler (right). Credit: Zhongzhe Liu Potholes are aggravating to drive over, and they can cause billions of dollars of damage every year to automobiles. Now, scientists report a brand-new way to repair roads that's also eco-friendly - by using a remnant of wastewater treatment called grit that's usually disposed of in landfills. The researchers will present their results today at the American Chemical Society Fall 2020 Virtual Meeting & Expo. Potholes are aggravating to drive over, and they can cause billions of dollars of damage every year to automobile wheels, tires and suspensions. Currently, road crews fill in these holes with hydrocarbon-containing asphalt, but that material can leach out, polluting the environment. Now, scientists report a brand-new way to repair roads that's also eco-friendly - by using a remnant of wastewater treatment called grit that's usually disposed of in landfills. The researchers will present their results today at the American Chemical Society (ACS) Fall 2020 Virtual Meeting & Expo. ACS is holding the meeting through Thursday. It features more than 6,000 presentations on a wide range of science topics. "We had an idea to divert wastewater grit from landfills and turn it into a marketable product," says Zhongzhe Liu, Ph.D., who is presenting the work. "We formulated it into a ceramic mortar that could be used as a patch for pothole repair." The substance, known as grit assisted patch (GAP), is ultimately safer for the environment than hydrocarbon-based asphalt. But grit, a heavy, unbiodegradable solid, requires processing to become GAP. First, wastewater containing sewage, food scraps and other waste is processed at treatment plants. The result is clean water that is released into waterways, but also solids from the preliminary treatment that are mostly sand and gravel, and this is referred to as grit. Because grit contains pathogens and impurities that make it unsuitable for direct recycling, it is usually taken to a landfill and buried. Liu, who is at California State University-Bakersfield, and his collaborators were looking for ways to make grit useful, perhaps as a road material. They decided to incorporate it into a chemically bonded phosphate ceramic (CBPC). CBPCs are routinely used to treat hazardous or radioactive waste for disposal, but no one had used this yet on wastewater products. Because a CBPC contains ingredients that would inactivate microbes, the researchers thought this could be a good way to kill pathogens and end up with a material that could be safely applied to roads. "In the first step of making a CBPC, we mix the wet grit with calcium oxide and magnesium oxide, which form an alkaline grit slurry that prevents the proliferation of pathogens," Liu says. "The second step is to add a weak acid, potassium dihydrogen phosphate, into the pathogen-minimized alkaline slurry to form the grit-CBPC mortar." Conventional asphalt patch contains bitumen, a sticky, black residue left over after petroleum distillation. The conventional patch contains polycyclic aromatic hydrocarbons (known as PAHs) that are a risk to human health. A grit-formulated patch eliminates this environmental concern because its matrix is composed of calcium and magnesium oxides that are not toxic to people. So far, the researchers have analyzed GAP performance in the lab, showing it has a compressive strength comparable to asphalt pavement, and they believe its longevity will be superior to that of asphalt-based patches. The group has filed a patent for GAP based on these initial findings. In the meantime, they are working on improving GAP's compressive strength even further, so it could potentially be used for other applications, such as building wheel stops at the end of parking spots. The next step for getting GAP on the market as a pothole patch is to evaluate its bond strength when in contact with existing pavement and its durability when exposed to environmental extremes. The team is currently working on demonstration-scale experiments to field test GAP on an operational roadway with regular traffic. If necessary, they will explore additives to further improve the mechanical properties and durability of the new material. In addition, they plan to conduct a side-by-side comparison of GAP and conventional patch to gain a thorough understanding of the advantages it provides in terms of carbon footprint and economic benefit.

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  • No limit yet for carbon nanotube fibers

    The cross-section of a fiber produced at Rice University contains tens of millions of carbon nanotubes. The lab continually improves its method to make fibers, which tests show are now stronger than Kevlar. Credit: Pasquali Research Group/Rice University Carbon nanotube fibers made at Rice University are now stronger than Kevlar and are inching up on the conductivity of copper. The Rice lab of chemical and biomolecular engineer Matteo Pasquali reported in Carbon it has developed its strongest and most conductive fibers yet, made of long carbon nanotubes through a wet spinning process. In the new study led by Rice graduate students Lauren Taylor and Oliver Dewey, the researchers noted that wet-spun carbon nanotube fibers, which could lead to breakthroughs in a host of medical and materials applications, have doubled in strength and conductivity every three years, a trend that spans almost two decades. While that may never mimic Moore's Law, which set a benchmark for computer chip advances for decades, Pasquali and his team are doing their part to advance the method they pioneered to make carbon nanotube fibers. The lab's threadlike fibers, with tens of millions of nanotubes in cross section, are being studied for use as bridges to repair damaged hearts, as electrical interfaces with the brain, for use in cochlear implants, as flexible antennas and for automotive and aerospace applications. They are also part of the Carbon Hub, a multiuniversity research initiative launched in 2019 by Rice with support from Shell, Prysmian and Mitsubishi to create a zero-emissions future. "Carbon nanotube fibers have long been touted for their potential superior properties," Pasquali said. "Two decades of research at Rice and elsewhere have made this potential a reality. Now we need a worldwide effort to increase production efficiency so these materials could be made with zero carbon dioxide emissions and potentially with concurrent production of clean hydrogen." "The goal of this paper is to put forth the record properties of the fibers produced in our lab," Taylor said. "These improvements mean we're now surpassing Kevlar in terms of strength, which for us is a really big achievement. With just another doubling, we would surpass the strongest fibers on the market." The flexible Rice fibers have a tensile strength of 4.2 gigapascals (GPa), compared to 3.6 GPa for Kevlar fibers. The fibers require long nanotubes with high crystallinity; that is, regular arrays of carbon-atom rings with few defects. The acidic solution used in the Rice process also helps reduce impurities that can interfere with fiber strength and enhances the nanotubes' metallic properties through residual doping, Dewey said. Rice University graduate students Lauren Taylor and Oliver Dewey work to refine the process of making threadlike fibers from carbon nanotubes. Their fibers now surpass the strength of Kevlar. Credit: Pasquali Research Group/Rice University "The length, or aspect ratio, of the nanotubes is the defining characteristic that drives the properties in our fibers," he said, noting the surface area of the 12-micrometer nanotubes used in Rice fiber facilitates better van der Waals bonds. "It also helps that the collaborators who grow our nanotubes optimize for solution processing by controlling the number of metallic impurities from the catalyst and what we call amorphous carbon impurities." The researchers said the fibers' conductivity has improved to 10.9 megasiemens (million siemens) per meter. "This is the first time a carbon nanotube fiber has passed the 10 megasiemens threshold, so we've achieved a new order of magnitude for nanotube fibers," Dewey said. Normalized for weight, he said the Rice fibers achieve about 80% of the conductivity of copper. "But we're surpassing platinum wire, which is a big achievement for us," Taylor said, "and the fiber thermal conductivity is better than any metal and any synthetic fibers, except for pitch graphite fibers." The lab's goal is to make the production of superior fibers efficient and inexpensive enough to be incorporated by industry on a large scale, Dewey said. Solution processing is common in the production of other kinds of fibers, including Kevlar, so factories could use familiar processes without major retooling. "The benefit of our method is that it's essentially plug-and-play," he said. "It's inherently scalable and fits in with the way synthetic fibers are already made." "There's a notion that carbon nanotubes are never going to be able to obtain all the properties that people have been hyping now for decades," Taylor said. "But we're making good gains year over year. It's not easy, but we still do believe this technology is going to change the world." Co-authors of the paper are Rice alumnus Robert Headrick; graduate students Natsumi Komatsu and Nicolas Marquez Peraca; Geoff Wehmeyer, an assistant professor of mechanical engineering; and Junichiro Kono, the Karl F. Hasselmann Professor in Engineering and a professor of electrical and computer engineering, of physics and astronomy, and of materials science and nanoengineering. Pasquali is the A.J. Hartsook Professor of Chemical and Biomolecular engineering, of chemistry and of materials science and nanoengineering. The U.S. Air Force Office of Scientific Research, the Robert A. Welch Foundation, the Department of Energy's Advanced Manufacturing Office and the Advanced Research Projects Agency-Energy supported the research. Reference Taylor et al., Improved Properties, Increased Production, and the Path to Broad Adoption of Carbon Nanotube Fibers, Carbon (2020), https://doi.org/10.1016/j.carbon.2020.07.058

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  • A light bright and tiny: NIST scientists build a better nanoscale LED

    The fin LED pixel design includes the glowing zinc oxide fin (purple), isolating dielectric material (green), and metal contact (yellow atop green). Image: B. Nikoobakht / N. Hanacek, NIST A new design for light-emitting diodes (LEDs) developed by a team including scientists at the National Institute of Standards and Technology (NIST) may hold the key to overcoming a long-standing limitation in the light sources' efficiency. The concept, demonstrated with microscopic LEDs in the lab, achieves a dramatic increase in brightness as well as the ability to create laser light - all characteristics that could make it valuable in a range of large-scale and miniaturized applications. The team, which also includes scientists from the University of Maryland, Rensselaer Polytechnic Institute and the IBM Thomas J. Watson Research Center, detailed its work in a paper published today in the peer-reviewed journal Science Advances. Their device shows an increase in brightness of 100 to 1,000 times over conventional tiny, submicron-sized LED designs. "It's a new architecture for making LEDs," said NIST's Babak Nikoobakht, who conceived the new design. "We use the same materials as in conventional LEDs. The difference in ours is their shape." LEDs have existed for decades, but the development of bright LEDs won a Nobel prize and ushered in a new era of lighting. However, even modern LEDs have a limitation that frustrates their designers. Up to a point, feeding an LED more electricity makes it shine more brightly, but soon the brightness drops off, making the LED highly inefficient. Called "efficiency droop" by the industry, the issue stands in the way of LEDs being used in a number of promising applications, from communications technology to killing viruses. While their novel LED design overcomes efficiency droop, the researchers did not initially set out to solve this problem. Their main goal was to create a microscopic LED for use in very small applications, such as the lab-on-a-chip technology that scientists at NIST and elsewhere are pursuing. This photo shows a comb-like array of fin LEDs, some of which are glowing (bright spots at tips). Image: B. Nikoobakht / NIST The team experimented with a whole new design for the part of the LED that shines: Unlike the flat, planar design used in conventional LEDs, the researchers built a light source out of long, thin zinc oxide strands they refer to as fins. (Long and thin are relative terms: Each fin is only about 5 micrometers in length, stretching about a tenth of the way across an average human hair's breadth.) Their fin array looks like a tiny comb that can extend to areas as large as 1 centimeter or more. "We saw an opportunity in fins, as I thought their elongated shape and large side facets might be able to receive more electrical current," Nikoobakht said. "At first we just wanted to measure how much the new design could take. We started increasing the current and figured we'd drive it until it burned out, but it just kept getting brighter." Their novel design shone brilliantly in wavelengths straddling the border between violet and ultraviolet, generating about 100 to 1,000 times as much power as typical tiny LEDs do. Nikoobakht characterizes the result as a significant fundamental discovery. "A typical LED of less than a square micrometer in area shines with about 22 nanowatts of power, but this one can produce up to 20 microwatts," he said. "It suggests the design can overcome efficiency droop in LEDs for making brighter light sources." "It's one of the most efficient solutions I have seen," said Grigory Simin, a professor of electrical engineering at the University of South Carolina who was not involved in the project. "The community has been working for years to improve LED efficiency, and other approaches often have technical issues when applied to submicrometer wavelength LEDs. This approach does the job well." The team made another surprising discovery as they increased the current. While the LED shone in a range of wavelengths at first, its comparatively broad emission eventually narrowed to two wavelengths of intense violet color. The explanation grew clear: Their tiny LED had become a tiny laser. "Converting an LED into a laser takes a large effort. It usually requires coupling a LED to a resonance cavity that lets the light bounce around to make a laser," Nikoobakht said. "It appears that the fin design can do the whole job on its own, without needing to add another cavity." A tiny laser would be critical for chip-scale applications not only for chemical sensing, but also in next-generation hand-held communications products, high-definition displays and disinfection. "It's got a lot of potential for being an important building block," Nikoobakht said. "While this isn't the smallest laser people have made, it's a very bright one. The absence of efficiency droop could make it useful."

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  • Organic chemistry - a brilliant tool

    An international team led by the chemist Heinz Langhals of LMU Munich succeeded in molecular deflection of light radiation by means of Diamantane. Novel applications such as efficient light collectors or broadband light absorbers are promising. Diamantane, the second smallest and thus molecular diamond, is a highly fascinating material for chemists. It can be applied as rigid spacer and stiff pillar in molecular architectures so that optically functional units can be three-dimensionally arranged in well-defined larger assemblies. Noteworthy is: The diamond allows the vibration-mediated transmission of optical energy in light-collecting systems in spite of his firmness; this proceeds according to a mechanism that was recently discovered by an international group of researchers led by the chemist Heinz Langhals of LMU Munich, in which slow molecular bending vibrations play the key role. The work refers to an international co-operation. Researchers at the University of Stanford isolated the preparatively only laboriously accessible Diamantane efficiently from crude oil. Chemists in Taipei were responsible for the targeted functionalization. The researchers at the LMU Munich constructed the optical functional unit from adapted components. The newly found mechanism of energy transfer in such units causes consequences in physics because it requires a correction and extension of the theory of FRET where the familiar dipole interaction for the energy transfer is disproved as the exclusive mechanism and slow molecular vibronic processes have to be considered. On the other hand, this allows a 90° deflection of light simulating a 45° oriented molecular mirror useful for optical devices such as solar light-collecting systems where the high stability and rigidity of diamondoid spacers mean a special advantage for the construction of well-defined complex molecular structures. Reference Langhals et al., OrthoFRET in Diamantane FRET in Orthogonal Stiff Dyads; Diamond Restriction for Frozen Vibrations, Journal of Organic Chemistry (2020), http://dx.doi.org/10.1021/acs.joc.0c01184

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  • New catalyst efficiently turns carbon dioxide into useful fuels and chemicals

    Reference Taehee Kim and Tayhas R. Palmore, A scalable method for preparing Cu electrocatalysts that convert CO2 into C2+ products, Nature Communications 11 (2020), http://dx.doi.org/10.1038/s41467-020-16998-9

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