Discovery of a New Class of Enzymes to Convert Plant Waste into Eco-friendly Products

A cross-institutional team of scientists has engineered a new family of enzymes to convert plant waste into sustainable and high-value products, such as nylon, plastics and chemicals.

Lignin – A Main Component of New Enzymes

The newly engineered enzyme is active on lignin – one of the main components of plants, which scientists have been trying for decades to find a way of breaking down efficiently. Lignin acts as scaffolding in plants and is central to water-delivery. It provides strength and defence against pathogens.

Professor McGeehan, Director of the Centre for Enzyme Innovation in the School of Biological Sciences at Portsmouth said, “To protect their sugar-containing cellulose, plants have evolved a fascinatingly complicated material called lignin that only a small selection of fungi and bacteria can tackle. However, lignin represents a vast potential source of sustainable chemicals, so if we can find a way to extract and use those building blocks, we can create great things.”

“Cellulose and lignin are among the most abundant biopolymers on earth. The success of plants is largely due to the clever mixture of these polymers to create lignocellulose, a material that is challenging to digest,” he further added.

Engineering of Naturally Occurring Enzymes

The team’s goal is to discover enzymes from nature, bring them into our laboratories to understand how they work, then engineer them to produce new tools for the biotechnology industry. In this case, the team has taken a naturally occurring enzyme and engineered it to perform a key reaction in the breakdown of one of the toughest natural plant polymers.

Current enzymes tend to work on only one of the building blocks of lignin, making the breakdown process inefficient. Using advanced 3D structural and biochemical techniques the team has been able to alter the shape of the enzyme to accommodate multiple building blocks. The results provide a route to making new materials and chemicals such as nylon, bioplastics, and even carbon fiber, from what has previously been a waste product.

The discovery also offers additional environmental benefits – creating products from lignin reduces our reliance on oil to make everyday products and offers an attractive alternative to burning it, helping to reduce CO2 emissions.

An International Research Team of Specialized Experts

The research team was made up of an international team of experts in structural biology, biochemistry, quantum chemistry and synthetic biology at the Universities of Portsmouth, Montana State, Georgia, Kentucky and California, and two US national laboratories, NREL and Oak Ridge.

Professor McGeehan said, “We now have proof-of-principle that we can successfully engineer this class of enzymes to tackle some of the most challenging lignin-based molecules and we will continue to develop biological tools that can convert waste into valuable and sustainable materials.”

The research was jointly funded by the Biotechnology and Biological Sciences Research Council (BBSRC), National Science Foundation (NSF), and the DOE EERE Bioenergy Technologies Office. The 3D enzyme structures that underpinned this work were solved at the Diamond Light Source, the UK’s national synchrotron science facility in Oxford. 

Source: UoP News

Newly Engineered Thermoplastic Alloy by Polyscope Polymers for Medical Segment

Polyscope Polymers B.V. has introduced a new engineering thermoplastic alloy combining the benefits of styrene maleic anhydride (SMA) and polymethyl methacrylate (PMMA) to meet the needs of the rapidly growing point-of-care (POC) microfluidic medical test device segment. 

Features of XILOY™ Alloy

The injection moldable polymer, called XILOY™ SO2315 SMA/PMMA alloy, offers excellent optical properties, biocompatibility with a variety of proprietary coatings, reagents, and blood and tissue products, and maintains high dimensional stability to assure accurate and reliable immunoassay test results. The material is in use on devices completing their final agency reviews and expected to be commercially available to medical professionals soon.

Use of SMA and PMMA Alloy to Mold Microfluidic Cassettes

The newest material being used to mold microfluidic cassettes is an alloy of SMA and PMMA. The specific reactivity of anhydride groups on the SMA portion of XILOY SO2315 copolymer is especially helpful in microfluidic chip applications for its intrinsic ability to react with the “bioanchor,” which captures and binds to analytes (substances/chemicals of interest, e.g. amino acids, peptides, proteins) in the fluid sample, simplifying the post-mold coating process while, at the same time, making it more robust and cost-effective. 

SMA also provides higher thermal stability than PS for tests requiring heat to process samples, plus it maintains very-high dimensional stability to assure micro channels operate properly and cassettes fit into test devices. SMA is not especially miscible with PS, leading to a copolymer that is more opaque than transparent. Instead, chemists combine it with PMMA, with which it is highly miscible. 

The PMMA portion of the copolymer provides excellent transparency for optical detection test methods and has good biological compatibility with human tissue and fluids. The resulting copolymer is chemically compatible with the proprietary coatings and reagents typically used on microfluidic cassettes. It also processes easily and maintains consistent tight dimensions for intricate molded micro patterns that are critical to accurate and reliable rest results. 

Use of XILOY SO2315 Copolymer in Further Applications

In addition to use for disposable microfluidic cassettes for POC medical diagnostic devices, XILOY SO2315 copolymer is also appropriate for use in a variety of demanding applications in lighting, display, housewares, and consumer disposable applications. 

 

Source: Polyscope Polymers BV

Covestro Joins Carbon to Upscale 3D Printing for Digital Mass Production

Covestro has partnered Silicon Valley based tech company Carbon to upscale 3D Printing process 

to meet industrial demand of mass production. 

Joint Forces to Prove Mass Production Viability

Silicon Valley based company Carbon has developed Digital Light Synthesis™ (DLS™) technology, 

which can accelerate the production of parts up to a hundredfold compared to previous processes. 

After years of R&D, Carbon developed a novel polyurethane liquid resin suitable for production parts.

Covestro is a key partner in the scale-up and high-volume production of this material.

 The company invested a significant sum to enable the production in commercial quantity. 

As a result, joint forces proving mass production viability of the 3D-printing process and the 

respective material. 

"Our biggest challenge in the upscaling of additive manufacturing until series production lies in the supply of suitable materials in the required quality and quantity," explains Patrick Rosso, global head of additive manufacturing at Covestro. "By partnering with companies like Carbon, we are pushing existing scale boundaries and supporting various industries along the value chain on their way to digital mass production.” 

Production Using DLS™ Technology on a Large Scale

Efficient manufacturing process DLS™ technology developed by Carbon, is now being used for the 

first time on a large scale. Like stereolithography, the workpiece is created in a vat of liquid plastic

 resin that is cured by means of UV radiation. 

At Carbon’s DLS™ technology, oxygen is supplied from below to counteract the curing and thus 

creating a liquid dead zone. For this purpose, the bottom of the vessel is made of a light- and 

air-permeable membrane, like a contact lens. Due to this dead zone, the printed part can be 

pulled continuously upward without the formation of individual layers. 

Production using DLS™ technology is up to 100 times faster than with stereolithography – another

 important prerequisite for industrial mass production. In that context, a proprietary process combines 

software, hardware and materials. It imparts the desired technical and mechanical properties to the 

finished parts. 

Rising Demand of 3D Printing in Industrial Mass 

Production

3D printing offers unique opportunities to produce three-dimensional, often complex shaped parts 

in one single step. While predominantly prototypes and sample parts have been produced in small 

numbers so far, many industries are increasingly interested in industrial mass production. 

Covestro is currently researching materials to enable an extended range of industrial applications. 

To this end, the company is upgrading laboratories for 3D printing at its Leverkusen, Pittsburgh and 

Shanghai sites, where it develops and tests material solutions for serial additive manufacturing in 

collaboration with different customers. 
 

Source: Covestro

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Hemp fiber-reinforced plastic wins product of the year

An audience at the 16th EIHA Hemp Conference, which took place in Germany in June, has voted for a hemp fiber reinforced plastic material as one of its hemp products of the year.

BioLite, a polypropylene (PP) reinforced with 30% hemp fibers benefits from the strength of the fibers, making it strong, light and durable, its manufacturer, Trifilon, says. The new material is suitable for lightweight automotive construction and consumer goods and was used in this instance to make a trolley case.

Michelin & GM Develop New Generation of Airless Wheel Technology

Michelin and General Motors presented a new generation of airless wheel technology, the MICHELIN Uptis Prototype (or “Unique Puncture-proof Tire System”), at the Movin’On Summit for sustainable mobility. GM intends to develop this airless wheel assembly with Michelin and aims to introduce it on passenger vehicles as early as 2024.

Michelin Uptis Prototype

Later this year, GM will initiate real-world testing and validation of the Uptis Prototype on a Michigan test fleet of Chevrolet Bolt EVs.

“General Motors is excited about the possibilities that Uptis presents, and we are thrilled to collaborate with Michelin on this breakthrough technology,” said Steve Kiefer, senior vice president, Global Purchasing and Supply Chain, General Motors. “Uptis is an ideal fit for propelling the automotive industry into the future and a great example of how our customers benefit when we collaborate and innovate with our supplier partners.”

Airless Technology

Airless technology makes the Uptis Prototype eliminate flats and blowouts. This means Uptis offers significant potential for reducing the use of raw materials and waste, contributing to GM’s vision for a world with zero crashes, zero emissions and zero congestion as it:

• Reduces the number of punctured or damaged tires that are scrapped before reaching the end of their life cycle.
• Reduces the use of raw materials, energy for production and emissions linked to the manufacture of spare tires and replacement tires that are no longer required.
• Lasts longer by eliminating irregular wear and tear caused by over- or under-inflation.
• Reduces dangers related to flats and blowouts. 

Source: General Motors

New Industrial Process to Develop CO2-based Elastic Textile Fibers - Covestro & RWTH

Dress with CO2: Two research projects have succeeded in making elastic textile fibers based on CO2 and so partly replacing crude oil as a raw material. Covestro and its partners, foremost the Institute of Textile Technology at RWTH Aachen University and various textile manufacturers, are developing the production process on an industrial scale and aim to make the innovative fibers ready for the market. They can be used for stockings and medical textiles, for example, and might replace conventional elastic fibers based on crude oil. .

Further Milestone in the Use of CO2 as an Alternative Raw Material

The elastic fibers are made with a chemical component that consists in part of CO2 instead of oil. This precursor called cardyon® is already used for foam in mattresses and sports floorings. And now it is being applied to the textile industry.

“That’s a further, highly promising approach to enable ever broader use of carbon dioxide as an alternative raw material in the chemical industry and expand the raw materials base,” says Dr. Markus Steilemann, CEO of Covestro. “Our goal is to use CO2 in more and more applications in a circular economy process and save crude oil.” 

Sustainable Production Process

The fibers are made from CO2-based thermoplastic polyurethane (TPU) using a technique called melt spinning, in which the TPU is melted, pressed into very fine threads and finally processed into a yarn of endless fibers. Unlike dry spinning, which is used to produce conventional elastic synthetic fibers such as Elastane or Spandex, melt spinning eliminates the need for environmentally harmful solvents. A new chemical method enables carbon dioxide to be incorporated in the base material, which also has a better CO2 footprint than traditional elastic fibers. 

“The CO2-based material could be a sustainable alternative to conventional elastic fibers in the near future,” states Professor Thomas Gries, Director of the Institute of Textile Technology at RWTH Aachen University. “Thanks to our expertise in industrial development and processing, we can jointly drive establishment of a new raw materials base for the textile industry.” 

Development of the method of producing fibers from CO2-based thermoplastic polyurethane has been funded by the European Institute of Innovation and Technology (EIT). It will now be optimized as part of the “CO2Tex” project, which is to be funded by the German Federal Ministry of Education and Research (BMBF) so as to enable industrial production in the future. “CO2Tex” is part of “BioTex Future,” a project initiative of RWTH Aachen University. The initiative is devoted to developing production and processing technologies to facilitate the future market launch of textile systems from bio-based polymeric materials.

Development Partners Display Interest

What makes the CO2-based TPU fibers so special is their properties: They are elastic and tear-proof and so can be used in textile fabrics. Initial companies from the textile and medical engineering sectors have already tested the CO2-based fibers and processed them into yarns, socks, compression tubes and tapes. 

The aim of launching CO2-based textiles on the market is to promote a material cycle in the textile and clothing industry based on sustainable resources.

Source: Covestro

New Research Unveils Direct Synthesis of Graphene using Carbon Dioxide

The chemical compound carbon dioxide knows the general public as a greenhouse gas in the atmosphere and because of its climate-warming effect. However, carbon dioxide can also be a useful source of chemical reactions. A working group of the Karlsruhe Institute of Technology (KIT) in the journal ChemSusChem reports on such an unusual application. It uses carbon dioxide as a starting material to produce the currently very intensively investigated technology material graphene. 

Carbon Dioxide - A Useful Source of Chemical Reactions

The burning of fossil fuels such as coal and oil supplies energy for electricity, heat and mobility, but also leads to an increase in the amount of carbon dioxide in the atmosphere and thus to global warming. To cut through this causal chain, scientists are motivated to search for alternative sources of energy, but also alternative uses for carbon dioxide. One possibility could be to see the carbon dioxide as a favorable starting material for the synthesis of recyclables and thus in the economic recovery cycle - possibly even profitable - reintroduce.

An example of this can be found in nature: during photosynthesis in the leaves of plants, biomass is rebuilt from light, water and carbon dioxide and the natural material cycle is closed. In the process, it is the task of the metal-based enzyme RuBisCo to absorb the carbon dioxide from the air and make it usable for further chemical reactions in the plant. Inspired by this metal-based natural transformation, researchers at KIT are now presenting a process in which the greenhouse gas carbon dioxide, together with hydrogen, is directly transferred to the technology material graphene with the aid of specially prepared, catalytically active metal surfaces at temperatures of up to 1000 degrees Celsius.

Graphene

Graphene is the two-dimensional shape of the chemical element carbon, which has interesting electrical properties and is therefore suitable for future, novel electronic components. Its discovery and manipulation in 2004 led to worldwide, intensive research and in 2010 brought the discoverers Andre Geim and Konstanin Novoselov the Nobel Prize in Physics. The two took the graphene by hand from a block of graphite using adhesive tape.

Simple One-step Process

A collaboration of several working groups at KIT is now published in the journal ChemSusChema method to separate graphene by means of a metal catalyst of carbon dioxide and hydrogen. "If the metal surface has the right balance of copper and palladium, the conversion of carbon dioxide to graphene will take place directly in a simple one-step process," said study leader Professor Mario Ruben of the Molecular Materials Working Group at the Institute of Nanotechnology (INT) and at the Institute of Inorganic Chemistry (AOC) of KIT. 

In further experiments, the researchers even succeeded in producing the graphene with several layers of thickness, which could be of interest for possible applications in batteries, electronic components or filter materials. The next research objective of the working group is to shape functioning electronic components from the graphene obtained.

Source: Karlsruhe Institute of Technology

Porsche’s New Bioconcept-Car Features Natural-fiber Composite Body Parts

Automaker Porsche launches the new 718 Cayman GT4 Clubsport body parts made of natural-fiber composite materials developed in the Application Center for Wood Fiber Research HOFZET, which is part of the Fraunhofer Institute for Wood Research, Wilhelm-Klauditz-Institut WKI, together with the Institute for Bioplastics and Biocomposites IfBB of Hannover University of Applied Sciences and Arts.

Features of Porsche’s New Bioconcept-Car

The Bioconcept-Car’s driver and passenger doors and rear wing are made using a mixture of organic fibers. Vegetable fibers as a component in organic composites are a sustainable alternative for lightweight vehicle bodies. 

The years of experience with the ‘Bioconcept-Car’ were integrated in material development for the parts of the new 718 Cayman GT4 Clubsport, the first car in series production to feature body parts made of a natural-fiber composite material. The driver and passenger doors as well as the rear wing are made using a mixture of organic fibers. And the Cayman is a real lightweight, weighing in at only 1320 kilograms. A factor here is the 60-percent weight saving resulting from the use of organic composite materials instead of steel in the doors.

The composite material consists of a thermoset polymer matrix system reinforced with organic fibers. An organic fiber mesh is used because the raw materials are readily available, it exhibits high tensile strength, and is particularly fine, homogenous and drapable, easily fitting part shapes. The ease with which it can be produced to precise dimensions facilitate machining and quality assurance, even in combination with other conventionally manufactured components.

Porsche Starts Series Production

Joining forces with Porsche Motorsport, scientists at Fraunhofer WKI first tested organic materials for series readiness under extreme conditions on a Porsche Cayman GT4 Clubsport using the mobile development laboratory of the German “Four Motors” racing team.

“The third generation of the ‘Bioconcept-Car’ has been on the racetrack since 2015. The tests combine the advantage of extreme stress with a vehicle that is also street-legal after modifications. The partnership with Porsche AG also enables development under the realistic conditions of an automobile manufacturer,” says Ole Hansen, project manager at the Fraunhofer WKI Application Center for Wood Fiber Research HOFZET. “We’ve been able to continuously improve the material properties over the last four years.”

The German Federal Ministry for Food and Agriculture BMEL recognized the potential benefits of natural fibers from the very beginning and today still accompanies the project as a strategic partner. The BMEL promotes the development of biogenic light-weight components in the funding program “Renewable Resources” with the central coordinating agency for renewable resources, Fachagentur Nachwachsende Rohstoffe e.V. FNR.

Basis for High-Volume Production

Fraunhofer WKI also considered other factors in its investigations, including concepts for end-of-life recycling or reuse and scale-up approaches for parts that are to be produced in greater quantities.

“After extensive testing under extreme conditions on the racetrack, we continued to evaluate our parts, which ultimately led to the conclusion that these ecologically beneficial organic materials fulfill the criteria for volume production,” Ole Hansen adds. Smudo, front-man of the popular German rap group “Fantastische Vier” and permanent pilot of the Four Motors ‘Bioconcept-Car’, has tested its practical viability, as has a special passenger who enjoyed a test drive on the Nürburgring race course last August: German Federal Minister for Food and Agriculture, Julia Klöckner.

Rising Popularity of Electric Cars

Registration statistics indicate that new cars are progressively becoming heavier, due to improved safety functions and more electronic equipment. This weight gain also means higher levels of fuel consumption, aspects contrary to the general goal of reducing CO2 emissions. Weight is also an important factor for e-cars, since they require larger and thus heavier batteries in order to maximize range, a decisive sales criterium. 

Accordingly, new developments in lightweight design are an absolute prerequisite for truly efficient e-cars. According to a study by business consultants at McKinsey, the share of lightweight parts in automobiles will have to rise from 30 to 70 percent by 2030 to compensate for the vehicle weight increase resulting from electric drives and motors.

Good Complement to Carbon Fibers

Researchers at Fraunhofer WKI posed the question of whether other fibrous materials could be used to reduce component weight, only using carbon fibers in those places where they represent a structural advantage. They investigated various readily available ecological materials in terms of their technical properties, availability and cost-efficiency, since a feasible solution for industry must have positive technical, ecological and economic impacts. Natural-fiber-reinforced plastics turned out to be the answer. The biogenic component improves the ecological impact of industrial high-performance composite materials during manufacturing, use and disposal.

Economically speaking, the use of renewable raw materials is beneficial because natural flax, hemp, wood and jute fibers are less expensive than carbon fibers and require less energy to manufacture. Thus, the advantages of weight reduction don’t come with a  prohibitive price tag.

Additional advantages in industrial processing and with applications in the vehicle being the naturally grown structure of organic composites gives materials acoustic damping properties and reduces splintering, which is important in the event of a collision.

Source: Fraunhofer

New Cost-effective Way for Graphene Production Using Eucalyptus Trees

Researchers have developed a cost-effective and eco-friendly way of producing graphene using one of Australia’s most abundant resources, eucalyptus trees.

Cheaper and more Sustainable Synthesis Method

Graphene is the thinnest and strongest material known to humans. It’s also flexible, transparent and conducts heat and electricity 10 times better than copper, making it ideal for anything from flexible nanoelectronics to better fuel cells.

The new approach by researchers from RMIT University (Australia) and the National Institute of Technology, Warangal (India), uses Eucalyptus bark extract and is cheaper and more sustainable than current synthesis methods.

Increasing Graphene Availability to Industries Globally

RMIT lead researcher, Distinguished Professor Suresh Bhargava, said the new method could reduce the cost of production from USD 100 per gram to a staggering USD 0.5 per gram.

“Eucalyptus bark extract has never been used to synthesize graphene sheets before and we are thrilled to find that it not only works, it’s in fact a superior method, both in terms of safety and overall cost,” said Bhargava.

“Our approach could bring down the cost of making graphene from around USD 100 per gram to just 50 cents, increasing it availability to industries globally and enabling the development of an array of vital new technologies.” 

Distinctive Features:

Graphene’s distinctive features make it a transformative material that could be used in the development of flexible electronics, more powerful computer chips and better solar panels, water filters and bio-sensors.

Professor Vishnu Shanker from the National Institute of Technology, Warangal, said the ‘green’ chemistry avoids the use of toxic reagents, potentially opening the door to the application of graphene not only for electronic devices but also biocompatible materials.

“Working collaboratively with RMIT’s Centre for Advanced Materials and Industrial Chemistry we’re harnessing the power of collective intelligence to make a lot more useful discoveries,” he said.

A Novel Approach to Graphene Synthesis

Chemical reduction is the most common method for synthesizing graphene oxide as it allows for the production of graphene at a low cost in bulk quantities.

This method however relies on reducing agents that are dangerous to both people and the environment.

Source: RMIT University

Wind and Chemical Industries Join Hands for Wind Turbine Recycling

WindEurope, Cefic (the European Chemical Industry Council) and EUCIA (the European Composites Industry Association) have come together to create a cross-sector platform to advance innovative approaches to the recycling of wind turbine blades. 

Industries Speak

WindEurope CEO, Giles Dickson, said: “Wind energy is an increasingly important part of Europe’s energy mix. The first generation of wind turbines are now starting to come to the end of their operational life and be replaced by modern turbines. Recycling the old blades is a top priority for us and teaming up with the chemical and compositors industries will enable us to do it the most effective way.”

Cefic Director General, Marco Mensink, commented: “The chemical industry plays a decisive role in the transition to a circular economy by investing in the research and development of new materials, which make wind turbine blades more reliable, affordable and recyclable. Innovation is born from collaboration and we look forward to working together to advance wind turbine blade recycling.”

EUCIA President, Roberto Frassine, added: “The wind energy sector has always been at the forefront of using composites as they are instrumental to sustainable energy generation. With this collaboration we hope to set a great industry standard that ultimately will also help customers in other industries like marine and building & infrastructure.”

Learnings from wind turbine recycling will then be transferred to other markets to enhance the overall sustainability of composites.

Recycling Is Crucial

In the next five years 12,000 wind turbines are expected to be decommissioned. Broadening the range of recycling options is critical for the industry’s development. 
In 2018 wind energy supplied 14% of the electricity in the EU with 130,000 wind turbines and this number will only grow in the coming decades. 
Wind turbines blades are made up of a composite material, which boosts the performance of wind energy by allowing lighter and longer blades. Today, 2.5 million tons of composite material are in use in the wind energy sector.

Composite Material- Background Info

Composite materials are being recycled today at commercial scale through cement co-processing, where the cement raw materials are being partially replaced by the glass fibers and fillers in the composite, and the organic fraction replaces coal as a fuel. 

Through that process, the CO2 output of the cement manufacturing process can be significantly reduced (up to 16 % reduction is possible if composites represent 75 % of cement raw materials). Besides recycling through cement co-processing, alternative technologies like mechanical recycling, solvolysis and pyrolysis are being developed, ultimately providing the industry with additional solutions for end-of-life.

Source: WindEurope

XG Sciences to work with Sinochem and Yuyao PGS on graphene-enhanced thermoplastic composites

XG Sciences recently announced that it has entered into a memorandum of understanding with Sinochem Plastics and Yuyao PGS New Material Technology (an advanced materials development company focusing on the combination of graphene nanoplatelets and thermoplastic composites) to participate in developing advanced composites in China, based on its xGnP graphene nanoplatelets.

The Agreement strengthens the on-going relationship among the parties through creation of the Graphene Applications Development Center (GADC), a joint venture company between Sinochem Plastics and Yuyao PGS New Material Technology in the Sino-Italy Ningbo Ecological Park in Yuyao City. The parties recently partnered to bring new graphene enhanced anti-corrosion coatings to industrial and marine applications.

Under the Agreement, graphene-enhanced thermoplastic composites will be developed by GADC and will exclusively leverage graphene nanoplatelets produced by XG Sciences. The parties target a range of thermoplastic materials and end-use markets including automotive, industrial and consumer items such a clothing. Products resulting from the collaboration will be manufactured and sold in China through Sinochem and PGS.

“We are pleased to be able to partner with Sinochem and PGS to further leverage the performance of our materials in new advanced composite applications”, said Dr. Philip Rose, Chief Executive Officer, XG Sciences. “This activity further supports the value of our product offering on the international stage and allows XGS to strengthen our relationship with both Sinochem and PGS and leverage their market reach for our products in the important China market”, Dr. Rose further added.

“We have been supporting XGS in the China market since 2015”, said Dr. Shi Yan, President, Yuyao PGS New Material Technology Co., Ltd., “and we are excited to now combine our efforts with Sinochem Plastics under the Graphene Applications Development Center umbrella to create a new platform of materials.”