Tag Archives: wood

A fire-retardant coating made of renewable nanocellulose materials

Firefighters everywhere are likely to appreciate the efforts of researchers at Texas A&M University (US) to a develop a non-toxic fire retardant coating. From a February 12, 2019 news item on Nanowerk (Note: A link has been removed),

Texas A&M University researchers are developing a new kind of flame-retardant coating using renewable, nontoxic materials readily found in nature, which could provide even more effective fire protection for several widely used materials.

Dr. Jaime Grunlan, the Linda & Ralph Schmidt ’68 Professor in the J. Mike Walker ’66 Department of Mechanical Engineering at Texas A&M, led the recently published research that is featured on the cover of a recent issue of the journal Advanced Materials Interfaces (“Super Gas Barrier and Fire Resistance of Nanoplatelet/Nanofibril Multilayer Thin Films”).

Successful development and implementation of the coating could provide better fire protection to materials including upholstered furniture, textiles and insulation.

“These coatings offer the opportunity to reduce the flammability of the polyurethane foam used in a variety of furniture throughout most people’s homes,” Grunlan noted.

A February 8, 2019 Texas A&M University news release (also on EurekAlert) by Steve Kuhlmann, which originated the news item, describes the work being done in collaboration with a Swedish team in more detail,

The project is a result of an ongoing collaboration between Grunlan and a group of researchers at KTH Royal Institute of Technology in Stockholm, Sweden, led by Lars Wagberg. The group, which specializes in utilizing nanocellulose, provided Grunlan with the ingredients he needed to complement his water-based coating procedure.

In nature, both the cellulose – a component of wood and various sea creatures – and clay – a component in soil and rock formations – act as mechanical reinforcements for the structures in which they are found.

“The uniqueness in this current study lies in the use of two naturally occurring nanomaterials, clay nanoplatelets and cellulose nanofibrils,” Grunlan said. “To the best of our knowledge, these ingredients have never been used to make a heat shielding or flame-retardant coating as a multilayer thin film deposited from water.”

Among the benefits gained from using this method include the coating’s ability to create an excellent oxygen barrier to plastic films – commonly used for food packaging – and better fire protection at a lower cost than other, more toxic ingredients traditionally used flame-retardant treatments.

To test the coatings, Grunlan and his colleagues applied the flexible polyurethane foam – often used in furniture cushions – and exposed it to fire using a butane torch to determine the level of protection the compounds provided.

While uncoated polyurethane foam immediately melts when exposed to flame, the foam treated with the researchers’ coating prevented the fire from damaging any further than surface level, leaving the foam underneath undamaged.

“The nanobrick wall structure of the coating reduces the temperature experienced by the underlying foam, which delays combustion,” Grunlan said. “This coating also serves to promote insulating char formation and reduces the release of fumes that feed a fire.”

With the research completed, Grunlan said the next step for the overall flame-retardant project is to transition the methods into industry for implementation and further development. 

Here’s a link to and a citation for the paper,

Super Gas Barrier and Fire Resistance of Nanoplatelet/Nanofibril Multilayer Thin Films by Shuang Qin, Maryam Ghanad Pour, Simone Lazar, Oruç Köklükaya, Joseph Gerringer, Yixuan Song, Lars Wågberg, Jaime C. Grunlan. Advanced Materials Interfaces Volume 6, Issue 2 January 23, 2019 1801424 DOI: https://doi.org/10.1002/admi.201801424 First published online: 16 November 2018

This paper is behind a paywall.

Wooden supercapacitors: a cellulose nanofibril story

A May 24, 2018 news item on Nanowerk announces a technique for making sustainable electrodes (Note: A link has been removed),

Carbon aerogels are ultralight, conductive materials, which are extensively investigated for applications in supercapacitor electrodes in electrical cars and cell phones. Chinese scientists have now found a way to make these electrodes sustainably. The aerogels can be obtained directly from cellulose nanofibrils, the abundant cell-wall material in wood, finds the study reported in the journal Angewandte Chemie (“Wood-Derived Ultrathin Carbon Nanofiber Aerogels”).

A May 24, 2018 Wiley Publications press release, which originated the news item, explains further,

Supercapacitors are capacitors that can take up and release a very large amount of energy in a very short time. Key requirements for supercapacitor electrodes are a large surface area and conductivity, combined with a simple production method. Another growing issue in supercapacitor production–mainly for smartphone and electric car technologies–is sustainability. However, sustainable and economical production of carbon aerogels as supercapacitor electrode materials is possible, propose Shu-Hong Yu and colleagues from the University of Science and Technology of China, Hefei, China.

Carbon aerogels are ultralight conductive materials with a very large surface area. They can be prepared by two production routes: the first and cheapest starts from mostly phenolic components and produces aerogels with improvable conductivity, while the second route is based on graphene- and carbon-nanotube precursors. The latter method delivers high-performance aerogels but is expensive and non-environmentally friendly. In their search for different precursors, Yu and colleagues have found an abundant, far less expensive, and sustainable source: wood pulp.

Well, not really wood pulp, but its major ingredient, nanocellulose. Plant cell walls are stabilized by fibrous nanocellulose, and this extractable material has very recently stimulated substantial research and technological development. It forms a highly porous, but very stable transparent network, and, with the help of a recent technique–oxidation with a radical scavenger called TEMPO–it forms a microporous hydrogel of highly oriented cellulose nanofibrils with a uniform width and length. As organic aerogels are produced from hydrogels by drying and pyrolysis, the authors attempted pyrolysis of supercritically or freeze-dried nanofibrillated cellulose hydrogel.

As it turns out, the method was not as straightforward as expected because ice crystal formation and insufficient dehydration hampered carbonization, according to the authors. Here, a trick helped. The scientists pyrolyzed the dried gel in the presence of the organic acid catalyst para-toluenesulfonic acid. The catalyst lowered the decomposition temperature and yielded a “mechanically stable and porous three-dimensional nanofibrous network” featuring a “large specific surface area and high electrical conductivity,” the authors reported.

The authors also demonstrated that their wood-derived carbon aerogel worked well as a binder-free electrode for supercapacitor applications. The material displayed electrochemical properties comparable to commercial electrodes. The method is an interesting and innovative way in which to fabricate sustainable materials suitable for use in high-performance electronic devices.

This is the first time I’ve seen work on wood-based nanocellulose from China. Cellulose according to its Wikipedia entry is: ” … the most abundant organic polymer on Earth.” For example, there’s more cellulose in cotton than there is wood. So, I find it interesting that in a country not known for its forests, nanocellulose (in this project anyway) is being derived from wood.

Here’s a link to and a citation for the paper,

Wood‐Derived Ultrathin Carbon Nanofiber Aerogels by Si‐Cheng Li, Bi‐Cheng Hu, Dr. Yan‐Wei Ding, Prof. Hai‐Wei Liang, Chao Li, Dr. Zi‐You Yu, Dr. Zhen‐Yu Wu, Prof. Wen‐Shuai Chen, Prof. Shu‐Hong Yu. Angewandt Chemie First published: 23 April 2018 DOI: https://doi.org/10.1002/anie.201802753

This paper is behind a paywall.

Stronger than steel and spider silk: artificial, biodegradable, cellulose nanofibres

This is an artificial and biodegradable are two adjectives you don’t usually see united by the conjunction, and. However, it is worth noting that the artificial material is initially derived from a natural material, cellulose. Here’s more from a May 16, 2018 news item on ScienceDaily,

At DESY’s [Deutsches Elektronen-Synchrotron] X-ray light source PETRA III, a team led by Swedish researchers has produced the strongest bio-material that has ever been made. The artifical, but bio-degradable cellulose fibres are stronger than steel and even than dragline spider silk, which is usually considered the strongest bio-based material. The team headed by Daniel Söderberg from the KTH Royal Institute of Technology in Stockholm reports the work in the journal ACS Nano of the American Chemical Society.

A May 16, 2018 DESY press release (also on EurekAlert), which originated the news item, provides more detail,

The ultrastrong material is made of cellulose nanofibres (CNF), the essential building blocks of wood and other plant life. Using a novel production method, the researchers have successfully transferred the unique mechanical properties of these nanofibres to a macroscopic, lightweight material that could be used as an eco-friendly alternative for plastic in airplanes, cars, furniture and other products. “Our new material even has potential for biomedicine since cellulose is not rejected by your body”, explains Söderberg.

The scientists started with commercially available cellulose nanofibres that are just 2 to 5 nanometres in diameter and up to 700 nanometres long. A nanometre (nm) is a millionth of a millimetre. The nanofibres were suspended in water and fed into a small channel, just one millimetre wide and milled in steel. Through two pairs of perpendicular inflows additional deionized water and water with a low pH-value entered the channel from the sides, squeezing the stream of nanofibres together and accelerating it.

This process, called hydrodynamic focussing, helped to align the nanofibres in the right direction as well as their self-organisation into a well-packed macroscopic thread. No glue or any other component is needed, the nanofibres assemble into a tight thread held together by supramolecular forces between the nanofibres, for example electrostatic and Van der Waals forces.

With the bright X-rays from PETRA III the scientists could follow and optimise the process. “The X-rays allow us to analyse the detailed structure of the thread as it forms as well as the material structure and hierarchical order in the super strong fibres,” explains co-author Stephan Roth from DESY, head of the Micro- and Nanofocus X-ray Scattering Beamline P03 where the threads were spun. “We made threads up to 15 micrometres thick and several metres in length.”

Measurements showed a tensile stiffness of 86 gigapascals (GPa) for the material and a tensile strength of 1.57 GPa. “The bio-based nanocellulose fibres fabricated here are 8 times stiffer and have strengths higher than natural dragline spider silk fibres,” says Söderberg. “If you are looking for a bio-based material, there is nothing quite like it. And it is also stronger than steel and any other metal or alloy as well as glass fibres and most other synthetic materials.” The artificial cellulose fibres can be woven into a fabric to create materials for various applications. The researchers estimate that the production costs of the new material can compete with those of strong synthetic fabrics. “The new material can in principle be used to create bio-degradable components,” adds Roth.

The study describes a new method that mimics nature’s ability to accumulate cellulose nanofibres into almost perfect macroscale arrangements, like in wood. It opens the way for developing nanofibre material that can be used for larger structures while retaining the nanofibres’ tensile strength and ability to withstand mechanical load. “We can now transform the super performance from the nanoscale to the macroscale,” Söderberg underlines. “This discovery is made possible by understanding and controlling the key fundamental parameters essential for perfect nanostructuring, such as particle size, interactions, alignment, diffusion, network formation and assembly.” The process can also be used to control nanoscale assembly of carbon tubes and other nano-sized fibres.

(There are some terminology and spelling issues, which are described at the end of this post.)

Let’s get back to a material that rivals spider silk and steel for strength (for some reason that reminded me of an old carnival game where you’d test your strength by swinging a mallet down on a ‘teeter-totter-like’ board and sending a metal piece up a post to make a bell ring). From a May 16, 2018 DESY press release (also on EurekAlert), which originated the news item,

The ultrastrong material is made of cellulose nanofibres (CNF), the essential building blocks of wood and other plant life. Using a novel production method, the researchers have successfully transferred the unique mechanical properties of these nanofibres to a macroscopic, lightweight material that could be used as an eco-friendly alternative for plastic in airplanes, cars, furniture and other products. “Our new material even has potential for biomedicine since cellulose is not rejected by your body”, explains Söderberg.

The scientists started with commercially available cellulose nanofibres that are just 2 to 5 nanometres in diameter and up to 700 nanometres long. A nanometre (nm) is a millionth of a millimetre. The nanofibres were suspended in water and fed into a small channel, just one millimetre wide and milled in steel. Through two pairs of perpendicular inflows additional deionized water and water with a low pH-value entered the channel from the sides, squeezing the stream of nanofibres together and accelerating it.

This process, called hydrodynamic focussing, helped to align the nanofibres in the right direction as well as their self-organisation into a well-packed macroscopic thread. No glue or any other component is needed, the nanofibres assemble into a tight thread held together by supramolecular forces between the nanofibres, for example electrostatic and Van der Waals forces.

With the bright X-rays from PETRA III the scientists could follow and optimise the process. “The X-rays allow us to analyse the detailed structure of the thread as it forms as well as the material structure and hierarchical order in the super strong fibres,” explains co-author Stephan Roth from DESY, head of the Micro- and Nanofocus X-ray Scattering Beamline P03 where the threads were spun. “We made threads up to 15 micrometres thick and several metres in length.”

Measurements showed a tensile stiffness of 86 gigapascals (GPa) for the material and a tensile strength of 1.57 GPa. “The bio-based nanocellulose fibres fabricated here are 8 times stiffer and have strengths higher than natural dragline spider silk fibres,” says Söderberg. “If you are looking for a bio-based material, there is nothing quite like it. And it is also stronger than steel and any other metal or alloy as well as glass fibres and most other synthetic materials.” The artificial cellulose fibres can be woven into a fabric to create materials for various applications. The researchers estimate that the production costs of the new material can compete with those of strong synthetic fabrics. “The new material can in principle be used to create bio-degradable components,” adds Roth.

The study describes a new method that mimics nature’s ability to accumulate cellulose nanofibres into almost perfect macroscale arrangements, like in wood. It opens the way for developing nanofibre material that can be used for larger structures while retaining the nanofibres’ tensile strength and ability to withstand mechanical load. “We can now transform the super performance from the nanoscale to the macroscale,” Söderberg underlines. “This discovery is made possible by understanding and controlling the key fundamental parameters essential for perfect nanostructuring, such as particle size, interactions, alignment, diffusion, network formation and assembly.” The process can also be used to control nanoscale assembly of carbon tubes and other nano-sized fibres.

Here’s a link to and a citation for the paper,

Multiscale Control of Nanocellulose Assembly: Transferring Remarkable Nanoscale Fibril Mechanics to Macroscale Fibers by Nitesh Mittal, Farhan Ansari, Krishne Gowda V, Christophe Brouzet, Pan Chen, Per Tomas Larsson, Stephan V. Roth, Fredrik Lundell, Lars Wågberg, Nicholas A. Kotov, and L. Daniel Söderberg. ACS Nano, Article ASAP DOI: 10.1021/acsnano.8b01084 Publication Date (Web): May 9, 2018

Copyright © 2018 American Chemical Society

This paper is open access and accompanied by this image illustrating the work,

Courtesy: American Chemical Society and the researchers [Note: The bottom two images of cellulose nanofibres, which are constittuents of an artificial cellulose fibre, appear to be from a scanning tunneling microsscope. Credit: Nitesh Mittal, KTH Stockholm

This news has excited interest at General Electric (GE) (its Wikipedia entry), which has highlighted the work in a May 25, 2018 posting (The 5 Coolest Things On Earth This Week) by Tomas Kellner on the GE Reports blog.

Terminology and spelling

I’ll start with spelling since that’s the easier of the two. In some parts of the world it’s spelled ‘fibres’ and in other parts of the world it’s spelled ‘fibers’. When I write the text in my post, it tends to reflect the spelling used in the news/press releases. In other words, I swing in whichever direction the wind is blowing.

For diehards only

As i understand the terminology situation, nanocellulose and cellulose nanomaterials are interchangeable generic terms. Further, cellulose nanofibres (CNF) seems to be another generic term and it encompasses both cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF). Yes, there appear to be two CNFs. Making matters more interesting is the fact that cellulose nanocrystals were originally christened nanocrystalline cellulose (NCC). For anyone who follows the science and technology scene, it becomes obvious that competing terminologies are the order of the day. Eventually the dust settles and naming conventions are resolved. More or less.

Ordinarily I would reference the Nanocellulose Wikipedia entry in my attempts to clarify the issues but it seems that the writers for the entry have not caught up to the current naming convention for cellulose nanocrystals, still referring to the material as nanocrystalline cellulose. This means, I can’t trust the rest of the entry, which has only one CNF (cellulose nanofibres).

I have paid more attention to the NCC/CNC situation and am not as familiar with the CNF situation. Using, NCC/CNC as an example of a terminology issue, I believe it was first developed in Canada and it was Canadian researchers who were pushing their NCC terminology while the international community pushed back with CNC.

In the end, NCC became a brand name, which was trademarked by CelluForce, a Canadian company in the CNC market. From the CelluForce Products page on Cellulose Nanocrystals,

CNC are not all made equal. The CNC produced by CelluForce is called CelluForce NCCTM and has specific properties and are especially easy to disperse. CelluForce NCCTM is the base material that CelluForce uses in all its products. This base material can be modified and tailored to suit the specific needs in various applications.

These, days CNC is almost universally used but NCC (not as a trademark) is a term still employed on occasion (and, oddly, the researchers are not necessarily Canadian).

Should anyone have better information about terminology issues, please feel free to comment.

Cellulose aerogels for new wood-based composites

‘Frozen smoke’ or ‘solid smoke’ as it’s sometimes described, aerogel fascinates scientists.The latest on cellulose aerogels derived from wood is the focus for a February 14, 2018 Nanowerk Sportlight article by Michael Berger (Note: Links have been removed),

Aerogels, sometimes called frozen smoke, are nanoscale foams: solid materials whose sponge-like structure is riddled by pores as small as nanometers across. They can be made from different materials, for instance silicon.

Aerogels are among the lightest solid substances in the world yet flexible, extremely strong and water repellent, which makes them very interesting materials for engineers.

Cellulose aerogels, made from nanofibrils found in plants, have several unique features, one of which is super high oil absorption capacity that is several times higher than commercial sorbents available in the market.

“Encouraged from our previous work on transparent wood (“Transparent wood for functional and structural applications”; “Optically Transparent Wood from a Nanoporous Cellulosic Template: Combining Functional and Structural Performance”; “Nanostructured Wood Hybrids for Fire-Retardancy Prepared by Clay Impregnation into the Cell Wall”), we started to develop porous wood/epoxy biocomposite materials, which preserves the original hierarchical and porous structure of wood,” Qi Zhou, an associate professor in the Department of Chemistry at KTH Royal Institute of Technology, tells Nanowerk.

“Our strategy is different from traditional wood modification methods,” explains Zhou. “It involves two steps, a simple chemical treatment to remove the lignin (delignification) at first, then back infiltration of the wood cell wall with epoxy, leaving the lumen (a void space) open. In traditional wood polymer composites, both the cell wall and cell lumen are filled with polymer.”

The scientists don’t seem to have any particular applications in mind but they are hopeful that new materials will inspire new uses. Here’s a link to and a citation for Zhou’s latest paper,

Wood Nanotechnology for Strong, Mesoporous, and Hydrophobic Biocomposites for Selective Separation of Oil/Water Mixtures by Qiliang Fu, Farhan Ansari, Qi Zhou, and Lars A. Berglund. ACS Nano, Article ASAP DOI: 10.1021/acsnano.8b00005 Publication Date (Web): February 7, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Wood’s natural nanotechnology

“Wood’s natural nanotechnology: is an unusual term and it comes at the end of this February 7, 2018 University of Maryland (US) news release about a technique which will make wood stronger than titanium alloy,

Engineers at the University of Maryland in College Park have found a way to make wood more than ten times times stronger and tougher than before, creating a natural substance that is stronger than titanium alloy.

“This new way to treat wood makes it twelve times stronger than natural wood and ten times tougher,” said Liangbing Hu, the leader of the team that did the research, to be published on Thursday [February 7, 2018] in the journal Nature. “This could be a competitor to steel or even titanium alloys, it is so strong and durable. It’s also comparable to carbon fiber, but much less expensive.” Hu is an associate professor of materials science and engineering and a member of the Maryland Energy Innovation Institute.

“It is both strong and tough, which is a combination not usually found in nature,” said Teng Li, the co-leader of the team and the Samuel P. Langley associate professor of mechanical engineering at the University of Maryland. His team measured the dense wood’s mechanical properties.  “It is as strong as steel, but six times lighter. It takes 10 times more energy to fracture than natural wood. It can even be bent and molded at the beginning of the process.”

The team’s process begins by removing the wood’s lignin, the part of the wood that makes it both rigid and brown in color. Then it is compressed under mild heat, at about 150 F. This causes the cellulose fibers to become very tightly packed. Any defects like holes or knots are crushed together.  The treatment process was extended a little further with a coat of paint.

The scientists found that the wood’s fibers are pressed together so tightly that they can form strong hydrogen bonds, like a crowd of people who can’t budge – who are also holding hands. The compression makes the wood five times thinner than its original size.

The team also tested the material by shooting a bullet-like projectile at it. Unlike natural wood, which was blown straight through, the fully treated wood actually stopped the projectile partway through.

“Soft woods like pine or balsa, which grow fast and are more environmentally friendly, could replace slower-growing but denser woods like teak, in furniture or buildings,” Hu said.

“The paper provides a highly promising route to the design of light weight high performance structural materials, with tremendous potential for a broad range of applications where high strength, large toughness and superior ballistic resistance are desired, “ said Dr. Huajian Gao, a professor at Brown University, who was not involved in the study. “It is particularly exciting to note that the method is versatile for various species of wood and fairly easy to implement.”

“This kind of wood could be used in cars, airplanes, buildings – any application where steel is used,” Hu said.

“The two-step process reported in this paper achieves exceptionally high strength, much beyond what [is] reported in the literature,” said Dr. Zhigang Suo, a professor of mechanics and materials at Harvard University, also not involved with the study. “Given the abundance of wood, as well as other cellulose-rich plants, this paper inspires imagination.”

“The most outstanding observation, in my view, is the existence of a limiting concentration of lignin, the glue between wood cells, to maximize the mechanical performance of the densified wood. Too little or too much removal lower the strength compared to a maximum value achieved at intermediate or partial lignin removal. This reveals the subtle balance between hydrogen bonding and the adhesion imparted by such polyphenolic compound. Moreover, of outstanding interest, is the fact that that wood densification leads to both, increased strength and toughness, two properties that usually offset each other,” said Orlando J. Rojas, a professor at Aalto University in Finland.

Hu’s research has explored the capacities of wood’s natural nanotechnology [emphasis mine]. They previously made a range of emerging technologies out of nanocellulose related materials: (1) super clear paper for replacing plastic; (2) photonic paper for improving solar cell efficiency by 30%; (3) a battery and a supercapacitor out of wood; (4) a battery from a leaf; (5) transparent wood for energy efficient buildings; (6) solar water desalination for drinking and specifically filtering out toxic dyes. These wood-based emerging technologies are being commercialized through a UMD spinoff company, Inventwood LLC.

At a guess, “wood’s natural nanotechnology” refers to the properties of wood and other forms of cellulose at the nanoscale.

Here’s a link to and a citation for the paper,

Processing bulk natural wood into a high-performance structural material by Jianwei Song, Chaoji Chen, Shuze Zhu, Mingwei Zhu, Jiaqi Dai, Upamanyu Ray, Yiju Li, Yudi Kuang, Yongfeng Li, Nelson Quispe, Yonggang Yao, Amy Gong, Ulrich H. Leiste, Hugh A. Bruck, J. Y. Zhu, Azhar Vellore, Heng Li, Marilyn L. Minus, Zheng Jia, Ashlie Martini, Teng Li, & Liangbing Hu. Nature volume 554, pages 224–228 (08 February 2018) doi:10.1038/nature25476 Published online: 07 February 2018

This paper is behind a paywall.

h/t Feb. 7, 2018 news item on Nanowerk and, finally, you can find out more about the wood-based emerging technologies being commcercialized by the University of Maryland here on the Inventwood website.

Cellulose- and chitin-based biomaterial to replace plastics?

Although the term is not actually used in the news release, one of the materials used to create a new biomaterial could safely be described as nanocellulose. From a Sept. 20, 2017 Pennsylvania State University (Penn State) news release (also on EurekAlert) by Jeff Mulhollem,

An inexpensive biomaterial that can be used to sustainably replace plastic barrier coatings in packaging and many other applications has been developed by Penn State researchers, who predict its adoption would greatly reduce pollution.

Completely compostable, the material — a polysaccharide polyelectrolyte complex — is comprised of nearly equal parts of treated cellulose pulp from wood or cotton, and chitosan, which is derived from chitin — the primary ingredient in the exoskeletons of arthropods and crustaceans. The main source of chitin is the mountains of leftover shells from lobsters, crabs and shrimp consumed by humans.

These environmentally friendly barrier coatings have numerous applications ranging from water-resistant paper, to coatings for ceiling tiles and wallboard, to food coatings to seal in freshness, according to lead researcher Jeffrey Catchmark, professor of agricultural and biological engineering, College of Agricultural Sciences.

“The material’s unexpected strong, insoluble adhesive properties are useful for packaging as well as other applications, such as better performing, fully natural wood-fiber composites for construction and even flooring,” he said. “And the technology has the potential to be incorporated into foods to reduce fat uptake during frying and maintain crispness. Since the coating is essentially fiber-based, it is a means of adding fiber to diets.”

The amazingly sturdy and durable bond between carboxymethyl cellulose and chitosan is the key, he explained. The two very inexpensive polysaccharides — already used in the food industry and in other industrial sectors — have different molecular charges and lock together in a complex that provides the foundation for impervious films, coatings, adhesives and more.

The potential reduction of pollution is immense if these barrier coatings replace millions of tons of petroleum-based plastic associated with food packaging used every year in the United States — and much more globally, Catchmark noted.

He pointed out that the global production of plastic is approaching 300 million tons per year. In a recent year, more than 29 million tons of plastic became municipal solid waste in the U.S. and almost half was plastic packaging. It is anticipated that 10 percent of all plastic produced globally will become ocean debris, representing a significant ecological and human health threat.

crab shells

The material is comprised of cellulose pulp from wood or cotton, and chitosan, derived from chitin, the primary ingredient in the exoskeletons of arthropods and crustaceans. The main source of chitin is shells from lobsters, crabs and shrimp. Image: © iStock Photo OKRAD

The polysaccharide polyelectrolyte complex coatings performed well in research, the findings of which were published recently in Green Chemistry. Paperboard coated with the biomaterial, comprised of nanostructured fibrous particles of carboxymethyl cellulose and chitosan, exhibited strong oil and water barrier properties. The coating also resisted toluene, heptane and salt solutions and exhibited improved wet and dry mechanical and water vapor barrier properties.

“These results show that polysaccharide polyelectrolyte complex-based materials may be competitive barrier alternatives to synthetic polymers for many commercial applications,” said Catchmark, who, in concert with Penn State, has applied for a patent on the coatings.

“In addition, this work demonstrates that new, unexpected properties emerge from multi-polysaccharide systems engaged in electrostatic complexation, enabling new high-performance applications.”

Catchmark began experimenting with biomaterials that might be used instead of plastics a decade or so ago out of concerns for sustainability. He became interested in cellulose, the main component in wood, because it is the largest volume sustainable, renewable material on earth. Catchmark studied its nanostructure — how it is assembled at the nanoscale.

He believed he could develop natural materials that are more robust and improve their properties, so that they could compete with synthetic materials that are not sustainable and generate pollution — such as the low-density polyethylene laminate applied to paper board, Styrofoam and solid plastic used in cups and bottles.

“The challenge is, to do that you’ve got to be able to do it in a way that is manufacturable, and it has to be less expensive than plastic,” Catchmark explained. “Because when you make a change to something that is greener or sustainable, you really have to pay for the switch. So it has to be less expensive in order for companies to actually gain something from it. This creates a problem for sustainable materials — an inertia that has to be overcome with a lower cost.”

lab vials

The amazingly sturdy and durable bond between carboxymethyl cellulose and chitosan is the key. The two very inexpensive polysaccharides, already used in the food industry and in other industrial sectors, have different molecular charges and lock together in a complex that provides the foundation for impervious films, coatings, adhesives and more. Image: Penn State

Funded by a Research Applications for Innovation grant from the College of Agricultural Sciences, Catchmark currently is working to develop commercialization partners in different industry sectors for a wide variety of products.

“We are trying to take the last step now and make a real impact on the world, and get industry people to stop using plastics and instead use these natural materials,” he said. “So they (consumers) have a choice — after the biomaterials are used, they can be recycled, buried in the ground or composted, and they will decompose. Or they can continue to use plastics that will end up in the oceans, where they will persist for thousands of years.”

Also involved in the research were Snehasish Basu, post-doctoral scholar, and Adam Plucinski, master’s degree student, now instructor of engineering at Penn State Altoona. Staff in Penn State’s Material Research Institute provided assistance with the project.

The U.S. Department of Agriculture supported this work. Southern Champion Tray, of Chattanooga, Tennessee, provided paperboard and information on its production for experiments.

Here’s a link to and a citation for the paper,

Sustainable barrier materials based on polysaccharide polyelectrolyte complexes by
Snehasish Basu, Adam Plucinski, and Jeffrey M. Catchmark. Green Chemistry 2017, 19, 4080-4092 DOI: 10.1039/C7GC00991G

This paper is behind a paywall. One comment, I found an anomaly on the page when I visited. At the top of the citation page, it states that this is issue 17 of Green Chemistry but the citation in the column on the right is “2017, 19 … “, which would be issue 19.

Preserving heritage smells (scents)

Preserving a smell? It’s an intriguing idea and forms the research focus for scientists at the University College London’s (UCL) Institute for Sustainable Heritage according to an April 6, 2017 Biomed Central news release on EurekAlert,

A ‘Historic Book Odour Wheel’ which has been developed to document and archive the aroma associated with old books, is being presented in a study in the open access journal Heritage Science. Researchers at UCL Institute for Sustainable Heritage created the wheel as part of an experiment in which they asked visitors to St Paul’s Cathedral’s Dean and Chapter library in London to characterize its smell.

The visitors most frequently described the aroma of the library as ‘woody’ (selected by 100% of the visitors who were asked), followed by ‘smoky’ (86%), ‘earthy'(71%) and ‘vanilla’ (41%). The intensity of the smells was assessed as between ‘strong odor’ and ‘very strong odor’. Over 70% of the visitors described the smell as pleasant, 14% as ‘mildly pleasant’ and 14% as ‘neutral’.

In a separate experiment, the researchers presented visitors to the Birmingham Museum and Art Gallery with an unlabelled historic book smell – sampled from a 1928 book they obtained from a second-hand bookshop in London – and collected the terms used to describe the smell. The word ‘chocolate’ – or variations such as ‘cocoa’ or ‘chocolatey’ – was used most often, followed by ‘coffee’, ‘old’, ‘wood’ and ‘burnt’. Participants also mentioned smells including ‘fish’, ‘body odour’, ‘rotten socks’ and ‘mothballs’.

Cecilia Bembibre, heritage scientist at UCL and corresponding author of the study said: “Our odour wheel provides an example of how scientists and historians could begin to identify, analyze and document smells that have cultural significance, such as the aroma of old books in historic libraries. The role of smells in how we perceive heritage has not been systematically explored until now.”

Attempting to answer the question of whether certain smells could be considered part of our cultural heritage and if so how they could be identified, protected and conserved, the researchers also conducted a chemical analysis of volatile organic compounds (VOCs) which they sampled from books in the library. VOCs are chemicals that evaporate at low temperatures, many of which can be perceived as scents or odors.

Combining their findings from the VOC analysis with the visitors’ characterizations, the authors created their Historic Book Odour wheel, which shows the chemical description of a smell (such as acetic acid) together with the sensory descriptions provided by the visitors (such as ‘vinegar’).

Cecilia Bembibre said: “By documenting the words used by the visitors to describe a heritage smell, our study opens a discussion about developing a vocabulary to identify aromas that have cultural meaning and significance.”

She added: “The Historic Book Odour Wheel also has the potential to be used as a diagnostic tool by conservators, informing on the condition of an object, for example its state of decay, through its olfactory profile.”

The authors suggest that, in addition to its use for the identification and conservation of smells, the Historic Book Odour Wheel could potentially be used to recreate smells and aid the design of olfactory experiences in museums, allowing visitors to form a personal connection with exhibits by allowing them to understand what the past smelled like.

Before this can be done, further research is needed to build on the preliminary findings in this study to allow them to inform and benefit heritage management, conservation, visitor experience design and heritage policy making.

Here’s what the Historic Book Odour Wheel looks like,

Odour wheel of historic book containing general aroma categories, sensory descriptors and chemical information on the smells as sampled (colours are arbitrary) Courtesy: Heritage Science [downloaded from https://heritagesciencejournal.springeropen.com/articles/10.1186/s40494-016-0114-1

Here’s a link to and a citation for the paper,

Smell of heritage: a framework for the identification, analysis and archival of historic odours by Cecilia Bembibre and Matija Strlič. Heritage Science20175:2 DOI: 10.1186/s40494-016-0114-1 Published: 7 April 2017

©  The Author(s) 2017

This paper is open access.

Mimicking the architecture of materials like wood and bone

Caption: Microstructures like this one developed at Washington State University could be used in batteries, lightweight ultrastrong materials, catalytic converters, supercapacitors and biological scaffolds. Credit: Washington State University

A March 3, 2017 news item on Nanowerk features a new 3D manufacturing technique for creating biolike materials, (Note: A link has been removed)

Washington State University nanotechnology researchers have developed a unique, 3-D manufacturing method that for the first time rapidly creates and precisely controls a material’s architecture from the nanoscale to centimeters. The results closely mimic the intricate architecture of natural materials like wood and bone.

They report on their work in the journal Science Advances (“Three-dimensional microarchitected materials and devices using nanoparticle assembly by pointwise spatial printing”) and have filed for a patent.

A March 3, 2017 Washington State University news release by Tina Hilding (also on EurekAlert), which originated the news item, expands on the theme,

“This is a groundbreaking advance in the 3-D architecturing of materials at nano- to macroscales with applications in batteries, lightweight ultrastrong materials, catalytic converters, supercapacitors and biological scaffolds,” said Rahul Panat, associate professor in the School of Mechanical and Materials Engineering, who led the research. “This technique can fill a lot of critical gaps for the realization of these technologies.”

The WSU research team used a 3-D printing method to create foglike microdroplets that contain nanoparticles of silver and to deposit them at specific locations. As the liquid in the fog evaporated, the nanoparticles remained, creating delicate structures. The tiny structures, which look similar to Tinkertoy constructions, are porous, have an extremely large surface area and are very strong.

Silver was used because it is easy to work with. However, Panat said, the method can be extended to any other material that can be crushed into nanoparticles – and almost all materials can be.

The researchers created several intricate and beautiful structures, including microscaffolds that contain solid truss members like a bridge, spirals, electronic connections that resemble accordion bellows or doughnut-shaped pillars.

The manufacturing method itself is similar to a rare, natural process in which tiny fog droplets that contain sulfur evaporate over the hot western Africa deserts and give rise to crystalline flower-like structures called “desert roses.”

Because it uses 3-D printing technology, the new method is highly efficient, creates minimal waste and allows for fast and large-scale manufacturing.

The researchers would like to use such nanoscale and porous metal structures for a number of industrial applications; for instance, the team is developing finely detailed, porous anodes and cathodes for batteries rather than the solid structures that are now used. This advance could transform the industry by significantly increasing battery speed and capacity and allowing the use of new and higher energy materials.

Here’s a link to and a citation for the paper,

Three-dimensional microarchitected materials and devices using nanoparticle assembly by pointwise spatial printing by Mohammad Sadeq Saleh, Chunshan Hu, and Rahul Panat. Science Advances  03 Mar 2017: Vol. 3, no. 3, e1601986 DOI: 10.1126/sciadv.1601986

This paper appears to be open access.

Finally, there is a video,

Hydrodynamic alignment and assembly of nano-fibrils results in cellulose fibers stronger than both aluminum and steel

A June 2, 2014 news item on Azonano describes the new fibres (which come from wood),

“Our filaments are stronger than both aluminium and steel per weight,” emphasizes lead author Prof. Fredrik Lundell from the Wallenberg Wood Science Center at the Royal Swedish Institute of Technology KTH in Stockholm. “The real challenge, however, is to make bio based materials with extreme stiffness that can be used in wind turbine blades, for example. With further improvements, in particular increased fibril alignment, this will be possible.”

The June 2, 2014 DESY ( one of the world’s leading accelerator centres) press release describes the research in detail,

A Swedish-German research team has successfully tested a new method for the production of ultra-strong cellulose fibres at DESY’s research light source PETRA III. The novel procedure spins extremely tough filaments from tiny cellulose fibrils by aligning them all in parallel during the production process. …

For their method, the researchers took tiny, nanometre-sized cellulose fibrils and fed them together with water through a small channel. Two additional water jets coming in perpendicular from left and right accelerate the fibril flow. “Following the acceleration, all nano fibrils align themselves more or less parallel with the flow,” explains co-author Dr. Stephan Roth from DESY, head of the experimental station P03 at PETRA III where the experiments took place. “Furthermore, salt is added to the outer streams. The salt makes the fibrils attach to each other, thereby locking the structure of the future filament.”

Finally, the wet filaments are left to dry in air where they shrink to form a strong fibre. “Drying takes a few minutes in air,” explains co-author Dr. Daniel Söderberg from KTH. “The resulting material is completely compatible with the biosphere, since the natural structure of the cellulose is maintained in the fibrils. Thus, it is biodegradable and compatible with human tissue.”

The bright X-ray light from PETRA III enabled the scientists to follow the process and check the configuration of the nano fibrils at various stages in the flow. “Research today is driven by cross-disciplanary collaborations,” underlines Söderberg. “Without the excellent competence and possibilities brought into the project by the team of DESY’s experimental station P03 this would not have been possible.”

As the scientists write, their fibres are much stronger than all other previously reported artificial filaments from cellulose nano fibrils. In fact, the artificial filaments can rival the strongest natural cellulose pulp fibres extracted from wood at the same degree of alignment of the nano fibrils. “In principle, we can make very long fibres,” says Lundell. “Up until now we have made samples that where ten centimetres long or so, but that is more of an equipment issue than a fundamental problem.”

For their experiments, the researchers have used nano fibrils extracted from fresh wood. “In principle, it should be possible to obtain fibrils from recycled paper also,” says Lundell. But he cautions: “The potential of recycled material in this context needs further investigations.”

Here’s a link to and a citation for the published paper,

Hydrodynamic alignment and assembly of nano-fibrils resulting in strong cellulose filaments by Karl M. O. Håkansson, Andreas B. Fall, Fredrik Lundell, Shun Yu, Christina Krywka, Stephan V. Roth, Gonzalo Santoro, Mathias Kvick, Lisa Prahl Wittberg, Lars Wågberg & L. Daniel Söderberg. Nature Communications, 2014; DOI: 10.1038/ncomms5018

This is an open access paper.

I posted a June 3, 2014 item on cellulose nanofibriil titled:  Doubling paper strength with nanofibrils; a nanocellulose.