New Process Allows Full Recovery of Starting Materials From Tough Polymer Composites - Technology Org
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New Process Allows Full Recovery of Starting Materials From Tough Polymer Composites - Technology Org
In a win for chemistry, inventors at the Department of Energy’s Oak Ridge National Laboratory have designed a closed-loop path for synthesizing an exceptionally tough carbon-fiber-reinforced polymer, or CFRP, and later recovering all of its starting materials.
A polymer, functionalized carbon fibers and a crosslinker are mixed and cured. The components can be retrieved by addition of an alcohol, pinacol. Credit: Philip Gray and Anisur Rahman/ORNL, U.S. Dept. of Energy
A lightweight, strong and tough composite material, CFRP is useful for reducing weight and increasing fuel efficiency of automobiles, airplanes and spacecraft. However, conventional CFRPs are difficult to recycle. Most have been single-use materials, so their carbon footprint is significant. By contrast, ORNL’s closed-loop technology, which is published in Cell Reports Physical Science, accelerates addressing that grand challenge.
“We incorporated dynamic crosslinking into a commodity polymer to functionalize it. Then, we added a crosslinker to make it like thermoset materials,” said ORNL chemist and inventor Md Anisur Rahman. “Dynamic crosslinking allows us to break chemical bonds and reprocess or recycle the carbon fiber composite materials.”
A conventional thermoset material is permanently crosslinked. Once synthesized, cured, molded and set into a shape, it cannot be reprocessed. ORNL’s system, on the other hand, adds dynamic chemical groups to the polymer matrix and its embedded carbon fibers. The polymer matrix and carbon fibers can undergo multiple reprocessing cycles without loss of mechanical properties, such as strength and toughness.
Rahman led the study with ORNL chemist Tomonori Saito, who was honored by Battelle in 2023 as ORNL Inventor of the Year. Rahman and ORNL postdoctoral fellow Menisha Karunarathna Koralalage conducted most of the experiments. The trio has applied for a patent for the innovation.
“We invented a tough and recyclable carbon fiber composite,” said Saito. “The fiber and the polymer have a very strong interfacial adhesion due to the presence of dynamic bonds.” The interface locks materials together through covalent interactions and unlocks them on demand using heat or chemistry. Saito added, “The functionalized fiber has dynamic exchangeable crosslinking with this polymer. The composite structure is really tough because of the interface characteristics. That makes a very, very strong material.”
Conventional polymers like thermoset epoxies are typically used to permanently bond materials such as metal, carbon, concrete, glass, ceramic and plastic to form multicomponent materials such as composites. However, in the ORNL material, the polymer, carbon fibers and crosslinker, once thermoset, can be reincarnated back into those starting materials. The material’s components can be released for recycling when a special alcohol called a pinacol replaces the crosslinker’s covalent bonds.
Closed-loop recycling at laboratory scale results in no loss of starting materials. “When we recycle the composites, we recover 100% of the starting materials — the crosslinker, the polymer, the fiber,” Rahman said.
“That’s the importance of our work,” Saito said. “Other composite recycling technologies tend to lose the component starting materials during the recycling process.”
Other advantages of the reversibly crosslinked CFRPs are quick thermosetting, self-adhesive behavior and repair of microcracks in the composite matrix.
In the future, closed-loop recycling of CFRPs may transform low-carbon manufacturing as circular lightweight materials become incorporated into clean-energy technologies.
The researchers drew inspiration from nature, which employs dynamic interfaces to create robust materials. Nacre, the iridescent mother-of-pearl inside the shells of marine mussels and other mollusks, is exceptionally tough: it can deform without breaking. Moreover, marine mussels strongly adhere to surfaces but dissipate energy to release when necessary.
The researchers aimed to optimize interfacial chemistry between the carbon fibers and the polymer matrix to boost interfacial adhesion and enhance CFRP toughness. “Our composite’s strength is almost two times higher than a conventional epoxy composite,” Rahman said. “Other mechanical properties are also very good.”
The tensile strength, or the stress a material can bear when it is pulled, was the highest ever reported among similar fiber-reinforced composite materials. It was 731 megapascals — stronger than stainless steel and stronger than a conventional epoxy-based CFRP composite for automobiles.
In the ORNL material, the dynamic covalent bonding between the fiber interface and the polymer had 43% greater interfacial adhesion compared to polymers without dynamic bonds.
The dynamic covalent bonds enable closed-loop recycling. In a conventional matrix material, the carbon fibers are difficult to separate from the polymer. ORNL’s chemical method, which clips fibers at the functional sites, makes it possible to separate fibers from the polymer for reuse.
Karunarathna Koralalage, Rahman and Saito modified a commodity polymer, called S-Bpin, with assistance from Natasha Ghezawi, a graduate student at the Bredesen Center for Interdisciplinary Research and Graduate Education of the University of Tennessee, Knoxville. They created upcycled styrene ethylene butylene styrene copolymer, which incorporates boronic ester groups that covalently bond with a crosslinker and fibers to generate the tough CFRP.
Because CFRP is a complex material, its detailed characterization required diverse expertise and instrumentation. ORNL’s Chris Bowland tested tensile properties. With Raman mapping, ORNL’s Guang Yang showed the distribution of chemical and structural species.
Catalin Gainaru and Sungjin Kim, both of ORNL, captured rheological data, and Alexei Sokolov, a UT-ORNL Governor’s Chair, elucidated it. Scanning electron microscopy by Bingrui Li, of ORNL and UT, revealed that carbon fiber maintained its quality after recycling.
Vivek Chawla and Dayakar Penumadu, both of UT, analyzed interlaminar shear strength. With X-ray photoelectron spectroscopy, ORNL’s Harry Meyer III confirmed what molecules attached to fiber surfaces. ORNL’s Amit Naskar, a renowned expert in carbon fiber, reviewed the paper.
The scientists found that the degree of dynamic crosslinking is important. “We found 5% crosslinking works better than 50%,” Rahman said. “If we increase the crosslinker amount, it starts making the polymer brittle. That’s because our crosslinker has three hand-like bulky structures, able to make more connections and decrease the polymer’s flexibility.”
Next, the research team would like to conduct similar studies with glass-fiber composites, which maintain high performance while lowering the cost and carbon footprint of applications in aerospace, automotive, marine, sporting, construction and engineering. They also hope to reduce costs of the new technology to optimize commercial prospects for a future licensee.
“This step will open more applications, especially for wind turbines, electric vehicles, aerospace materials and even sporting goods,” Rahman said.
The Vehicle Technologies Office in DOE’s Office of Energy Efficiency and Renewable Energy sponsored the research. DOE’s Office of Electricity sponsored Raman mapping.
UT-Battelle manages ORNL for DOE’s Office of Science. The single largest supporter of basic research in the physical sciences in the United States, the Office of Science is working to address some of the most pressing challenges of our time. For more information, please visit energy.gov/science.
Source: Oak Ridge National Laboratory
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Fiber-reinforced Polymer (FRP) Composites Market Outlook, Analysis, Report 2022-2029
BlueWeave Consulting, a leading strategic consulting and market research firm, in its recent study, estimated the global fiber-reinforced polymer (FRP) composites market size at USD 238.7 billion in 2022. During the forecast period between 2023 and 2029, the global fiber-reinforced polymer (FRP) composites market size is projected to grow at an impressive CAGR of 7.21% reaching a value of USD 385.79 billion by 2029. Expanding automotive and consumer electronics manufacturing in nations like China and India is one of the key driving reasons for the global fiber-reinforced polymer (FRP) composites industry. Government spending on infrastructure development is also contributing to the growth in the market for FRP composites.
Global Fiber-reinforced Polymer (FRP) Composites Market – Overview
Fiber-reinforced Polymer (FRP) is a composite material composed of a polymer matrix reinforced with fibers. The most common fibers used are glass, carbon, or aramid, although other fibers, such as paper, wood, or asbestos, have occasionally been utilized. Fibers and a polymer matrix are the two main building blocks of FRP composite materials. FRP enables the alignment of thermoplastics' glass fibers to meet specified design objectives. The strength and resistance to deformation of the polymer can be increased by specifying the orientation of the reinforcing fibers.
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Based on application, the global fiber-reinforced polymer (FRP) Composites market is segmented into automotive, construction, firefighting, electronics, defense, and others. The construction sector accounts for the largest market share, as these materials offer a wide range of applications in this industry. Fiber-reinforced polymers are prominently used as reinforcements in concrete structures and underwater piping to prevent corrosion and impact. The automotive industry also covers a substantial market share owing to expanding automobile production, particularly in China and India, as they are used for the production of low-cost and light automobile parts.
Impact of COVID-19 on the Global Fiber-reinforced Polymer (FRP) Composites Market
The COVID-19 pandemic negatively impacted the growth of the global fiber-reinforced polymer (FRP) composites market. The lockdown implemented by the governments of various economies to curb the spread of the virus halted the operations of the end user sectors, particularly in the construction and automobile industries. In addition, constraints on FRP composites' production processes and supply networks themselves resulted in a severe scarcity of supplies, even after the pandemic, forcing the producers to suffer significant losses. However, the market is projected to pick up its pace during the forecast period as industries resume their operations.
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Major players operating in the global fiber-reinforced polymer (FRP) Composites market include American Fiberglass Rebar, American Grating, LLC, Engineered Composites Ltd., B&B FRP Manufacturing Inc., TUF-BAR, FRP Composites Inc., Ten Cate NV, Zoltek Companies, Inc., Hyosung Corporation, Mitsubishi Rayon Co., Ltd., SGL Group, and DowAksa. To further enhance their market share, these companies employ various strategies, including mergers and acquisitions, partnerships, joint ventures, license agreements, and new product launches.
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Massive growth of Short Fiber Reinforced Thermoplastic Composite Market 2030
The short fiber reinforced thermoplastic composite market is a rapidly growing industry that involves the use of composite materials made up of a thermoplastic matrix reinforced with short fibers, typically made of materials such as glass, carbon, or aramid.
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Continuous Fiber Reinforced Thermoplastic Composites for Electric Vehicles Market is expected to hold a significant market share in 2021 and is expected to grow during the period of 2022-2028.
Global Continuous Fiber Reinforced Thermoplastic Composites for Electric Vehicles market included in this report are analysis of the impact of COVID-19 outbreak on the points influencing the market growth. Additionally, the Continuous Fiber Reinforced Thermoplastic Composites for Electric Vehicles market by major key players, by type, by application and by major region, breaks down the outlook, business assessment, competitive scenario, trends and forecasts by upcoming years. The study of the Report is conducted on the basis of an important research methodology which provides an analytical examination of the global market on the basis of the various segments which have been marginalized by the industry as a summary and pre-scale of the market due to their different prospects
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