Textination Newsline

• Small, lightweight, stretchable, cost-efficient thermoelectric devices signify a breakthrough in sustainable energy development and waste heat recovery.
• Next-gen flexible energy harvesting systems will owe their efficiency to the integration of graphene nanotubes. They offer easy processability, stable thermoelectric performance, flexibility, and robust mechanical properties.
• Nanocomposites have high market potential in manufacturing generators for medical and smart wearables, vehicles sensors, and efficient building management.

Around half of the world’s useful energy is wasted as heat due to the limited efficiency of energy conversion devices. For example, one-third of a vehicle’s energy dissipates as waste heat in exhaust gases. At the same time, vehicles contain more and more electronic devices requiring electrical energy. As another example, lightweight wearable sensors for health and environmental monitoring are also becoming increasingly demanding. The potential to convert waste heat or solar energy into useful electrical power has emerged as an opportunity for more sustainable energy management. Convenient thermoelectric generators (TEGs) currently have only low effectiveness and a relatively large size and weight. Based on expensive or corrosion-vulnerable materials, they are rigid and often contain toxic elements.
 
Recently developed, easy-to-process, self-supporting and flexible nonwoven nanocomposite sheets demonstrate excellent thermoelectric properties combined with good mechanical robustness. A recent paper in ACS Applied Nano Materials described how researches combined a thermoplastic polyurethane (TPU) with TUBALLTM graphene nanotubes to fabricate a nanocomposite material capable of harvesting electrical energy from sources of waste heat.

Thanks to their high aspect ratio and specific surface area, graphene nanotubes provide TPU with electrical conductivity, making it possible to achieve high thermoelectrical performance while maintaining or improving mechanical properties. “Stiffness, strength, and tensile toughness were improved by 7, 25, and 250 times compared to buckypapers, respectively. Nanocomposite sheet shows low electrical resistivity of 7.5*10-3 Ohm×cm, high Young’s modulus of 1.8 GPa, failure strength of 80 MPa, and elongation at break of 41%,” said Dr. Beate Krause, Group Leader, Leibniz-Institut für Polymerforschung Dresden e. V.

Graphene nanotubes, being a fundamentally new material, provide an opportunity to replace current TEG materials with more environmentally friendly ones. The sensors powered by such thermoelectric generators could act as a “smart skin” for vehicles and buildings, providing sensoring capabilities to monitor performance and prevent potential issues before they lead to breakdowns, ensuring optimal operational efficiency. In aircraft, no-wire nanocomposites could serve as stand-alone sensors for monitoring deicing systems, eliminating the need for an extensive network of electrical cables. The high flexibility, strength, and reliability of graphene nanotube-enabled thermoelectric materials also extend their applications into the realm of smart wearable and medical devices.

Producing infection control clothing requires a lot of energy and uses lots of material resources. Fraunhofer researchers have now developed a technology which helps to save materials and energy when producing nonwovens. A digital twin controls key manufacturing process parameters on the basis of mathematical modeling. As well as improving mask manufacturing, the ProQuIV solution can also be used to optimize the production parameters for other applications involving these versatile technical textiles, enabling manufacturers to respond flexibly to customer requests and changes in the market.

Nonwoven infection control masks were being used in their millions even before the COVID-19 pandemic and are regarded as simple mass-produced items. Nevertheless, the manufacturing process used to make them needs to meet strict requirements regarding precision and reliability. According to DIN (the German Institute for Standardization), the nonwoven in the mask must filter out at least 94 percent of the aerosols in the case of the FFP-2 mask and 99 percent in the case of the FFP-3 version. At the same time, the mask must let enough air through to ensure that the wearer can still breathe properly. Many manufacturers are looking for ways to optimize the manufacturing process. Furthermore, production needs to be made more flexible so that companies are able to process and deliver versatile nonwovens for a wide range of different applications and sectors.

ProQuIV, the solution developed by the Fraunhofer Institute for Industrial Mathematics ITWM in Kaiserslautern, fulfills both of these aims. The abbreviation “ProQuIV” stands for “Production and Quality Optimization of Nonwoven Infection Control Clothing” (Produktions- und Qualitätsoptimierung von Infektionsschutzkleidung aus Vliesstoffen). The basic idea is that manufacturing process parameters are characterized with regard to their impact on the uniformity of the nonwoven, and this impact is then linked to properties of the end product; for example, a protective mask. This model chain links all relevant parameters to an image analysis and creates a digital twin of the production process. The digital twin enables real-time monitoring and automatic control of nonwoven manufacturing and thus makes it possible to harness potential for optimization.

Dr. Ralf Kirsch, who works in the Flow and Material Simulation department and heads up the Filtration and Separation team, explains: “With ProQuIV, the manufacturers need less material overall, and they save energy. And the quality of the end product is guaranteed at all times.”

Nonwoven manufacturing with heat and air flow
Nonwovens for filtration applications are manufactured in what is known as the
meltblown process. This involves melting down plastics such as polypropylene and forcing them through nozzles so they come out in the form of threads referred to as filaments. The filaments are picked up on two sides by air flows which carry them forward almost at the speed of sound and swirl them around before depositing them on a collection belt. This makes the filaments even thinner: By the end of the process, their thickness is in the micrometer or even submicrometer range. They are then cooled, and binding agents are added in order to create the nonwoven. The more effectively the temperature, air speed and belt speed are coordinated with each other, the more uniform the distribution of the fibers at the end and therefore the more homogeneous the material will appear when examined under a transmitted light microscope. Lighter and darker areas can thereby be identified — this is referred to by experts as cloudiness. The Fraunhofer team has developed a method to measure a cloudiness index on the basis of image data. The light areas have a low fiber volume ratio, which means that they are less dense and have a lower filtration rate. Darker areas have a higher fiber volume and therefore a higher filtration rate. On the other hand, the higher air flow resistance in these areas means that they filter a smaller proportion of the air that is breathed in. A larger proportion of the air flows through the more open areas which have a less effective filtration effect.

Production process with real-time control
In the case of ProQuIV, the transmitted light images from the microscope are used to calibrate the models prior to use. The experts analyze the current condition of the textile sample and use this information to draw conclusions about how to optimize the system — for example, by increasing the temperature, reducing the belt speed or adjusting the strength of the air flows. “One of the key aims of our research project was to link central parameters such as filtration rate, flow resistance and cloudiness of a material with each other and to use this basis to generate a method which models all of the variables in the production process mathematically,” says Kirsch. The digital twin monitors and controls the ongoing production process in real time. If the system deviates slightly from where it should be — for example, if the temperature is too high — the settings are corrected automatically within seconds.

Fast and efficient manufacturing
“This means that it is not necessary to interrupt production, take material samples and readjust the machines. Once the models have been calibrated, the manufacturer can be confident that the nonwoven coming off the belt complies with the specifications and quality standards,” explains Kirsch. ProQuIV makes production much more efficient — there is less material waste, and the energy consumption is also reduced. Another advantage is that it allows manufacturers to develop new nonwoven-based products quickly — all they have to do is change the target specifications in the modeling and adjust the parameters. This enables production companies to respond flexibly to customer requests or market trends.

This might sound logical but can be quite complex when it comes to development. The way that the values for filtration performance and flow resistance increase, for example, is not linear at all, and they are not proportional to the fiber volume ratio either. This means that doubling the filament density does not result in double the filtration performance and flow resistance — the relationship between the parameters is much more complex than that. “This is precisely why the mathematical modeling is so important. It helps us to understand the complex relationship between the individual process parameters,” says ITWM researcher Kirsch. The researchers are able to draw on their extensive expertise in simulation and modeling for this work.

More applications are possible
The next step for the Fraunhofer team is to reduce the breathing resistance of the nonwovens for the wearer without impairing the protective effect. This is made possible by electrically charging the fibers and employing a principle similar to that of a feather duster. The electric charge causes the textile fabric to attract the tiniest of particles which could otherwise slip through the pores. For this purpose, the strength of the electrostatic charge is integrated into the modeling as a parameter.

The Fraunhofer researchers’ plans for the application of this method extend far beyond masks and air filters. Their technology is generally applicable to the production of nonwovens — for example, it can also be used in materials for the filtration of liquids. Furthermore, ProQuIV methods can be used to optimize the manufacture of nonwovens used in sound-insulating applications.

Nonwoven production received more attention than ever before from the general public in Corona times, because the technical textile is crucial for infection protection. The ultra-fine nonwoven products are manufactured in so-called meltblown processes. A cross-departmental team at the Fraunhofer Institute for Industrial Mathematics ITWM in Kaiserslautern is optimizing the entire production chain in the »ProQuIV« project. Simulations help to guarantee the product quality of the filter material despite fluctuations in production.

The abbreviation »ProQuIV« stands for »Production and Quality Optimization of Nonwoven Infection Protection Clothing«. This is because bottlenecks in the production of these materials were particularly evident at the beginning of the Covid 19 crisis. For the meltblown nonwovens, this optimization of the product quality is also particularly difficult because the textiles react very sensitively to fluctuations in the manufacturing processes and material impurities.

Digital Twin Keeps an Eye on the Big Picture
»Meltblown« is the name of the industrial manufacturing process whose ultra-fine fiber nonwovens are responsible for providing the crucial filtering function in face masks. In this process, the molten polymer is forced through nozzles into a forward-flowing, high-speed stream. It is stretched and cooled in a highly turbulent air flow.

»The overall process of filter media production – from the polymer melt to the filter medium – presents a major challenge in simulation,« explains Dr. Konrad Steiner, head of the »Flow and Materials Simulation« department. »In the project, we kept the big picture in mind and developed a completely integrated evaluation chain as a digital twin. In doing so, we take several key components into account at once: We simulate the typical production processes of nonwovens, the formation of the fiber structures and then the material properties – here, in particular, the filter efficiency. This allows us to quantitatively evaluate the influences of the manufacturing process on the product properties.« In each of these individual areas, Fraunhofer ITWM and its experts are among the leading research groups internationally.

Homogeneity of the Material – Fewer Clouds in the Simulation Sky
In the meltblown process, a key factor is the behavior of the filaments in the turbulent, hot and fast air flow. The properties of the filaments are strongly influenced by this air flow. The quality of the filaments – and thus the quality of the nonwovens – is influenced by many factors. Dr. Dietmar Hietel, head of the »Transport Processes« department, knows what this means more precisely in practice. His team has been working at Fraunhofer ITWM for years on the simulation of various processes involving filaments, threads, and fibers. »The focus of the project is the so-called cloudiness, i.e. the non-uniformity of the fiber distributions in the nonwoven,« explains Hietel. »We are investigating the question: How homogeneous is the fabric? Because the quality of the products can be greatly improved if we increase the uniformity. Our simulations help figure out how to do that.«

Objective Evaluation of the Homogeneity of Nonwovens
The researchers also use appropriate image analysis techniques to quantify this cloudiness. The power spectrum plays a special role here. »The cloudiness index (CLI) describes homogeneity complementary to local basis weight and its variance,« describes Dr. Katja Schladitz. She brings her expertise in image processing to the project. »Our CLI ensures a robust assessment of the homogeneity and can thus be used for different material classes and imaging techniques to be used as an objective measure.« The frequencies that go into the CLI calculation can be chosen so that the CLI is meaningful for the particular application area.

Filtration: How Efficient Are the Filters?
For the upscaling to industrial processes such as mask production, the ITWM expertise in filters is also included in the project. The »Filtration and Separation« team led by Dr. Ralf Kirsch has been working for years on the mathematical modeling and simulation of various separation processes.

»What's special about this project is that we calculated the efficiency of the filters for fluctuations of varying degrees in the fiber volume fraction,« emphasizes Kirsch. »This allows us to specify up to what level of cloudiness the required filter efficiency can be achieved at all.« As a current example of this, the figure depicts in the graphic the efficiency of a filter material for N95 masks as a function of the inhomogeneity of the nonwoven.

ITMW Methods Support Across the Entire Process Chain
In »ProQuIV«, digital twins and calculations from Fraunhofer ITWM support a holistic view and better understanding of the processes. The production of technical textiles thus not only becomes more efficient, but the nonwovens can be developed virtually without having to realize this in advance in a test facility. In this way, production capacities can be increased while maintaining or even increase the quality. Together with long-term partners from industry, the research can be put into practice quickly and efficiently.

Simulations save textile companies experiments, allow new insights, enable systematic parameter variations and solve upscaling problems that can otherwise lead to bad investments during the transition from laboratory plant to industrial plant. However, virtual implementation of nonwoven production also opens up new opportunities for optimization at other levels. For example, acoustic insulating nonwovens or even hygiene nonwovens can also be optimized in terms of their product quality precisely with regard to the material properties to be achieved – while taking into account the process fluctuations that occur.

The project is part of the Fraunhofer-Gesellschaft's »Fraunhofer versus Corona« program and was completed in April 2021. The results will flow into several follow-up projects with the nonwovens industry.

• Circular economy for plastics: Fraunhofer, SABIC, and Procter & Gamble join forces

The Fraunhofer Cluster of Excellence Circular Plastics Economy CCPE and its Institute for Environmental, Safety and Energy Technology UMSICHT have developed an advanced recycling process for used plastics. The pilot project with SABIC and Procter & Gamble serves to demonstrate the feasibility of closed-loop recycling for single-use facemasks.

The transformation from a linear to a circular plastics economy can only succeed with a multi-stakeholder approach. The Fraunhofer Cluster of Excellence Circular Plastics Economy CCPE combines the competencies of six institutes of the Fraunhofer-Gesellschaft and cooperates closely with partners from industry. Together, we work on systemic, technical and social innovations and keep an eye on the entire life cycle of plastic products.  

Fraunhofer Institute for Environmental, Safety and Energy Technology UMSICHT is a pioneer in sustainable energy and raw materials management by supplying and transferring scientific results into companies, society and politics. Together with partners, the dedicated UMSICHT team researches and develops sustainable products, processes and services which inspire.

Fraunhofer Institute UMSICHT, SABIC and Procter & Gamble (P&G) are collaborating in an innovative circular economy pilot project which aimed to demonstrate the feasibility of closed-loop recycling of single-use facemasks.

Due to COVID-19, use of billions of disposable facemasks is raising environmental concerns especially when they are thoughtlessly discarded in public spaces, including - parks, open-air venues and beaches. Apart from the challenge of dealing with such huge volumes of essential personal healthcare items in a sustainable way, simply throwing the used masks away for disposal on landfill sites or in incineration plants represents a loss of valuable feedstock for new material.

“Recognizing the challenge, we set out to explore how used facemasks could potentially be returned into the value chain of new facemask production,” says Dr. Peter Dziezok, Director R&D Open Innovation at P&G. “But creating a true circular solution from both a sustainable and an economically feasible perspective takes partners. Therefore, we teamed up with Fraunhofer CCPE and Fraunhofer UMSICHT’s expert scientists and SABIC’s T&I specialists to investigate potential solutions.”

As part of the pilot, P&G collected used facemasks worn by employees or given to visitors at its manufacturing and research sites in Germany. Although those masks are always disposed of responsibly, there was no ideal route in place to recycle them efficiently. To help demonstrate a potential step change in this scenario, special collection bins were set up, and the collected used masks were sent to Fraunhofer for further processing in a dedicated research pyrolysis plant.

“A single-use medical product such as a face mask has high hygiene requirements, both in terms of disposal and production. Mechanical recycling, would have not done the job” explains Dr. Alexander Hofmann, Head of Department Recycling Management at Fraunhofer UMSICHT. “In our solution, therefore, the masks were first automatically shredded and then thermochemically converted to pyrolysis oil.

Pyrolysis breaks the plastic down into molecular fragments under pressure and heat, which will also destroy any residual pollutants or pathogens, such as the Coronavirus. In this way it is possible to produce feedstock for new plastics in virgin quality that can also meet the requirements for medical products” adds Hofmann, who is also Head of Research Department “Advanced Recycling” at Fraunhofer CCPE.

The pyrolysis oil was then sent to SABIC to be used as feedstock for the production of new PP resin. The resins were produced using the widely recognized principle of mass balance to combine the alternative feedstock with fossil-based feedstock in the production process. Mass balance is considered a crucial bridge between today’s linear economy and the more sustainable circular economy of the future.

“The high-quality circular PP polymer obtained in this pilot clearly demonstrates that closed-loop recycling is achievable through active collaboration of players from across the value chain,” emphasizes Mark Vester, Global Circular Economy Leader at SABIC. “The circular material is part of our TRUCIRCLE™ portfolio, aimed at preventing valuable used plastic from becoming waste and at mitigating the depletion of fossil resources.”

Finally, to close the loop, the PP polymer was supplied to P&G, where it was processed into non-woven fibers material. “This pilot project has helped us to assess if the close loop approach could work for hygienic and medical grade plastics.” says Hansjörg Reick, P&G Senior Director Open Innovation. “Of course, further work is needed but the results so far have been very encouraging”.

The entire closed loop pilot project from facemask collection to production was developed and implemented within only seven months. The transferability of advanced recycling to other feedstocks and chemical products is being further researched at Fraunhofer CCPE.