Tag Archives: cellulose nanofibrils

Cellulose and natural nanofibres

Specifically, the researchers are describing these as cellulose nanofibrils. On the left of the image, the seed look mores like an egg waiting to be fried for breakfast but the image on the right is definitely fibrous-looking,

Through contact with water, the seed of Neopallasia pectinata from the family of composite plants forms a slimy sheath. The white cellulose fibres anchor it to the seed surface. Courtesy: Kiel University (CAU)

A December 18, 2018 news item on Nanowerk describes the research into seeds and cellulose,

The seeds of some plants such as basil, watercress or plantain form a mucous envelope as soon as they come into contact with water. This cover consists of cellulose in particular, which is an important structural component of the primary cell wall of green plants, and swelling pectins, plant polysaccharides.

In order to be able to investigate its physical properties, a research team from the Zoological Institute at Kiel University (CAU) used a special drying method, which gently removes the water from the cellulosic mucous sheath. The team discovered that this method can produce extremely strong nanofibres from natural cellulose. In future, they could be especially interesting for applications in biomedicine.

A December 18, 2018 Kiel University press release, which originated the news item, offers further details about the work,

Thanks to their slippery mucous sheath, seeds can slide through the digestive tract of birds undigested. They are excreted unharmed, and can be dispersed in this way. It is presumed that the mucous layer provides protection. “In order to find out more about the function of the mucilage, we first wanted to study the structure and the physical properties of this seed envelope material,” said Zoology Professor Stanislav N. Gorb, head of the “Functional Morphology and Biomechanics” working group at the CAU. In doing so they discovered that its properties depend on the alignment of the fibres that anchor them to the seed surface

Diverse properties: From slippery to sticky

The pectins in the shell of the seeds can absorb a large quantity of water, and thus form a gel-like capsule around the seed in a few minutes. It is anchored firmly to the surface of the seed by fine cellulose fibres with a diameter of just up to 100 nanometres, similar to the microscopic adhesive elements on the surface of highly-adhesive gecko feet. So in a sense, the fibres form the stabilising backbone of the mucous sheath.

The properties of the mucous change, depending on the water concentration. “The mucous actually makes the seeds very slippery. However, if we reduce the water content, it becomes sticky and begins to stick,” said Stanislav Gorb, summarising a result from previous studies together with Dr Agnieszka Kreitschitz. The adhesive strength is also increased by the forces acting between the individual vertically-arranged nanofibres of the seed and the adhesive surface.

Specially dried

In order to be able to investigate the mucous sheath under a scanning electron microscope, the Kiel research team used a particularly gentle method, so-called critical-point drying (CPD). They dehydrated the mucous sheath of various seeds step-by-step with liquid carbon dioxide – instead of the normal method using ethanol. The advantage of this method is that evaporation of liquid carbon dioxide can be controlled under certain pressure and temperature conditions, without surface tension developing within the sheath. As a result, the research team was able to precisely remove water from the mucous, without drying out the surface of the sheath and thereby destroying the original cell structure. Through the highly-precise drying, the structural arrangement of the individual cellulose fibres remained intact.

Almost as strongly-adhesive as carbon nanotubes

The research team tested the dried cellulose fibres regarding their friction and adhesion properties, and compared them with those of synthetically-produced carbon nanotubes. Due to their outstanding properties, such as their tensile strength, electrical conductivity or their friction, these microscopic structures are interesting for numerous industrial applications of the future.

“Our tests showed that the frictional and adhesive forces of the cellulose fibres are almost as strong as with vertically-arranged carbon nanotubes,” said Dr Clemens Schaber, first author of the study. The structural dimensions of the cellulose nanofibers are similar to the vertically aligned carbon nanotubes. Through the special drying method, they can also vary the adhesive strength in a targeted manner. In Gorb’s working group, the zoologist and biomechanic examines the functioning of biological nanofibres, and the potential to imitate them with technical means. “As a natural raw material, cellulose fibres have distinct advantages over carbon nanotubes, whose health effects have not yet been fully investigated,” continued Schaber. Nanocellulose is primarily found in biodegradable polymer composites, which are used in biomedicine, cosmetics or the food industry.

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

Friction-Active Surfaces Based on Free-Standing Anchored Cellulose Nanofibrils by Clemens F. Schaber, Agnieszka Kreitschitz, and Stanislav N. Gorb. ACS Appl. Mater. Interfaces, 2018, 10 (43), pp 37566–37574 DOI: 10.1021/acsami.8b05972 Publication Date (Web): September 19, 2018

Copyright © 2018 American Chemical Society

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.

Biodegradable films from cellulose nanofibrils

A team at Purdue University (Indiana, US) has developed a new process for biodegradable films based on cellulose according to a June 8, 2016 news item on phys.org,

Purdue University researchers have developed tough, flexible, biodegradable films from cellulose, the main component of plant cell walls. The films could be used for products such as food packaging, agricultural groundcovers, bandages and capsules for medicine or bioactive compounds.

Food scientists Srinivas Janaswamy and Qin Xu engineered the cellophane-like material by solubilizing cellulose using zinc chloride, a common inorganic salt, and adding calcium ions to cause the cellulose chains to become tiny fibers known as nanofibrils, greatly increasing the material’s tensile strength. The zinc chloride and calcium ions work together to form a gel network, allowing the researchers to cast the material into a transparent, food-grade film.

A June 7, 2016 Purdue University news release by Natalie van Hoose, which originated the news item, discusses the need for these films and provides a few more technical details about the work (Note: A link has been removed),

“We’re looking for innovative ways to adapt and use cellulose – an inexpensive and widely available material – for a range of food, biomedical and pharmaceutical applications,” said Janaswamy, research assistant professor of food science and principal author of the study. “Though plastics have a wide variety of applications, their detrimental impact on the environment raises a critical need for alternative materials. Cellulose stands out as a viable option, and our process lays a strong foundation for developing new biodegradable plastics.”

Cellulose’s abundance, renewability and ability to biodegrade make it a promising substitute for petroleum-based products. While a variety of products such as paper, cellophane and rayon are made from cellulose, its tightly interlinked structure and insolubility – qualities that give plants strength and protection – make it a challenging material to work with.

Janaswamy and Xu loosened the cellulose network by adding zinc chloride, which helps push cellulose’s closely packed sheets apart, allowing water to penetrate and solubilize it. Adding calcium ions spurs the formation of nanofibrils through strong bonds between the solubilized cellulose sheets. The calcium ions boost the tensile strength of the films by about 250 percent.

The production process preserves the strength and biodegradability of cellulose while rendering it transparent and flexible.

Because the zinc chloride can be recycled to repeat the process, the method offers an environmentally friendly alternative to conventional means of breaking down cellulose, which tend to rely on toxic chemicals and extreme temperatures.

“Products based on this film can have a no-waste lifecycle,” said Xu, research assistant professor of food science and first author of the study. “This process allows us to create a valuable product from natural materials – including low-value or waste materials such as corn stover or wood chips- that can eventually be returned to the Earth.”

The methodology could be adapted to mass-produce cellulose films, the researchers said.

The next step in the project is to find ways of making the cellulose film insoluble to water while maintaining its ability to biodegrade.

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

A facile route to prepare cellulose-based films by Qin Xu, Chen Chen, Katelyn Rosswurm, Tianming Yao, Srinivas Janaswamy. Carbohydrate Polymers Volume 149, 20 September 2016, Pages 274–281 doi:10.1016/j.carbpol.2016.04.114

This paper is behind a paywall.

4D printing: a hydrogel orchid

In 2013, the 4th dimension for printing was self-assembly according to a March 1, 2013 article by Tuan Nguyen for ZDNET. A Jan. 25, 2016 Wyss Institute for Biologically Inspired Engineering at Harvard University news release (also on EurekAlert) points to time as the fourth dimension in a description of the Wyss Institute’s latest 4D printed object,

A team of scientists at the Wyss Institute for Biologically Inspired Engineering at Harvard University and the Harvard John A. Paulson School of Engineering and Applied Sciences has evolved their microscale 3D printing technology to the fourth dimension, time. Inspired by natural structures like plants, which respond and change their form over time according to environmental stimuli, the team has unveiled 4D-printed hydrogel composite structures that change shape upon immersion in water.

“This work represents an elegant advance in programmable materials assembly, made possible by a multidisciplinary approach,” said Jennifer Lewis, Sc.D., senior author on the new study. “We have now gone beyond integrating form and function to create transformable architectures.”

In nature, flowers and plants have tissue composition and microstructures that result in dynamic morphologies that change according to their environments. Mimicking the variety of shape changes undergone by plant organs such as tendrils, leaves, and flowers in response to environmental stimuli like humidity and/or temperature, the 4D-printed hydrogel composites developed by Lewis and her team are programmed to contain precise, localized swelling behaviors. Importantly, the hydrogel composites contain cellulose fibrils that are derived from wood and are similar to the microstructures that enable shape changes in plants.

By aligning cellulose fibrils (also known as, cellulose nanofibrils or nanofibrillated cellulose) during printing, the hydrogel composite ink is encoded with anisotropic swelling and stiffness, which can be patterned to produce intricate shape changes. The anisotropic nature of the cellulose fibrils gives rise to varied directional properties that can be predicted and controlled. Just like wood, which can be split easier along the grain rather than across it. Likewise, when immersed in water, the hydrogel-cellulose fibril ink undergoes differential swelling behavior along and orthogonal to the printing path. Combined with a proprietary mathematical model developed by the team that predicts how a 4D object must be printed to achieve prescribed transformable shapes, the new method opens up many new and exciting potential applications for 4D printing technology including smart textiles, soft electronics, biomedical devices, and tissue engineering.

“Using one composite ink printed in a single step, we can achieve shape-changing hydrogel geometries containing more complexity than any other technique, and we can do so simply by modifying the print path,” said Gladman [A. Sydney Gladman, Wyss Institute a graduate research assistant]. “What’s more, we can interchange different materials to tune for properties such as conductivity or biocompatibility.”

The composite ink that the team uses flows like liquid through the printhead, yet rapidly solidifies once printed. A variety of hydrogel materials can be used interchangeably resulting in different stimuli-responsive behavior, while the cellulose fibrils can be replaced with other anisotropic fillers of choice, including conductive fillers.

“Our mathematical model prescribes the printing pathways required to achieve the desired shape-transforming response,” said Matsumoto [Elisabetta Matsumoto, Ph.D., a postdoctoral fellow at the Wyss]. “We can control the curvature both discretely and continuously using our entirely tunable and programmable method.”

Specifically, the mathematical modeling solves the “inverse problem”, which is the challenge of being able to predict what the printing toolpath must be in order to encode swelling behaviors toward achieving a specific desired target shape.

“It is wonderful to be able to design and realize, in an engineered structure, some of nature’s solutions,” said Mahadevan [L. Mahadevan, Ph.D., a Wyss Core Faculty member] , who has studied phenomena such as how botanical tendrils coil, how flowers bloom, and how pine cones open and close. “By solving the inverse problem, we are now able to reverse-engineer the problem and determine how to vary local inhomogeneity, i.e. the spacing between the printed ink filaments, and the anisotropy, i.e. the direction of these filaments, to control the spatiotemporal response of these shapeshifting sheets. ”

“What’s remarkable about this 4D printing advance made by Jennifer and her team is that it enables the design of almost any arbitrary, transformable shape from a wide range of available materials with different properties and potential applications, truly establishing a new platform for printing self-assembling, dynamic microscale structures that could be applied to a broad range of industrial and medical applications,” said Wyss Institute Founding Director Donald Ingber, M.D., Ph.D., who is also the Judah Folkman Professor of Vascular Biology at Harvard Medical School and the Vascular Biology Program at Boston Children’s Hospital and Professor of Bioengineering at Harvard SEAS [School of Engineering and Applied Science’.

Here’s an animation from the Wyss Institute illustrating the process,

And, here’s a link to and a citation for the paper,

Biomimetic 4D printing by A. Sydney Gladman, Elisabetta A. Matsumoto, Ralph G. Nuzzo, L. Mahadevan, & Jennifer A. Lewis. Nature Materials (2016) doi:10.1038/nmat4544 Published online 25 January 2016

This paper is behind a paywall.

Cellulose Nanofibrillated Fiber Based Transistors from the University of Wisconsin-Madison

There’s a team of researchers at the University of Wisconsin-Madison working to substitute silicon used in computer chips with cellulose derived from wood (my May 27, 2015 posting). Their latest effort, featuring mobile electronics, is described in a July 1, 2015 news item on Azonano,

A report published by the U.S. Environmental Protection Agency in 2012 showed that about 152 million mobile devices are discarded every year, of which only 10 percent is recycled — a legacy of waste that consumes a tremendous amount of natural resources and produces a lot of trash made from expensive and non-biodegradable materials like highly purified silicon.

Now researchers from the University of Wisconsin-Madison have come up with a new solution to alleviate the environmental burden of discarded electronics. They have demonstrated the feasibility of making microwave biodegradable thin-film transistors from a transparent, flexible biodegradable substrate made from inexpensive wood, called cellulose nanofibrillated fiber (CNF). This work opens the door for green, low-cost, portable electronic devices in future.

A June 30, 2015 American Institute of Physics news release by Zhengzheng Zhang, which originated the news item, describes the research in more detail,

“We found that cellulose nanofibrillated fiber based transistors exhibit superior performance as that of conventional silicon-based transistors,” said Zhenqiang Ma, the team leader and a professor of electrical and computer engineering at the UW-Madison. “And the bio-based transistors are so safe that you can put them in the forest, and fungus will quickly degrade them. They become as safe as fertilizer.”

Nowadays, the majority of portable electronics are built on non-renewable, non-biodegradable materials such as silicon wafers, which are highly purified, expensive and rigid substrates, but cellulose nanofibrillated fiber films have the potential to replace silicon wafers as electronic substrates in environmental friendly, low-cost, portable gadgets or devices of the future.

Cellulose nanofibrillated fiber is a sustainable, strong, transparent nanomaterial made from wood. Compared to other polymers like plastics, the wood nanomaterial is biocompatible and has relatively low thermal expansion coefficient, which means the material won’t change shape as the temperature changes. All these superior properties make cellulose nanofibril an outstanding candidate for making portable green electronics.

To create high-performance devices, Ma’s team employed silicon nanomembranes as the active material in the transistor — pieces of ultra-thin films (thinner than a human hair) peeled from the bulk crystal and then transferred and glued onto the cellulose nanofibrill substrate to create a flexible, biodegradable and transparent silicon transistor.To create high-performance devices, Ma’s team employed silicon nanomembranes as the active material in the transistor — pieces of ultra-thin films (thinner than a human hair) peeled from the bulk crystal and then transferred and glued onto the cellulose nanofibrill substrate to create a flexible, biodegradable and transparent silicon transistor.

But to make portable electronics, the biodegradable transistor needed to be able to operate at microwave frequencies, which is the working range of most wireless devices. The researchers thus conducted a series of experiments such as measuring the current-voltage characteristics to study the device’s functional performance, which finally showed the biodegradable transistor has superior microwave-frequency operation capabilities comparable to existing semiconductor transistors.

“Biodegradable electronics provide a new solution for environmental problems brought by consumers’ pursuit of quickly upgraded portable devices,” said Ma. “It can be anticipated that future electronic chips and portable devices will be much greener and cheaper than that of today.”

Next, Ma and colleagues plan to develop more complicated circuit system based on the biodegradable transistors.

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

Microwave flexible transistors on cellulose nanofibrillated fiber substrates by Jung-Hun Seo, Tzu-Hsuan Chang, Jaeseong Lee, Ronald Sabo, Weidong Zhou, Zhiyong Cai, Shaoqin Gong, and Zhenqiang Ma.  Applied Physics Letters, Volume 106, Issue 26 or  Appl. Phys. Lett. 106, 262101 (2015); http://dx.doi.org/10.1063/1.4921077

This is an open access paper.

Tiny, electrically conductive 3D-printed chair made from cellulose

Sweden’s Chalmers University of Technology researchers have just announced that they’ve printed a very small 3D chair with electrical properties using cellulose nanomaterials. From a June 17, 2015 news item on Nanowerk,

A group of researchers at Chalmers University of Technology have managed to print and dry three-dimensional objects made entirely by cellulose for the first time with the help of a 3D-bioprinter. They also added carbon nanotubes to create electrically conductive material. The effect is that cellulose and other raw material based on wood will be able to compete with fossil-based plastics and metals in the on-going additive manufacturing revolution, which started with the introduction of the 3D-printer.

Here’s the 3D-printed chair,

The tiny chair made of cellulose is a demonstrational object, printed using the 3D bioprinter at Chalmers University of Technology. Photo: Peter Widing

The tiny chair made of cellulose is a demonstrational object, printed using the 3D bioprinter at Chalmers University of Technology. Photo: Peter Widing

A June 17, 2015 Chalmers University of Technology press release (also on EurekAlert*), which originated the news item, describes the problem with printing from cellulose nanomaterials and how it was solved,

The difficulty using cellulose in additive manufacturing is that cellulose does not melt when heated. Therefore, the 3D printers and processes designed for printing plastics and metals cannot be used for materials like cellulose. The Chalmers researchers solved this problem by mixing cellulose nanofibrils in a hydrogel consisting of 95-99 percent water. The gel could then in turn be dispensed with high fidelity into the researchers’ 3D bioprinter, which was earlier used to produce scaffolds for growing cells, where the end application is patient-specific implants.

The next challenge was to dry the printed gel-like objects without them losing their three-dimensional shape.

“The drying process is critical,” Paul Gatenholm explains. “We have developed a process in which we freeze the objects and remove the water by different means as to control the shape of the dry objects. It is also possible to let the structure collapse in one direction, creating thin films.”

Furthermore, the cellulose gel was mixed with carbon nanotubes to create electrically conductive ink after drying. Carbon nanotubes conduct electricity, and another project at Wallenberg Wood Science Center aims at developing carbon nanotubes using wood.

Using the two gels together, one conductive and one non-conductive, and controlling the drying process, the researchers produced three-dimensional circuits, where the resolution increased significantly upon drying.

The two gels together provide a basis for the possible development of a wide range of products made by cellulose with in-built electric currents.

“Potential applications range from sensors integrated with packaging, to textiles that convert body heat to electricity, and wound dressings that can communicate with healthcare workers,” says Paul Gatenholm. “Our research group now moves on with the next challenge, to use all wood biopolymers, besides cellulose.”

The research findings are presented this week at the conference New Materials From Trees that takes place in Stockholm, Sweden, June 15-17 [2015].

The research team members are Ida Henriksson, Cristina de la Pena, Karl Håkansson, Volodymyr Kuzmenko and Paul Gatenholm at Chalmers University of Technology.

This research reminds me of another effort, a computer chip fashioned of cellulose nanofibrils (CNF) from the University of Wisconsin-Madison (mentioned in my May 27, 2015 post).

* EurekAlert link added June 18, 2015.

SAPPI to locate cellulose nanofibril facility in the Netherlands

SAPPI (formerly South African Pulp and Paper Industries) has announced it will build a nanocellulose facility in the Netherlands. From a March 11, 2015 news item on Nanowerk,

Sappi Limited, a leading global producer of dissolving wood pulp and graphics, speciality and packaging papers, is pleased to announce that it will build a pilot-scale plant for low-cost Cellulose NanoFibrils (nanocellulose) production at the Brightlands Chemelot Campus in Sittard-Geleen in the Netherlands. The pilot plant is expected to be operational within nine months.

A March 11, 2015 SAPPI media release (also on PR Newswire), which originated the news item, provides more detail about SAPPI’s nanocellulose business plans and the proposed pilot plant,

Commenting on the decision, Andrea Rossi, Group Head Technology, Sappi Limited, explained that the pilot plant will help with Sappi’s move into new adjacent business fields based on renewable raw materials. Sappi’s strategy includes seeking growth opportunities by producing innovative performance materials from renewable resources. The raw material for the pilot plant would be supplied from any of Sappi’s Saiccor, Ngodwana and Cloquet dissolving wood pulp plants. The pilot plant is the precursor for Sappi to consider the construction of a commercial CNF plant.

He goes on to say “the pilot plant will test the manufacturing of dry re-dispersible Cellulose NanoFibrils (CNF) using the proprietary technology developed by Sappi and Edinburgh Napier University. The location of the pilot plant at Brightlands Chemelot Campus provides Sappi with easy access to multiple partners with whom Sappi will seek to co-develop products that will incorporate CNF across a large variety of product applications to optimise performance and to create unique characteristics for these products.

The CNF produced by Sappi will have unique morphology, specifically modified for either hydrophobic or hydrophilic applications. Products produced using Sappi’s CNF will be optimally suitable for conversion in lighter and stronger fibre-reinforced composites and plastics, in food and pharmaceutical applications, and in rheology modifiers as well as in barrier and other paper and coating applications.

Speaking on behalf of Brightlands Chemelot Campus, the CEO Bert Kip said “We’re proud that a globally leading company like Sappi has chosen our campus for their new facility. The initiative perfectly fits with our focus area on bio-based materials and our new pilot plant infrastructure.”

In December 2014, Sappi and Edinburgh Napier University announced the results of their 3 year project to find a low cost energy-saving process that would allow Sappi to produce the nanocellulose on a commercially viable basis – and importantly without producing large volumes of chemical waste water associated with existing techniques. At the time, Professor Rob English, who led the research with his Edinburgh Napier colleague, Dr. Rhodri Williams, said “What is significant about our process is the use of unique chemistry, which has allowed us to very easily break down the wood pulp fibers into nanocellulose. There is no expensive chemistry required and, most significantly, the chemicals used can be easily recycled and reused without generating large quantities of waste water.

Math Jennekens, R&D Director at Sappi Europe who is the project coordinator and will oversee the pilot plant, said “We are very excited to be able to move from a bench top environment into real-world production. Our targeted run-rate will be 8 tons per annum. We will produce a dry powder that can be easily redispersed in water. The nanocellulose is unmodified which makes it easier to combine with other materials. The product will be used to build partnerships to test the application of our nanocellulose across the widest range of uses.”

He went on to thank the Government of the Province of Limburg in the Netherlands for their significant support and financial contribution towards the establishment of the pilot plant.

This business with a pilot production plant reminds me of CelluForce which has a cellulose nanocrystal (CNC) or, as it’s also known, nanocellulose crystal (NCC) production plant located in Windsor, Québec. They too announced a production plant which opened to fanfare in January 2012. in my Oct. 3, 2013 post (scroll down about 60% of the way) I noted that production had stopped in August 2013 due to a growing stockpile. As of March 11, 2015, I was not able to find any updates about the stockpile on the CelluForce website. The most recent CelluForce information I’ve been able to find is in a Feb. 19, 2015 posting (scroll down about 40% of the way).

Final words on TAPPI’s June 2014 Nanotechnology for Renewable Materials conference

A July 8, 2014 news item on Nanowerk provides some statistics about the recently ended (June 23 – 26, 2014) TAPPI (Technical Association for the Pulp, Paper, Packaging and Converting Industries) Conference on Nanotechnology for Renewable Materials,

Over 230 delegates from 25 countries gathered in Vancouver, British Columbia, Canada last week at TAPPI’s 9th International Conference on Nanotechnology for Renewable Nanomaterials. “This year’s conference was exceptional,” noted co-chair Wadood Hamad, Priniciple Scientist, FPInnovations. “The keynote and technical presentations were of very high quality. The advancements made in many applications show great promise, and we will see expanded commercial use of these renewable biomaterials.”

An identical news item dated July 7, 2014 on Nanotechnology Now,notes the commercial announcements made during the conference,

Several key commercial announcements were made at this year’s conference, highlighting the tangible growth in this emerging market area of renewable biopolymers:

Celluforce, which opened their commercial plant in January 2012, shared six advanced commercial projects.

Imerys announced the launch of their new FiberLean™ MFC innovative composite, which enables a 10-15% reduction in fiber usage for papermaking applications.

Representatives from the newly formed BioFilaments shared information on their unique high performance biomaterial derived from wood cellulose to be used as reinforcing agents and rheological modifiers.

Blue Goose Biorefineries presented their patent-pending process for producing cellulose nanocrystals from wood pulp.

Nippon Paper Industries introduced Cellenpia, their cellulose nanofibers produced from their pre-commercial plant.

GL&V presented their commercial system, developed with the University of Maine, to produce cellulose nanofibrils at a very low energy cost.

American Process Inc. presented their latest results of producing lignin-coated nanocellulose particles using their AVAP® technology which produces a material that is more easily dispersed and has enhanced properties.

I wish them good luck with their projects.

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.

Doubling paper strength with nanofibrils; a nanocellulose story

A June 3, 2014 Cerealus news release on PR Newswire announces a successful commercial trial for a new nanoscale process making paper stronger,

Cerealus, working with the University of Maine Process Development Center continues to be a leader in innovative technologies for Paper and Forestry research. Utilizing Cerealus’ unique starch encapsulation technology and UMaine’s proprietary developments, the collaborative effort enabled a novel bio-based cellulose nanofibrils (CNF) process to be used in paper and paperboard manufacturing at significantly higher levels than previously possible to develop high strength, lightweight and lower cost paper and paperboard.

The latest commercial trial doubled cellulose Nanofibril utilization in paper with the patent pending starch encapsulation technology, marketed as Cerenano™. This project confirms the promise of nanotechnology to deliver dramatic improvement in sheet density, porosity, surface quality and Z-direction strength (internal bond). Paper mills can expect:

  •     Tighter sheet
  •     More uniform surface
  •     Better printability
  •     Reduced opacity
  •     Reduced energy requirements

The collaborative private/public partnership has significantly improved the economic prospects for deploying nanotechnology in paper, wood and forestry products. A recent report estimates the current addressable market for nano cellulose at $500 million for North America.

Mike Bilodeau, Director of the UMaine Process Development Center underscored the commercial scalability of this project by saying, “This technology represents a significant break-through in the ability to leverage the unique properties of cellulose nanofibrils in paper and paperboard products.”

Tony Jabar, CEO and founder of Cerealus goes on to say, “Cerealus takes great pride in taking a lead role to create cutting edge nanocellulose technology. Successful paper makers appreciate innovation as a key to sustained profitability in the challenging paper making sector of our economy. This new development is our third generation technology and demonstrates the value of our collaboration with the University of Maine Process Development Center.”

Cerenano™ is a high performance additive that enables efficient loading of high levels of starch thus creating strong internal bond strength. The successful commercial trial demonstrated positive economic benefits and commercial scalability. The likely next phase in product development will be size press applications.

The University of Maine is working with several private companies and federal agencies to accelerate the commercialization of cellulose nanofibrils. This effort has significant implications to the health of National Forests and private timberland, as well as strategic and economic impacts to the domestic Forest Products Industry.

You can find Cerealus here and Cerenano™ page here where there’s a link to a 50 pp. presentation on Cerenano. From the presentation,

Using Renewable Nanotechnology (and Other Novel Approaches) to Improve Base Paper Performance
AWA Conferences & Events
AWA Silicone Technology Seminar 2014
March 19, 2014
Park Plaza Hotel Amsterdam Airport
Amsterdam, Netherlands
Robert Hamilton
Stirling Consulting, Inc.

I was particularly interested to see this (from p. 3 of the presentation),

Cellulose Nanofibrils (CNF)
The Renewable Nanomaterial

• CNF can be made from any plant matter.
# Process uses a series of mechanical refining steps.
# Resulting material is FDA compliant and compatible with any aqueous system. CNF is cellulose.

• Not to be confused with Cellulose NanoCrystals (CNC)
# Produced using more expensive strong acid hydrolysis process.

It’s the first time I’ve stumbled across a comparison of any kind between CNC (also known as NCC, nanocrystalline cellulose) and CNF and I find it quite instructive.