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Chemist Unlocks Plastic Alternatives Using Proteins and Clothing Scraps Photo: Challa Kumar, professor emeritus of chemistry, in his lab. (Contributed photo)
21.12.2023

Chemist Unlocks Plastic Alternatives Using Proteins and Clothing Scraps

Challa Kumar has developed methods to create novel plastic-like materials using proteins and fabric.

Every year, 400 million tons of plastic waste are generated worldwide. Between 19 and 23 million tons of that plastic waste makes its way into aquatic ecosystems, and the remaining goes into the ground. An additional 92 million tons of cloth waste is generated annually.

Challa Kumar, professor emeritus of chemistry, “fed up” with the tremendous amount of toxic waste people continually pump into the environment, felt compelled to do something. As a chemist, doing something meant using his expertise to develop new, sustainable materials.

“Everyone should think about replacing fossil fuel-based materials with natural materials anywhere they can to help our civilization to survive,” Kumar says. “The house is on fire, we can’t wait. If the house is on fire and you start digging a well – that is not going to work. It’s time to start pouring water on the house.”

Challa Kumar has developed methods to create novel plastic-like materials using proteins and fabric.

Every year, 400 million tons of plastic waste are generated worldwide. Between 19 and 23 million tons of that plastic waste makes its way into aquatic ecosystems, and the remaining goes into the ground. An additional 92 million tons of cloth waste is generated annually.

Challa Kumar, professor emeritus of chemistry, “fed up” with the tremendous amount of toxic waste people continually pump into the environment, felt compelled to do something. As a chemist, doing something meant using his expertise to develop new, sustainable materials.

“Everyone should think about replacing fossil fuel-based materials with natural materials anywhere they can to help our civilization to survive,” Kumar says. “The house is on fire, we can’t wait. If the house is on fire and you start digging a well – that is not going to work. It’s time to start pouring water on the house.”

Kumar has developed two technologies that use proteins and cloth, respectively, to create new materials. UConn’s Technology Commercialization Services (TCS) has filed provisional patents for both technologies.

Inspired by nature’s ability to construct a diverse array of functional materials, Kumar and his team developed a method to produce continuously tunable non-toxic materials.

“Chemistry is the only thing standing in our way,” Kumar says. “If we understand protein chemistry, we can make protein materials as strong as a diamond or as soft as a feather.”

The first innovation is a process to transform naturally occurring proteins into plastic-like materials. Kumar’s student, Ankarao Kalluri ’23 Ph.D., worked on this project.

Proteins have “reactor groups” on their surfaces which can react with substances with which they come into contact. Using his knowledge of how these groups work, Kumar and his team used a chemical link to bind protein molecules together.

This process creates a dimer – a molecule composed to two proteins. From there, the dimer is joined with another dimer to create tetramer, and so on until it becomes a large 3D molecule. This 3D aspect of the technology is unique, since most synthetic polymers are linear chains.

This novel 3D structure allows the new polymer to behave like a plastic. Just like the proteins of which it is made, the material can stretch, change shape, and fold. Thus, the material can be tailored via chemistry for a variety of specific applications.

Unlike synthetic polymers, because Kumar’s material is made of proteins and a bio-linking chemical, it can biodegrade, just like plant and animal proteins do naturally.

“Nature degrades proteins by ripping apart the amide bonds that are in them,” Kumar says. “It has enzymes to handle that sort of chemistry. We have the same amide linkages in our materials. So, the same enzymes that work in biology should also work on this material and biodegrade it naturally.”

In the lab, the team found that the material degrades within a few days in acidic solution. Now, they are investigating what happens if they bury this material in the ground, which is the fate of many post-consumer plastics.

They have demonstrated that the protein-based material can form a variety of plastic-like products, including coffee cup lids and thin transparent films. It could also be used to make fire-resistant roof tiles, or higher-end materials like, car doors, rocket cone tips, or heart valves.

The next steps for this technology are to continue testing their mechanical properties, like strength or flexibility, as well as toxicity.

“I think we need to have social consciousness that we cannot put out materials into the environment that are toxic,” Kumar says. “We just cannot. We have to stop doing that. And we cannot use materials derived from fossil fuels either.”

Kumar’s second technology uses a similar principle, but instead of just proteins, uses proteins reinforced with natural fibers, specifically cotton.

“We are creating a lot of textile waste each year due to the fast-changing fashion industry” Kumar says. “So why not use that waste to create useful materials – convert waste to wealth.”

Just like the plastic-like protein materials (called “Proteios,” derived from original Greek words), Kumar expects composite materials made from proteins and natural fibers will biodegrade without producing toxic waste.

In the lab, Kumar’s former student, doctoral candidate Adekeye Damilola, created many objects with protein-fabric composites, which include small shoes, desks, flowers, and chairs. This material contains textile fibers which serve as the linking agent with the proteins, rather than the cross-linking chemical Kumar uses for the protein-based plastics.

The crosslinking provides the novel material with the strength to withstand the weight that would be put on something like a chair or a table. The natural affinity between fibers and proteins is why it’s so hard to get food stains out of clothing. This same attraction makes strong protein-fabric materials.

While Kumar’s team has only worked with cotton so far, they expect other fiber materials, like hemp fibers or jute, would behave similarly due to their inherent but common chemical properties with cotton.

“The protein naturally adheres to the surface of the protein,” Kumar says. “We used that understanding to say ‘Hey, if it binds so tightly to cotton, why don’t we make a material out of it.’ And it works, it works amazingly.”

With the support of TCS, Professor Kumar is currently seeking industry partners to bring these technologies to market. For more information contact Michael Invernale at michael.invernale@uconn.edu.

Source:

Anna Zarra Aldrich '20 (CLAS), Office of the Vice President for Research

Firefighter Photo: 12019 at Pixabay
11.12.2023

Study tests firefighter turnout gear with, without PFAS


Transitioning away from per- and polyfluoroalkyl substances (PFAS), which offer water- and oil-repelling properties on the outer shells of firefighter turnout gear, could bring potential performance tradeoffs, according to a new study from North Carolina State University.

The study showed that turnout gear without PFAS outer shell coatings were not oil-repellent, posing a potential flammability hazard to firefighters if exposed to oil and flame, said Bryan Ormond, assistant professor of textile engineering, chemistry and science at NC State and corresponding author of a paper describing the research.

“All oil repellents can also repel water, but all water repellents don’t necessarily repel oil,” Ormond said. “Diesel fuel is really difficult to repel, as is hydraulic fluid; in our testing, PFAS-treated materials repel both. In our tests, turnout gear without PFAS repelled water but not oil or hydraulic fluid.


Transitioning away from per- and polyfluoroalkyl substances (PFAS), which offer water- and oil-repelling properties on the outer shells of firefighter turnout gear, could bring potential performance tradeoffs, according to a new study from North Carolina State University.

The study showed that turnout gear without PFAS outer shell coatings were not oil-repellent, posing a potential flammability hazard to firefighters if exposed to oil and flame, said Bryan Ormond, assistant professor of textile engineering, chemistry and science at NC State and corresponding author of a paper describing the research.

“All oil repellents can also repel water, but all water repellents don’t necessarily repel oil,” Ormond said. “Diesel fuel is really difficult to repel, as is hydraulic fluid; in our testing, PFAS-treated materials repel both. In our tests, turnout gear without PFAS repelled water but not oil or hydraulic fluid.

“Further, oils seem to spread out even more on the PFAS-free gear, potentially increasing the hazard.”

PFAS chemicals – known as forever chemicals because of their environmental persistence – are used in food packaging, cookware and cosmetics, among other uses, but have recently been implicated in higher risks of cancer, higher cholesterol levels and compromised immune systems in humans. In response, firefighters have sought alternative chemical compounds – like the hydrocarbon wax coating used in the study – on turnout gear to repel water and oils.

Besides testing the oil- and water-repelling properties of PFAS-treated and PFAS-free outer garments, the NC State researchers also compared how the outer shells aged in job-related exposures like weathering, high heat and repeated laundering, and whether the garments remained durable and withstood tears and rips.

The study showed that PFAS-treated and PFAS-free outer shells performed similarly after exposure to UV rays and various levels of heat and moisture, as well as passes through heating equipment – similar to a pizza oven – and through washing machines.

“Laundering the gear is actually very damaging to turnout gear because of the washing machine’s agitation and cleaning agents used,” Ormond said.

“We also performed chemical analyses to see what’s happening during the weathering process,” said Nur Mazumder, an NC State doctoral student in fiber and polymer science and lead author of the paper. “Are we losing the PFAS chemistries, the PFAS-free chemistries or both when we age the garments? It turns out that we lost significant amounts of both of these finishes after the aging tests.”

Both types of garments performed similarly when tested for strength against tearing the outer shell fabric. The researchers say the PFAS and PFAS-free coatings didn’t seem to affect this attribute.

Ormond said that future work will explore how much oil repellency is needed by firefighters out in the field.
“Even with PFAS treatment, you see a difference between a splash of fluid and soaked-in fluid,” Ormond said. “For all of its benefits, PFAS-treated gear, when soaked, is dangerous to firefighters. So we need to really ask ‘What do firefighters need?’ If you’re not experiencing this need for oil repellency, there’s no worry about switching to non-PFAS gear. But firefighters need to know the non-PFAS gear will absorb oil, regardless of what those oils are.”

Andrew Hall, another NC State doctoral student in fiber and polymer science and co-author on the paper, is also testing dermal absorption, or taking the aged outer shell materials and placing them on a skin surrogate for a day or two. Are outer shell chemicals absorbed in the skin surrogate after these admittedly extreme exposure durations?

“Firefighting as a job is classified as a carcinogen but it shouldn’t have to be,” Ormond said. “How do we make better gear for them? How do we come up with better finishes and strategies for them?

“These aren’t just fabrics,” Ormond said. “They are highly engineered pieces of material that aren’t easily replaced.”

The paper appears in the Journal of Industrial Textiles. Funding for the research came from the Federal Emergency Management Agency’s Assistance to Firefighters Grants Program.

Source:

North Carolina State University, Mick Kulikowski

Photo: zephylwer0, Pixabay
29.08.2023

Taming a fire: A new way with nanoscale material

High-temperature flames are used to create a wide variety of materials – but once you start a fire, it can be difficult to control how the flame interacts with the material you are trying to process. Researchers have now developed a technique that utilizes a molecule-thin protective layer to control how the flame’s heat interacts with the material – taming the fire and allowing users to finely tune the characteristics of the processed material.

“Fire is a valuable engineering tool – after all, a blast furnace is only an intense fire,” says Martin Thuo, corresponding author of a paper on the work and a professor of materials science and engineering at North Carolina State University. “However, once you start a fire, you often have little control over how it behaves.

High-temperature flames are used to create a wide variety of materials – but once you start a fire, it can be difficult to control how the flame interacts with the material you are trying to process. Researchers have now developed a technique that utilizes a molecule-thin protective layer to control how the flame’s heat interacts with the material – taming the fire and allowing users to finely tune the characteristics of the processed material.

“Fire is a valuable engineering tool – after all, a blast furnace is only an intense fire,” says Martin Thuo, corresponding author of a paper on the work and a professor of materials science and engineering at North Carolina State University. “However, once you start a fire, you often have little control over how it behaves.

“Our technique, which we call inverse thermal degradation (ITD), employs a nanoscale thin film over a targeted material. The thin film changes in response to the heat of the fire, and regulates the amount of oxygen that can access the material. That means we can control the rate at which the material heats up – which, in turn, influences the chemical reactions taking place within the material. Basically, we can fine-tune how and where the fire changes the material.”

Here’s how ITD works. You start out with your target material, such as a cellulose fiber. That fiber is then coated with a nanometer thick layer of molecules. The coated fibers are then exposed to an intense flame. The outer surface of the molecules combusts easily, raising the temperature in the immediate vicinity. But the inner surface of the molecular coating chemically changes, creating an even thinner layer of glass around the cellulose fibers. This glass limits the amount of oxygen that can access the fibers, preventing the cellulose from bursting into flames. Instead, the fibers smolder – burning slowly, from the inside out.

“Without the ITD’s protective layer, applying flame to cellulose fibers would just result in ash,” Thuo says. “With the ITD’s protective layer, you end up with carbon tubes.

“Without the ITD’s protective layer, applying flame to cellulose fibers would just result in ash,” Thuo says. “With the ITD’s protective layer, you end up with carbon tubes.

“We can engineer the protective layer in order to tune the amount of oxygen that reaches the target material. And we can engineer the target material in order to produce desirable characteristics.”

The researchers conducted proof-of-concept demonstrations with cellulose fibers to produce microscale carbon tubes.

The researchers could control the thickness of the carbon tube walls by controlling the size of the cellulose fibers they started with; by introducing various salts to the fibers (which further controls the rate of burning); and by varying the amount of oxygen that passes through the protective layer.

“We have several applications in mind already, which we will be addressing in future studies,” Thuo says. “We’re also open to working with the private sector to explore various practical uses, such as developing engineered carbon tubes for oil-water separation – which would be useful for both industrial applications and environmental remediation.”

The paper, “Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts,” is published in the journal Angewandte Chemie. Co-authors are Dhanush Jamadgni and Alana Pauls, Ph.D. students at NC State; Julia Chang and Andrew Martin, postdoctoral researchers at NC State; Chuanshen Du, Paul Gregory, Rick Dorn and Aaron Rossini of Iowa State University; and E. Johan Foster at the University of British Columbia.

Source:

North Carolina State University, Matt Shipman

Photo: pixabay, Hilary Clark
01.02.2022

Cotton Fibers 2.0: Fireproof and comfortable

A new chemical process developed by Empa turns cotton into a fire-resistant fabric, that nevertheless retains the skin-friendly properties of cotton.

Conventional flame retardant cotton textiles suffer from release of formaldehyde and are uncomfortable to wear. Empa scientists managed to circumvent this problem by creating a physically and chemically independent network of flame retardants inside the fibers. This approach retains the inherently positive properties of cotton fibers, which account for three-quarters of the world's demand for natural fibers in clothing and home textiles. Cotton is skin-friendly because it can absorb considerable amounts of water and maintain a favorable microclimate on the skin.

A new chemical process developed by Empa turns cotton into a fire-resistant fabric, that nevertheless retains the skin-friendly properties of cotton.

Conventional flame retardant cotton textiles suffer from release of formaldehyde and are uncomfortable to wear. Empa scientists managed to circumvent this problem by creating a physically and chemically independent network of flame retardants inside the fibers. This approach retains the inherently positive properties of cotton fibers, which account for three-quarters of the world's demand for natural fibers in clothing and home textiles. Cotton is skin-friendly because it can absorb considerable amounts of water and maintain a favorable microclimate on the skin.

For firefighters and other emergency service personnel, protective clothing provides the most important barrier. For such purposes, cotton is mainly used as an inner textile layer that needs additional properties: For example, it must be fireproof or protect against biological contaminants. Nevertheless, it should not be hydrophobic, which would create an uncomfortable microclimate. These additional properties can be built into the cotton fibers by suitable chemical modifications.

Durability vs. toxicity
"Until now, it has always taken a compromise to make cotton fireproof," says Sabyasachi Gaan, a chemist and polymer expert who works at Empa's Advanced Fibers lab. Wash-durable flame retardant cotton in industry is produced by treating the fabric with flame retardants, which chemically links to the cellulose in the cotton. Currently, the textile industry has no other choice than to utilize formaldehyde-based chemicals – and formaldehyde is classified as a carcinogen. This has been an unsolved problem for decades. While formaldehyde-based flame retardant treatments are durable, they have additional drawbacks: The -OH groups of cellulose are chemically blocked, which considerably reduces the capability of cotton to absorb water, which results in an uncomfortable textile.

Gaan knows the chemistry of cotton fibers well and has spent many years at Empa developing flame retardants based on phosphorus chemistry that are already used in many industrial applications. Now he has succeeded in finding an elegant and easy way to anchor phosphorous in form of an independent network inside the cotton.

Independent network between cotton fibers
Gaan and his colleagues Rashid Nazir, Dambarudhar Parida and Joel Borgstädt utilized a tri-functional phosphorous compound (trivinylphosphine oxide), which has the capability of reacting only with specifically added molecules (nitrogen compounds like piperazin) to form its own network inside cotton. This makes the cotton permanently fire-resistant without blocking the favorable -OH groups. In addition, the physical phosphine oxide network also likes water. This flame retardant treatment does not include carcinogenic formaldehyde, which would endanger textile workers during textile manufacturing. The phosphine oxide networks, thus formed, does not wash out: After 50 launderings, 95 percent of the flame retardant network is still present in the fabric.

To render additional protective functionalities to the flame retardant cotton developed at Empa, the researchers also incorporated in situ generated silver nanoparticles inside the fabric. This works nicely in a one-step process together with generating the phosphine oxide networks. Silver nanoparticles provide the fiber with antimicrobial properties and survive 50 laundry cycles, too.

A high-tech solution from the pressure cooker
"We have used a simple approach to fix the phosphine oxide networks inside the cellulose," Gaan says. "For our lab experiments, we first treated the cotton with an aqueous solution of phosphorus and nitrogen compounds and then steamed it in a readily available pressure cooker to facilitate the crosslinking reaction of the phosphorus and the nitrogen molecules." The application process is compatible with equipment used in the textile industry. "Steaming textiles after dyeing, printing and finishing is a normal step in textile industry. So it doesn't require an additional investment to apply our process," states the Empa chemist.

Meanwhile, this newly developed phosphorus chemistry and its application is protected by a patent application. "Two important hurdles remain," Gaan says. "For future commercialization we need to find a suitable chemical manufacturer who can produce and supply trivinylphosphine oxide. In addition, trivinylphosphine oxide has to be REACH-registered in Europe."

Contact:
Dr. Sabyasachi Gaan
Advanced Fibers
Phone: +41 58 765 7611
sabyasachi.gaan@empa.ch
 
Contact:
Prof. Dr. Manfred Heuberger
Advanced Fibers
Phone: +41 58 765 7878
manfred.heuberger@empa.ch

A gel that releases drugs
The novel phosphorus chemistry can also be used to develop other materials, e.g. to make hydrogels that can release drugs upon changes in pH. Such gels could find application in treating wounds that heal slowly. In such wounds, the pH of the skin surface increases and the new phosphorus-based gels can be triggered to release medication or a dye that alerts doctors and nurses to the problem. Empa has also patented the production of such hydrogels.

Source:

EMPA, Rainer Klose

02.01.2018

THAILAND'S TEXTILE INDUSTRY ON NEW PATHS

  • Good chances for synthetic fibers and functional textiles

Bangkok (GTAI) - Thailand's textile industry is in transition and is increasingly positioning itself in new markets with higher added value. Synthetic fibers became an important foothold on the basis of innovative raw materials, while functional textiles are grateful to customers in a dozen sectors. In addition, there is the traditional silk craft, which can be marketed by international design and attractive fashion shows - and this at top prices.

  • Good chances for synthetic fibers and functional textiles

Bangkok (GTAI) - Thailand's textile industry is in transition and is increasingly positioning itself in new markets with higher added value. Synthetic fibers became an important foothold on the basis of innovative raw materials, while functional textiles are grateful to customers in a dozen sectors. In addition, there is the traditional silk craft, which can be marketed by international design and attractive fashion shows - and this at top prices.

The Thai textile industry is changing. As a part of the long-term national development strategy “Thailand 4.0” , new technologies are designed to help innovative products breakthrough in key emerging markets, backed by concerted efforts in design, fashion and marketing. The industrial foundation ensures the availability of a complete value chain from fiber production, yarn spinning, fabric weaving and processing to the production of clothing.
The long-term strategy has been outlined by the Thailand Textile Institute (THTI) in its "Thailand Textile and Fashion Industries Development Strategy 2015-2030". Three phases are planned from the regional center for textile and fashion retail, to the development of creative products for international brands, and finally the breakthrough as the global market leader in fashion design, including Thai components. The concrete catalog of measures includes an industrial fashion zone, a pilot fiber plant, a development center for yarn, fabrics and fashion products as well as a regional fashion academy.

Broad spectrum for innovations
A diversified petrochemical industry with high-quality downstream products provides a rich foundation for a wide variety of synthetic fibers. The main products are polyester, nylon, rayon and acrylic polymers. The range of applications is quite broad, including apparel, medical technique, hygiene and automotive manufacturing. For polyester, Thailand ranks ninth in the world with an annual production of 621,000 tons, the larger producers include Indorama Polyester, Teijin Polyester or Thai Toray.

Increased research and development efforts with both artificial and natural textile fibers are paving the way for functional textiles. There are a dozen applications in this broad future market: Agrotex, Mobiltex, Medtex, Hometex, Oekotex, Packtex, Buildtex, Clothtex, Indutex, Geotex, Protex and Sportex. The leaders in this branch are companies such as Asahi Kasei, Perma, Saha Seiren, PJ Garment or TP Corporation. Thailand also wants to play an active role in shaping the future market of "smart fabrics" - such as fabrics with UV protection or antibacterial and fire-resistant properties.

Renaissance of the silk
On elegant paths also the traditional over generations grown art of silk crafts is moving. Thanks to the rich raw material base, the kingdom is considered to be the world's fourth largest silk producer. In the preference of visitors from abroad, silk products are at the eighth place in the souvenir statistics 2015 with USD 149 mio.
The origins of silk were characterized by the craftsmanship weaving with regional origin characteristics such as at the Lumphun Broocade Thai Silk, the Phu Thai Praewa Silk or the Surin Hole Silk. The change to innovative products took place with the growing demands of customers. New technologies produced goods of higher value, which were also became promoted with new stronger marketing ideas.

Jim Thompson and Passaya are considered two major pioneers of world-class luxury silk brands. Jim Thompson generates USD 72 mio thanks to modern design and premium products. Passaya won international awards for outstanding innovations in design as well as in the production process. Public support has been provided by promotional events such as "Proud Pastra", which recently completed USD 1.5 mio  in trade surplus. The Ministry of Commerce also intends to establish a silk center in the northeastern Korat under the state-sponsored so-called OTOP scheme (One Tambon One Product).

The entire industry has currently  4,700 textile and garment manufacturers with over 500,000 workers, including 730 textile companies for technical textiles. The export value amounted to USD 6.45 billion in 2016, which represented about 3 percent of total exports. The national retail sector recorded steady growth rates averaging 3.5 percent per year over the period 2011-2016.

In addition to production, Thailand also tries to profile itself as a fashion hub for regional and international fashion shows. The most important events are the "Bangkok International Couture Fashion Week", "Elle Bangkok Fashion Week" and the "Bangkok International Fashion Fair". The first national designer brands have already made their debuts on the catwalk, such as Sretsis, Naraya, Dry Clean Only or Disaya. Sretsis, founded by three sisters, became successfully supported by some big names such as Beyoncé, Paris Hilton, January Jones and Zooey Deschanel.

More information:
Thailand
Source:

Waldemar Duscha, www.gtai.de