Tag Archives: cellulose nanofibrils

Nanocellulose and food waste, an Australian perspective

A trio of Australian academics (Alan Labas, Benjamin Matthew Long, and Dylan Liu, all from Federation University Australia) have written a September 26, 2023 essay about nanocellulose derived from food waste for The Conversation, Note: Links have been removed,

Food waste is a global problem with approximately 1.3 billion tonnes of food wasted each year throughout the food lifecycle – from the farm to food manufacturers and households.

Across the food supply chain, Australians waste around 7.6 million tonnes of food each year. This costs our economy approximately A$36.6 billion annually.

In a recent study published in Bioresource Technology Reports, we have found a way to use food waste for making a versatile material known as nanocellulose. In particular, we used acid whey – a significant dairy production waste material that it usually difficult to dispose of.

For those who may not be familiar with nanocellulose, a lot of research was done here in Canada with a focus on using forest and agricultural waste products to produce nanocellulose. (See the CelluForce and Blue Goose Biorefineries websites for more about nanocellulose production, which in both their cases results in a specific material known as cellulose nanocrystals [CNC].) There’s more about the different kinds of nanocellulose later in this post.

The September 26, 2023 essay offers a good description of nanocellulose,

Nanocellulose is a biopolymer, which means it’s a naturally produced long chain of sugars. It has remarkable properties – bacterial nanocellulose is strong, chemically stable and biocompatible, meaning it’s not harmful to human cells. This makes it a highly marketable product with applications in packaging, wound treatments, drug delivery or food production.

Then, there’s this about the production process, from the September 26, 2023 essay, Note: A link has been removed,

The traditional approach for making nanocellulose can be expensive, uses large amounts of energy and takes a long time. Some types of nanocellulose production [emphasis mine] also use a chemical process that produces unwanted waste byproducts.

By contrast, our new approach uses just food waste and a symbiotic culture of bacteria and yeasts (SCOBY) – something you may be familiar with as a kombucha starter. Our process is low cost, consumes little energy and produces no waste.

… Lovers of home-brewed kombucha may actually be familiar with the raw nanocellulose material – it forms as a floating off-white structure called a pellicle. Some people already use this kombucha by-product as vegan leather.) A similar pellicle formed on our acid whey mixture.

I’m not sure if the “types of nanocellulose production” the writers are referring to are different types of nanocellose materials or different types of nanocellulose extraction.

A little more about nanocellulose

The Nanocellulose Wikipedia entry highlights the different materials that can be derived from nanocellulose, Note: Links have been removed,

Nanocellulose is a term referring to nano-structured cellulose. This may be either cellulose nanocrystal (CNC or NCC [nanocellulose crystal]), cellulose nanofibers (CNF) also called nanofibrillated cellulose (NFC), or bacterial nanocellulose, which refers to nano-structured cellulose produced by bacteria.

CNF is a material composed of nanosized cellulose fibrils with a high aspect ratio (length to width ratio). Typical fibril widths are 5–20 nanometers with a wide range of lengths, typically several micrometers. It is pseudo-plastic and exhibits thixotropy, the property of certain gels or fluids that are thick (viscous) under normal conditions, but become less viscous when shaken or agitated. When the shearing forces are removed the gel regains much of its original state. The fibrils are isolated from any cellulose containing source including wood-based fibers (pulp fibers) through high-pressure, high temperature and high velocity impact homogenization, grinding or microfluidization (see manufacture below).[1][2][3]

Nanocellulose can also be obtained from native fibers by an acid hydrolysis, giving rise to highly crystalline and rigid nanoparticles which are shorter (100s to 1000 nanometers) than the cellulose nanofibrils (CNF) obtained through homogenization, microfluiodization or grinding routes. The resulting material is known as cellulose nanocrystal (CNC).[4]

Nanochitin is similar in its nanostructure to nanocellulose.

Interestingly, Canadian development efforts are not mentioned in the essay until the very end, where we are lost in a plethora of other mentions, Note 1: Links have been removed; Note 2: All emphases mine,

A lthough wood-driven nanocellulose was first produced in 1983 by Herrick[7] and Turbak,[6] its commercial production postponed till 2010, mainly due to the high production energy consumption and high production cost. Innventia AB (Sweden) established the first nanocellulose pilot production plant 2010.[109] Companies and research institutes actively producing micro and nano fibrillated cellulose include: American Process (US), Borregaard (Norway), CelluComp (UK), Chuetsu Pulp and Paper (Japan), CTP/FCBA (France), Daicel (Japan), Dai-ichi Kyogo (Japan), Empa (Switzerland), FiberLean Technologies (UK), InoFib (France), Nano Novin Polymer Co. (Iran), Nippon Paper (Japan), Norske Skog (Norway), Oji Paper (Japan), RISE (Sweden), SAPPI (Netherlands), Seiko PMC (Japan), Stora Enso (Finland), Sugino Machine (Japan), Suzano (Brazil), Tianjin Haojia Cellulose Co. Ltd (China), University of Maine (US), UPM (Finland), US Forest Products Lab (US), VTT (Finland), and Weidmann Fiber Technology (Switzerland).[110] Companies and research institutes actively producing cellulose nanocrystals include: Alberta Innovates (Canada), American Process (US), Blue Goose Biorefineries (Canada), CelluForce (Canada), FPInnovations (Canada), Hangzhou Yeuha Technology Co. (China), Melodea (Israel/Sweden), Sweetwater Energy (US), Tianjin Haojia Cellulose Co. Ltd (China), and US Forest Products Lab (US).[110] Companies and research institutes actively producing cellulose filaments include: Kruger (Canada), Performance BioFilaments (Canada), and Tianjin Haojia Cellulose Co. Ltd (China).[110] Cellucomp (Scotland) produces Curran, a root-vegetable based nanocellulose.[111]

This leaves me with a couple of questions: Is my understanding of the nanocellulose story insular or Is the Wikipedia entry a little US-centric? It’s entirely possible the answer to both questions could be yes.

Why so much interest in nanocellulose? Money

From the September 26, 2023 essay, Note: A link has been removed,

Demand for nanocellulose is growing worldwide. The global market was valued at US$0.4 billion in 2022 (A$0.6bn) and is expected to grow to US$2 billion by 2030 (A$3.1bn). Bacterial nanocellulose produced from food waste can help to satisfy this demand.

This growth is in part due to how we can use nanocellulose instead of petroleum-based and other non-renewable materials in things like packaging. Among its desirable properties, nanocellulose is also fully biodegradable.

If you have time, do read the September 26, 2023 essay in its entirety.

H/t to September 27, 2023 news item on phys.org

Nanocellulose sensors: 3D printed and biocompatible

I do like to keep up with nanocellulose doings, especially when there’s some Canadian involvement, and an October 8, 2019 news item on Nanowerk alerted me to a newish application for the product,

Physiological parameters in our blood can be determined without painful punctures. Empa researchers are currently working with a Canadian team to develop flexible, biocompatible nanocellulose sensors that can be attached to the skin. The 3D-printed analytic chips made of renewable raw materials will even be biodegradable in future.

The idea of measuring parameters that are relevant for our health via the skin has already taken hold in medical diagnostics. Diabetics, for example, can painlessly determine their blood sugar level with a sensor instead of having to prick their fingers.

An October 8, 2019 Empa (Swiss Federal Laboratories for Materials Science and Technology) press release, which originated the news item, provides more detail,

A transparent foil made of wood

Nanocellulose is an inexpensive, renewable raw material, which can be obtained in form of crystals and fibers, for example from wood. However, the original appearance of a tree no longer has anything to do with the gelatinous substance, which can consist of cellulose nanocrystals and cellulose nanofibers. Other sources of the material are bacteria, algae or residues from agricultural production. Thus, nanocellulose is not only relatively easy and sustainable to obtain. Its mechanical properties also make the “super pudding” an interesting product. For instance, new composite materials based on nanocellulose can be developed that could be used as surface coatings, transparent packaging films or even to produce everyday objects like beverage bottles.

Researchers at Empa’s Cellulose & Wood Materials lab and Woo Soo Kim from the Simon Fraser University [SFU] in Burnaby, Canada, are also focusing on another feature of nanocellulose: biocompatibility. Since the material is obtained from natural resources, it is particularly suitable for biomedical research.

With the aim of producing biocompatible sensors that can measure important metabolic values, the researchers used nanocellulose as an “ink” in 3D printing processes. To make the sensors electrically conductive, the ink was mixed with silver nanowires. The researchers determined the exact ratio of nanocellulose and silver threads so that a three-dimensional network could form.

Just like spaghetti – only a wee bit smaller

It turned out that cellulose nanofibers are better suited than cellulose nanocrystals to produce a cross-linked matrix with the tiny silver wires. “Cellulose nanofibers are flexible similar to cooked spaghetti, but with a diameter of only about 20 nanometers and a length of just a few micrometers,” explains Empa researcher Gilberto Siqueira.

The team finally succeeded in developing sensors that measure medically relevant metabolic parameters such as the concentration of calcium, potassium and ammonium ions. The electrochemical skin sensor sends its results wirelessly to a computer for further data processing. The tiny biochemistry lab on the skin is only half a millimeter thin.

While the tiny biochemistry lab on the skin – which is only half a millimeter thin – is capable of determining ion concentrations specifically and reliably, the researchers are already working on an updated version. “In the future, we want to replace the silver [nano] particles with another conductive material, for example on the basis of carbon compounds,” Siqueira explains. This would make the medical nanocellulose sensor not only biocompatible, but also completely biodegradable.

I like the images from Empa better than the ones from SFU,

Using a 3D printer, the nanocellulose “ink” is applied to a carrier plate. Silver particles provide the electrical conductivity of the material. Image: Empa
Empa researcher Gilberto Siqueira demonstrates the newly printed nanocellulose circuit. After a subsequent drying, the material can be further processed. Image: Empa

SFU produced a news release about this work back in February 2019. Again, I prefer what the Swiss have done because they’re explaining/communicating the science, as well as , communicating benefits. From a February 13, 2019 SFU news release (Note: Links have been removed),

Simon Fraser University and Swiss researchers are developing an eco-friendly, 3D printable solution for producing wireless Internet-of-Things (IoT) sensors that can be used and disposed of without contaminating the environment. Their research has been published as the cover story in the February issue of the journal Advanced Electronic Materials.

SFU professor Woo Soo Kim is leading the research team’s discovery, which uses a wood-derived cellulose material to replace the plastics and polymeric materials currently used in electronics.

Additionally, 3D printing can give flexibility to add or embed functions onto 3D shapes or textiles, creating greater functionality.

“Our eco-friendly, 3D-printed cellulose sensors can wirelessly transmit data during their life, and then can be disposed without concern of environmental contamination,” says Kim, a professor in the School of Mechatronic Systems Engineering. The SFU research is being carried out at PowerTech Labs in Surrey, which houses several state-of-the-art 3D printers used to advance the research.

“This development will help to advance green electronics. For example, the waste from printed circuit boards is a hazardous source of contamination to the environment. If we are able to change the plastics in PCB to cellulose composite materials, recycling of metal components on the board could be collected in a much easier way.”

Kim’s research program spans two international collaborative projects, including the latest focusing on the eco-friendly cellulose material-based chemical sensors with collaborators from the Swiss Federal Laboratories for Materials Science.

He is also collaborating with a team of South Korean researchers from the Daegu Gyeongbuk Institute of Science and Technology’s (DGIST)’s department of Robotics Engineering, and PROTEM Co Inc, a technology-based company, for the development of printable conductive ink materials.

In this second project, researchers have developed a new breakthrough in the embossing process technology, one that can freely imprint fine circuit patterns on flexible polymer substrate, a necessary component of electronic products.

Embossing technology is applied for the mass imprinting of precise patterns at a low unit cost. However, Kim says it can only imprint circuit patterns that are imprinted beforehand on the pattern stamp, and the entire, costly stamp must be changed to put in different patterns.

The team succeeded in developing a precise location control system that can imprint patterns directly resulting in a new process technology. The result will have widespread implications for use in semiconductor processes, wearable devices and the display industry.

This paper was made available online back in December 2018 and then published in print in February 2019. As to why there’d be such large gaps between the paper’s publication dates and the two institution’s news/press releases, it’s a mystery to me. In any event, here’s a link to and a citation for the paper,

3D Printed Disposable Wireless Ion Sensors with Biocompatible Cellulose Composites by Taeil Kim, Chao Bao, Michael Hausmann, Gilberto Siqueira, Tanja Zimmermann, Woo Soo Kim. Advanced Electronic Materials DOI: https://doi.org/10.1002/aelm.201970007 First published online December 19, 2018. First published in print: 08 February 2019 (Adv. Electron. Mater. 2/2109) Volume 5, Issue 2 February 2019 1970007

This paper is behind a paywall.

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.

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).