Tag Archives: nanocellulose

Cellulose- and chitin-based biomaterial to replace plastics?

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

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

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

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

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

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

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

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

crab shells

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

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

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

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

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

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

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

lab vials

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

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

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

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

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

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

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

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

Bio-based standup pouches (food packaging) made from cellulose

CAPTION: VTT has developed lightweight 100% bio-based stand-up pouches with high technical performance. (Photo by VTT)

A March 14, 2017 news item on ScienceDaily describes a new nanocellulose-based product developed by the Technical Research Centre of Finland (VTT),

VTT Technical Research Centre of Finland Ltd has developed lightweight 100% bio-based stand-up pouches with high technical performance. High performance in both oxygen, grease and mineral oil barrier properties has been reached by using different biobased coatings on paper substrate. The pouches exploit VTT’s patent pending high consistency enzymatic fibrillation of cellulose (HefCel) technology.

A March 14, 2017 VTT press release (also on EurekAlert), which originated the news item, describes why the researchers want to change how food is packaged,

“One-third of food produced for human consumption is lost or wasted globally. Packaging with efficient barrier properties is a crucial factor in the reduction of the food loss. Our solution offers an environmentally friendly option for the global packaging industry”, says Senior Scientist Jari Vartiainen of VTT.

VTT’s HefCel technology provides a low-cost method for the production of nanocellulose resulting in a tenfold increase in the solids content of nanocellulose. Nanocellulose has been shown to be potentially very useful for a number of future technical applications. The densely packed structure of nanocellulose films and coatings enable their outstanding oxygen, grease and mineral oil barrier properties.

HefCel technology exploits industrial enzymes and simple mixing technology as tools to fibrillate cellulose into nanoscale fibrils without the need for high energy consuming process steps. The resulting nanocellulose is in the consistency of 15-25% when traditional nanocellulose production methods result in 1-3% consistency.

The stand-up pouch is the fastest growing type of packaging, growing at a rate of 6.5% per year from 2015-2020. Fossil-based plastic films still dominate the packaging market. However, the development of environmentally friendly new materials is of growing importance. Nanocellulose has been shown to be potentially very useful for a number of future technical applications.

VTT has solid expertise in various bio-based raw materials and their application technologies for producing bio-based coatings, films and even multilayered structures both at lab-scale and pilot-scale. A versatile set of piloting facilities are available from raw material sourcing through processing to application testing and demonstration.

I’m glad to hear they’re finding uses for nanocellulose and I keep wondering when Canadian scientists who at one point were leaders in developing crystal nanocellulose (CNC or sometimes known as nanocrystalline cellulose [NCC]) will be making announcements about potential products.

The Swiss come to a better understanding of nanomaterials

Just to keep things interesting, after the report suggesting most of the information that the OECD (Organization for Economic Cooperation and Development) has on nanomaterials is of little value for determining risk (see my April 5, 2017 posting for more) the Swiss government has released a report where they claim an improved understanding of nanomaterials than they previously had due to further research into the matter. From an April 6, 2017 news item on Nanowerk,

In the past six years, the [Swiss] National Research Programme “Opportunities and Risks of Nanomaterials” (NRP 64) intensively studied the development, use, behaviour and degradation of engineered nanomaterials, including their impact on humans and on the environment.

Twenty-three research projects on biomedicine, the environment, energy, construction materials and food demonstrated the enormous potential of engineered nanoparticles for numerous applications in industry and medicine. Thanks to these projects we now know a great deal more about the risks associated with nanomaterials and are therefore able to more accurately determine where and how they can be safely used.

An April 6, 2017 Swiss National Science Foundation press release, which originated the news item, expands on the theme,

“One of the specified criteria in the programme was that every project had to examine both the opportunities and the risks, and in some cases this was a major challenge for the researchers,” explains Peter Gehr, President of the NRP 64 Steering Committee.

One development that is nearing industrial application concerns a building material strengthened with nanocellulose that can be used to produce a strong but lightweight insulation material. Successful research was also carried out in the area of energy, where the aim was to find a way to make lithium-ion batteries safer and more efficient.

Promising outlook for nanomedicine

A great deal of potential is predicted for the field of nanomedicine. Nine of the 23 projects in NRP 64 focused on biomedical applications of nanoparticles. These include their use for drug delivery, for example in the fight against viruses, or as immune modulators in a vaccine against asthma. Another promising application concerns the use of nanomagnets for filtering out harmful metallic substances from the blood. One of the projects demonstrated that certain nanoparticles can penetrate the placenta barrier, which points to potential new therapy options. The potential of cartilage and bone substitute materials based on nanocellulose or nanofibres was also studied.

The examination of potential health risks was the focus of NRP 64. A number of projects examined what happens when nanoparticles are inhaled, while two focused on ingestion. One of these investigated whether the human gut is able to absorb iron more efficiently if it is administered in the form of iron nanoparticles in a food additive, while the other studied silicon nanoparticles as they occur in powdered condiments. It was ascertained that further studies will be required in order to determine the doses that can be used without risking an inflammatory reaction in the gut.

What happens to engineered nanomaterials in the environment?

The aim of the seven projects focusing on environmental impact was to gain a better understanding of the toxicity of nanomaterials and their degradability, stability and accumulation in the environment and in biological systems. Here, the research teams monitored how engineered nanoparticles disseminate along their lifecycle, and where they end up or how they can be discarded.

One of the projects established that 95 per cent of silver nanoparticles that are washed out of textiles are collected in sewage treatment plants, while the remaining particles end up in sewage sludge, which in Switzerland is incinerated. In another project a measurement device was developed to determine how aquatic microorganisms react when they come into contact with nanoparticles.

Applying results and making them available to industry

“The findings of the NRP 64 projects form the basis for a safe application of nanomaterials,” says Christoph Studer from the Federal Office of Public Health. “It has become apparent that regulatory instruments such as testing guidelines will have to be adapted at both national and international level.” Studer has been closely monitoring the research programme in his capacity as the Swiss government’s representative in NRP 64. In this context, the precautionary matrix developed by the government is an important instrument by means of which companies can systematically assess the risks associated with the use of nanomaterials in their production processes.

The importance of standardised characterisation and evaluation of engineered nanomaterials was highlighted by the close cooperation among researchers in the programme. “The research network that was built up in the framework of NRP 64 is functioning smoothly and needs to be further nurtured,” says Professor Bernd Nowack from Empa, who headed one of the 23 projects.

The results of NRP 64 show that new key technologies such as the use of nanomaterials need to be closely monitored through basic research due to the lack of data on its long-term effects. As Peter Gehr points out, “We now know a lot more about the risks of nanomaterials and how to keep them under control. However, we need to conduct additional research to learn what happens when humans and the environment are exposed to engineered nanoparticles over longer periods, or what happens a long time after a one-off exposure.”

You can find out more about the Opportunities and Risks of Nanomaterials; National Research Programme (NRP 64) here.

Harvard University announced new Center on Nano-safety Research

The nano safety center at Harvard University (Massachusetts, US) is a joint center with the US National Institute of Environmental Health  Sciences according to an Aug. 29, 2016 news item on Nanowerk,

Engineered nanomaterials (ENMs)—which are less than 100 nanometers (one millionth of a millimeter) in diameter—can make the colors in digital printer inks pop and help sunscreens better protect against radiation, among many other applications in industry and science. They may even help prevent infectious diseases. But as the technology becomes more widespread, questions remain about the potential risks that ENMs may pose to health and the environment.

Researchers at the new Harvard-NIEHS [US National Institute of Environmental Health Sciences] Nanosafety Research Center at Harvard T.H. Chan School of Public Health are working to understand the unique properties of ENMs—both beneficial and harmful—and to ultimately establish safety standards for the field.

An Aug. 16, 2016 Harvard University press release, which originated the news item, provides more detail (Note: Links have been removed),

“We want to help nanotechnology develop as a scientific and economic force while maintaining safeguards for public health,” said Center Director Philip Demokritou, associate professor of aerosol physics at Harvard Chan School. “If you understand the rules of nanobiology, you can design safer nanomaterials.”

ENMs can enter the body through inhalation, ingestion, and skin contact, and toxicological studies have shown that some can penetrate cells and tissues and potentially cause biochemical damage. Because the field of nanoparticle science is relatively new, no standards currently exist for assessing the health risks of exposure to ENMs—or even for how studies of nano-biological interactions should be conducted.

Much of the work of the new Center will focus on building a fundamental understanding of why some ENMs are potentially more harmful than others. The team will also establish a “reference library” of ENMs, each with slightly varied properties, which will be utilized in nanotoxicology research across the country to assess safety. This will allow researchers to pinpoint exactly what aspect of an ENM’s properties may impact health. The researchers will also work to develop standardized methods for nanotoxicology studies evaluating the safety of nanomaterials.

The Center was established with a $4 million dollar grant from the National Institute of Environmental Health Science (NIEHS) last month, and is the only nanosafety research center to receive NIEHS funding for the next five years. It will also play a coordinating role with existing and future NIEHS nanotoxicology research projects nantionwide. Scientists from the Harvard John A. Paulson School of Engineering and Applied Sciences (SEAS), MIT, University of Maine, and University of Florida will collaborate on the new effort.

The Center builds on the existing Center for Nanotechnology and Nanotoxicology at Harvard Chan School, established by Demokritou and Joseph Brain, Cecil K. and Philip Drinker Professor of Environmental Physiology, in the School’s Department of Environmental Health in 2010.

A July 5, 2016 Harvard University press release announcing the $4M grant provides more information about which ENMs are to be studied,

The main focus of the new HSPH-NIEHS Center is to bring together  scientists from across disciplines- material science, chemistry, exposure assessment, risk assessment, nanotoxicology and nanobiology- to assess the potential  environmental Health and safety (EHS) implications of engineered nanomaterials (ENMs).

The $4 million dollar HSPH based Center  which is the only Nanosafety Research  Center to be funded by NIEHS this funding cycle, … The new HSPH-NIEHS Nanosafety Center builds upon the nano-related infrastructure in [the] collaborating Universities, developed over the past 10 years, which includes an inter-disciplinary research group of faculty, research staff and students, as well as state-of-the-art platforms for high throughput synthesis of ENMs, including metal and metal oxides, cutting edge 2D/3D ENMs such as CNTs [carbon nanotubes] and graphene, nanocellulose, and advanced nanocomposites, [emphasis mine] coupled with innovative tools to assess the fate and transport of ENMs in biological systems, statistical and exposure assessment tools, and novel in vitro and in vivo platforms for nanotoxicology research.

“Our mission is to integrate material/exposure/chemical sciences and nanotoxicology-nanobiology   to facilitate assessment of potential risks from emerging nanomaterials.  In doing so, we are bringing together the material synthesis/applications and nanotoxicology communities and other stakeholders including industry,   policy makers and the general public to maximize innovation and growth and minimize environmental and public health risks from nanotechnology”, quoted by  Dr Philip Demokritou, …

This effort certainly falls in line with the current emphasis on interdisciplinary research and creating standards and protocols for researching the toxicology of engineered nanomaterials.

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.

Paper as good at storing electrical energy as commercial supercapacitors

This is another potential nanocellulose application according to a Dec. 3, 2015 news item on ScienceDaily,

Researchers at Linköping University’s Laboratory of Organic Electronics, Sweden, have developed power paper — a new material with an outstanding ability to store energy. The material consists of nanocellulose and a conductive polymer. …

One sheet, 15 centimetres in diameter and a few tenths of a millimetre thick can store as much as 1 F, which is similar to the supercapacitors currently on the market. The material can be recharged hundreds of times and each charge only takes a few seconds.

A Dec. 3, 2015 Linköping University press release (also on EurekAlert), which originated the news item, provides more detail,

It’s a dream product in a world where the increased use of renewable energy requires new methods for energy storage — from summer to winter, from a windy day to a calm one, from a sunny day to one with heavy cloud cover.

“Thin films that function as capacitors have existed for some time. What we have done is to produce the material in three dimensions. We can produce thick sheets,” says Xavier Crispin, professor of organic electronics and co-author to the article just published in Advanced Science.

Other co-authors are researchers from KTH Royal Institute of Technology, Innventia, Technical University of Denmark and the University of Kentucky.

The material, power paper, looks and feels like a slightly plasticky paper and the researchers have amused themselves by using one piece to make an origami swan — which gives an indication of its strength.

The structural foundation of the material is nanocellulose, which is cellulose fibres which, using high-pressure water, are broken down into fibres as thin as 20 nm in diameter. With the cellulose fibres in a solution of water, an electrically charged polymer (PEDOT:PSS), also in a water solution, is added. The polymer then forms a thin coating around the fibres.

“The covered fibres are in tangles, where the liquid in the spaces between them functions as an electrolyte,” explains Jesper Edberg, doctoral student, who conducted the experiments together with Abdellah Malti, who recently completed his doctorate.

The new cellulose-polymer material has set a new world record in simultaneous conductivity for ions and electrons, which explains its exceptional capacity for energy storage. It also opens the door to continued development toward even higher capacity. Unlike the batteries and capacitors currently on the market, power paper is produced from simple materials – renewable cellulose and an easily available polymer. It is light in weight, it requires no dangerous chemicals or heavy metals and it is waterproof.

This press release also offers insight into funding and how scientists view requests for reports and oversight,

The Power Papers project has been financed by the Knut and Alice Wallenberg Foundation since 2012.

“They leave us to our research, without demanding lengthy reports, and they trust us. We have a lot of pressure on us to deliver, but it’s ok if it takes time, and we’re grateful for that,” says Professor Magnus Berggren, director of the Laboratory of Organic Electronics at Linköping University.

Naturally, commercialization efforts are already in the works. (Canadian nanocellulose community watch out! The Swedes are coming!),

The new power paper is just like regular pulp, which has to be dehydrated when making paper. The challenge is to develop an industrial-scale process for this.

“Together with KTH, Acreo and Innventia we just received SEK 34 million from the Swedish Foundation for Strategic Research to continue our efforts to develop a rational production method, a paper machine for power paper,” says Professor Berggren.

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

An Organic Mixed Ion–Electron Conductor for Power Electronics by Abdellah Malti, Jesper Edberg, Hjalmar Granberg, Zia Ullah Khan, Jens W. Andreasen, Xianjie Liu, Dan Zhao, Hao Zhang, Yulong Yao, Joseph W. Brill, Isak Engquist, Mats Fahlman, Lars Wågberg, Xavier Crispin, and Magnus Berggren. Advanced Science DOI: 10.1002/advs.201500305 Article first published online: 2 DEC 2015

© 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is open access.

Cellulose nanocrystals and a computational approach to new materials

There’s been a lot of research into cellulose nanomaterials as scientists work to develop applications for cellulose nanocrystals (CNC)* and cellulose nanofibrils (CNF). To date, there have been no such breakthroughs or, as they used to say, no such ‘killer apps’. An Oct. 2, 2015 news item on Nanowerk highlights work which made finally lead the way,

Theoretically, nanocellulose could be the next hot supermaterial.

A class of biological materials found within numerous natural systems, most notably trees, cellulose nanocrystals have captured researchers’ attention for their extreme strength, toughness, light weight, and elasticity. The materials are so strong and tough, in fact, that many people think they could replace Kevlar in ballistic vests and combat helmets for military. Unlike their source material (wood), cellulose nanocrystals are transparent, making them exciting candidates for protective eyewear, windows, or displays.

Although there is a lot of excitement around the idea of nanocellulose-based materials, the reality often falls flat.

“It’s difficult to make these theoretical properties materialize in experiments,” said Northwestern Engineering’s Sinan Keten. “Researchers will make composite materials with nanocellulose and find that they fall short of theory.”

Keten, an assistant professor of mechanical, civil, and environmental engineering at Northwestern University’s McCormick School of Engineering, and his team are bringing the world one step closer to a materials-by-design approach toward developing nanocomposites with cellulose. They have developed a novel, multi-scale computational framework that explains why these experiments do not produce the ideal material and proposes solutions for fixing these shortcomings, specifically by modifying the surface chemistry of cellulose nanocrystals to achieve greater hydrogen bonding with polymers.

An Oct. 2, 2015 (McCormick School of Engineering) Northwestern University news release (also on EurekAlert), which originated the news item, provides more context for the research before describing a new technique for better understanding the materials,

Found within the cellular walls of wood, cellulose nanocrystals are an ideal candidate for polymer nanocomposites — materials where a synthetic polymer matrix is embedded with nanoscale filler particles. Nanocomposites are commonly made synthetic fillers, such as silica, clay, or carbon black, and are used in a myriad of applications ranging from tires to biomaterials.

“Cellulose nanocrystals are an attractive alternative because they are naturally bioavailable, renewable, nontoxic, and relatively inexpensive,” Keten said. “And they can be easily extracted from wood pulp byproducts from the paper industry.”

Problems arise, however, when researchers try to combine the nanocellulose filler particles with the polymer matrix. The field has lacked an understanding of how the amount of filler affects the composite’s overall properties as well as the nature of the nanoscale interactions between the matrix and the filler.

Keten’s solution improves this understanding by focusing on the length scales of the materials rather than the nature of the materials themselves. By understanding what factors influence properties on the atomic scale, his computational approach can predict the nanocomposite’s properties as it scales up in size — with a minimal need for experimentation.

“Rather than just producing a material and then testing it to see what its properties are, we instead strategically tune design parameters in order to develop materials with a targeted property in mind,” Sinko said. “When you are equalizing music, you can turn knobs to adjust the bass, treble, etc. to produce a desired sound. In materials-by-design, we similarly can ‘turn the knobs’ of specific parameters to adjust the resulting properties.”

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

Tuning Glass Transition in Polymer Nanocomposites with Functionalized Cellulose Nanocrystals through Nanoconfinement by Xin Qin, Wenjie Xia, Robert Sinko, and Sinan Keten. Nano Lett., Article ASAP
DOI: 10.1021/acs.nanolett.5b02588 Publication Date (Web): September 4, 2015

Copyright © 2015 American Chemical Society

This paper is open access.

*Cellulose nanocrystals (CNC) are also known as nancellulose crystals (NCC).

Cellulose nanocrystals and supercapacitors at McMaster University (Canada)

Photos: Xuan Yang and Kevin Yager.

Photos: Xuan Yang and Kevin Yager. Courtesy McMaster University

I love that featherlike structure holding up a tiny block of something while balanced on what appears to be a series of medallions. What it has to do with supercapacitors (energy storage) and cellulose nanocrystals is a mystery but that’s one of the images you’ll find illustrating an Oct. 7, 2015 news item on Nanotechnology Now featuring research at McMaster University,

McMaster Engineering researchers Emily Cranston and Igor Zhitomirsky are turning trees into energy storage devices capable of powering everything from a smart watch to a hybrid car.

The scientists are using cellulose, an organic compound found in plants, bacteria, algae and trees, to build more efficient and longer-lasting energy storage devices or supercapacitors. This development paves the way toward the production of lightweight, flexible, and high-power electronics, such as wearable devices, portable power supplies and hybrid and electric vehicles.

A Sept. 10, 2015 McMaster University news release, which originated the news item, describes the research in more detail,

Cellulose offers the advantages of high strength and flexibility for many advanced applications; of particular interest are nanocellulose-based materials. The work by Cranston, an assistant chemical engineering professor, and Zhitomirsky, a materials science and engineering professor, demonstrates an improved three-dimensional energy storage device constructed by trapping functional nanoparticles within the walls of a nanocellulose foam.

The foam is made in a simplified and fast one-step process. The type of nanocellulose used is called cellulose nanocrystals and looks like uncooked long-grain rice but with nanometer-dimensions. In these new devices, the ‘rice grains’ have been glued together at random points forming a mesh-like structure with lots of open space, hence the extremely lightweight nature of the material. This can be used to produce more sustainable capacitor devices with higher power density and faster charging abilities compared to rechargeable batteries.

Lightweight and high-power density capacitors are of particular interest for the development of hybrid and electric vehicles. The fast-charging devices allow for significant energy saving, because they can accumulate energy during braking and release it during acceleration.

For anyone interested in a more detailed description of supercapacitors, there’s my favourite one which involves Captain America’s shield along with some serious science in my April 28, 2014 posting.

Getting back to the research at McMaster, here’s a link to and a citation for the paper,

Cellulose Nanocrystal Aerogels as Universal 3D Lightweight Substrates for Supercapacitor Materials by Xuan Yang, Kaiyuan Shi, Igor Zhitomirsky, and Emily D. Cranston. Advanced Materials DOI: 10.1002/adma.201502284View/save citation First published online 2 September 2015

This paper is behind a paywall.

One final bit, cellulose nanocrystals (CNC) are sometimes referred to as nanocrystalline cellulose (NCC).

Carrot-based helmets: a nanocellulose commercialization story

NanoCelluComp, a European Commission-funded project, whose name bears a close resemblance to a Scottish company, CelluComp, ended last year (my March 5, 2014 post). Both, NanoCelluComp and CelluComp, were/are involved in research featuring carrots and nanocellulose.

An Aug. 6, 2015 news item on ScienceDaily describes some Swiss/Scottish research into using carrot nanofibers in helmets,

Crackpot idea or recipe for success? This is a question entrepreneurs often face. Is it worth converting the production process to a new, ecologically better material? Empa [Swiss Federal Laboratories for Materials Science and Technology or Eidgenössische Materialprüfungs- und Forschungsansta] has developed an analysis method that enables companies to simulate possible scenarios — and therefore avoid bad investments. Here’s an example: Nanofibers made of carrot waste from the production of carrot juice, which can be used to reinforce synthetic parts.

All over the world, research is being conducted into biodegradable and recyclable synthetics. However, fiber-reinforced components remain problematic — if glass or carbon fibers are used. Within the scope of an EU research project, the Scottish company Cellucomp Limited has now developed a method to obtain nanofibers from carrot waste. [emphasis mine] These fibers would be both cost-effective and biodegradable. However, is the method, which works in the lab, also marketable on a large scale?

Here’s a composite image illustrating the notion of a carrot-based helmet,

Motorcycle helmets consist of fiber-reinforced synthetic material. Instead of glass fibers, a biological alternative is now also possible: plant fibers from the production of carrot juice. Empa researchers are now able to analyze whether this kind of production makes sense from an ecological and economical perspective – before money is actually invested in production plants.  Photo: 4ever.eu, composite photo: Empa

Motorcycle helmets consist of fiber-reinforced synthetic material. Instead of glass fibers, a biological alternative is now also possible: plant fibers from the production of carrot juice. Empa researchers are now able to analyze whether this kind of production makes sense from an ecological and economical perspective – before money is actually invested in production plants.
Photo: 4ever.eu, composite photo: Empa

An Aug. 6, 2015 Empa press release (also on EurekAlert), which originated the news item, provides more details abut the drive to commercialize this nanocellulose product,

An MPAS (multi-perspective application selection) method developed at Empa helps identify the industrial sectors where new materials might be useful from a technical and economical perspective. At the same time, MPAS also considers the ecological aspect of these new materials. The result for our example: Nanofibers made of carrot waste might be used in the production of motorcycle helmets or side walls for motorhomes in the future.

Three-step analysis

In order to clarify a new material’s market potential, Empa researchers Fabiano Piccinno, Roland Hischier and Claudia Som proceed in three steps for the MPAS method. First of all, the field of possible applications is defined: Which applications come into question based on the technical properties and what categories can they be divided into? Can the new material replace an existing one?

The second step concerns the technical feasibility and market potential: Can the material properties required be achieved with the technical process? Might the product quality vary from one production batch to the next? Can the lab process be upgraded to an industrial scale cost-effectively? Is the material more suited to the low-cost sector or expensive luxury goods? And finally: Does the product meet the legal standards and the customers’ certification needs?

In the third step, the ecological aspect is eventually examined: Is this new material for the products identified really more environmentally friendly – once all the steps from product creation to recycling have been factored in? Which factors particularly need to be considered during production stage to manufacture the material in as environmentally friendly a way as possible?

Industrial production on a five-ton scale – calculated theoretically

The MPAS approach enables individual scenarios for a future production to be calculated with an extremely high degree of accuracy. In the case of the carrot waste nanofibers, for instance, it is crucial whether five tons of fresh carrots or only 209 kilograms of carrot waste (fiber waste from the juicing process) are used as the base material for their production. The issue of whether the solvent is ultimately recycled or burned affects the production costs. And the energy balance depends on how the enzymes that loosen the fibers from the carrots are deactivated. In the lab, this takes place via heat; for production on an industrial level, the use of bleaching agents would be more cost-effective.

Conclusion: six possible applications for “carrot fibers“

For fiber production from carrot waste, the MPAS analysis identified six possible customer segments for the Scottish manufacturer Cellucomp that are worth taking a closer look at: Protective equipment and devices for recreational sport, special vehicles, furniture, luxury consumer goods and industrial manufacturing. The researchers listed the following examples: Motorcycle helmets and surfboards, side walls for motorhomes, dining tables, high-end loudspeaker boxes and product protection mats for marble-working businesses. Similarly detailed analyses can also be conducted for other renewable materials – before a lot of money is actually invested in production plants.

There are other attempts to commercialize nanocellulose (as I understand it, cellulose is one of the most common materials on earth and can be derived from several sources including trees, bananas, pineapples, and more) mentioned in my July 30, 2015 post. I will repeat a question from that post, where are the Canadian research efforts to develop and commercialize nanocellulose? If you have information, please do let me know.

Replacing metal with nanocellulose paper

The quest to find uses for nanocellulose materials has taken a step forward with some work coming from the University of Maryland (US). From a July 24, 2015 news item on Nanowerk,

Researchers at the University of Maryland recently discovered that paper made of cellulose fibers is tougher and stronger the smaller the fibers get … . For a long time, engineers have sought a material that is both strong (resistant to non-recoverable deformation) and tough (tolerant of damage).

“Strength and toughness are often exclusive to each other,” said Teng Li, associate professor of mechanical engineering at UMD. “For example, a stronger material tends to be brittle, like cast iron or diamond.”

A July 23, 2015 University of Maryland news release, which originated the news item, provides details about the thinking which buttresses this research along with some details about the research itself,

The UMD team pursued the development of a strong and tough material by exploring the mechanical properties of cellulose, the most abundant renewable bio-resource on Earth. Researchers made papers with several sizes of cellulose fibers – all too small for the eye to see – ranging in size from about 30 micrometers to 10 nanometers. The paper made of 10-nanometer-thick fibers was 40 times tougher and 130 times stronger than regular notebook paper, which is made of cellulose fibers a thousand times larger.

“These findings could lead to a new class of high performance engineering materials that are both strong and tough, a Holy Grail in materials design,” said Li.

High performance yet lightweight cellulose-based materials might one day replace conventional structural materials (i.e. metals) in applications where weight is important. This could lead, for example, to more energy efficient and “green” vehicles. In addition, team members say, transparent cellulose nanopaper may become feasible as a functional substrate in flexible electronics, resulting in paper electronics, printable solar cells and flexible displays that could radically change many aspects of daily life.

Cellulose fibers can easily form many hydrogen bonds. Once broken, the hydrogen bonds can reform on their own—giving the material a ‘self-healing’ quality. The UMD discovered that the smaller the cellulose fibers, the more hydrogen bonds per square area. This means paper made of very small fibers can both hold together better and re-form more quickly, which is the key for cellulose nanopaper to be both strong and tough.

“It is helpful to know why cellulose nanopaper is both strong and tough, especially when the underlying reason is also applicable to many other materials,” said Liangbing Hu, assistant professor of materials science at UMD.

To confirm, the researchers tried a similar experiment using carbon nanotubes that were similar in size to the cellulose fibers. The carbon nanotubes had much weaker bonds holding them together, so under tension they did not hold together as well. Paper made of carbon nanotubes is weak, though individually nanotubes are arguably the strongest material ever made.

One possible future direction for the research is the improvement of the mechanical performance of carbon nanotube paper.

“Paper made of a network of carbon nanotubes is much weaker than expected,” said Li. “Indeed, it has been a grand challenge to translate the superb properties of carbon nanotubes at nanoscale to macroscale. Our research findings shed light on a viable approach to addressing this challenge and achieving carbon nanotube paper that is both strong and tough.”

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

Anomalous scaling law of strength and toughness of cellulose nanopaper by Hongli Zhu, Shuze Zhu, Zheng Jia, Sepideh Parvinian, Yuanyuan Li, Oeyvind Vaaland, Liangbing Hu, and Teng Li. PNAS (Proceedings of the National Academy of Sciences) July 21, 2015 vol. 112 no. 29 doi: 10.1073/pnas.1502870112

This paper is behind a paywall.

There is a lot of research on applications for nanocellulose, everywhere it seems, except Canada, which at one time was a leader in the business of producing cellulose nanocrystals (CNC).

Here’s a sampling of some of my most recent posts on nanocellulose,

Nanocellulose as a biosensor (July 28, 2015)

Microscopy, Paper and Fibre Research Institute (Norway), and nanocellulose (July 8, 2015)

Nanocellulose markets report released (June 5, 2015; US market research)

New US platform for nanocellulose and occupational health and safety research (June 1, 2015; Note: As you find new applications, you need to concern yourself with occupational health and safety.)

‘Green’, flexible electronics with nanocellulose materials (May 26, 2015; research from China)

Treating municipal wastewater and dirty industry byproducts with nanocellulose-based filters (Dec. 23, 2014; research from Sweden)

Nanocellulose and an intensity of structural colour (June 16, 2014; research about replacing toxic pigments with structural colour from the UK)

I ask again, where are the Canadians? If anybody has an answer, please let me know.