Tag Archives: Tanja Zimmermann

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.

Nanocellulosic 3D-printed ears

It’s been a while since I’ve had a story abut cellulose nanocrystals (CNC) and this one comes from Switzerland’s Empa (Swiss Federal Laboratories for Materials Science and Technology) in a January 15, 2019 news item on Nanowerk (Note: A link has been removed),

Cellulose obtained from wood has amazing material properties. Empa researchers are now equipping the biodegradable material with additional functionalities to produce implants for cartilage diseases using 3D printing (ACS Nano, “Dynamics of Cellulose Nanocrystal Alignment during 3D Printing”).

It all starts with an ear. Empa researcher Michael Hausmann removes the object shaped like a human ear from the 3D printer and explains: “In viscous state cellulose nanocrystals can easily be shaped together with nother biopolymers into complex 3-dimensional structures using a 3D printer, such as the Bioplotter.”

Once cross-linked, the structures remain stable despite their soft mechanical properties. Hausmann is currently investigating the characteristics of the nanocellulose composite hydrogels in order to further optimize their stability as well as the printing process. The researcher already used X-ray analysis to determine how cellulose is distributed and organized within the printed structures.

At this point in time the printed ear is entirely and solely made of cellulose nanocrystals and a biopolymer. However, the objective is to incorporate both human cells and therapeutics into the base structure in order to produce biomedical implants.

Here’s one of the researchers (Michael Hausmann) showing off their ‘ear’,

A 3D-printed ear: Empa researcher Michael Hausmann uses nanocellulose as the basis for novel implants (Image: Empa)

Doesn’t look like much does, eh? It’s scaffolding or, you could say, a kind of skeleton and a January 15, 2019 Empa press release, which originated the news item, describes it and explains how it will house new cells,

A new project is currently underway, looking into how chondrocytes (cartilage cells) can be integrated into the scaffold to yield artificial cartilage tissue. As soon as the colonization of the hydrogel with cells is established, nanocellulose based composites in the shape of an ear could serve as an implant for children with an inherited auricular malformation as for instance, in microtia, where the external ears are only incompletely developed. A reconstruction of the auricle can esthetically and medically correct the malformation; otherwise the hearing ability can be severely impaired. In the further course of the project, cellulose nanocrystals containing hydrogels will also be used for the replacement of articular cartilage (e.g. knee) in cases of joint wear due to, for example, chronic arthritis.

Once the artificial tissue has been implanted in the body, the biodegradable polymer material is expected to degrade over time. The cellulose itself is not degradable in the body, but biocompatible. However, it is not only its biocompatibility that makes nanocellulose the perfect material for implant scaffolds. “It is also the mechanical performance of cellulose nanocrystals that make them such promising candidates because the tiny but highly stable fibers can extremely well reinforce the produced implant,” said Hausmann.

Moreover, nanocellulose allows the incorporation of various functions by chemical modifications into the viscous hydrogel. Thus, the structure, the mechanical properties and the interactions of the nanocellulose with its environment can be specifically tailored to the desired end product. “For instance, we can incorporate active substances that promote the growth of chondrocytes or that sooth joint inflammation into the hydrogel,” says the Empa researcher.

And last but not least, as raw material cellulose is the most abundant natural polymer on earth. Therefore, the use of cellulose nanocrystals not only benefits from the mere elegance of the novel process but also from the availability of the raw material.

The white nanocellulose ear lies glossy on the glass carrier. Just out of the Bioplotter, it is already robust and dimensionally stable. Hausmann can give the go-ahead for the next steps. 

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

Dynamics of Cellulose Nanocrystal Alignment during 3D Printing by Michael K. Hausmann, Patrick A. Rühs, Gilberto Siqueira, Jörg Läuger, Rafael Libanori, Tanja Zimmermann, and André R. Studart. ACS Nano, 2018, 12 (7), pp 6926–6937 DOI: 10.1021/acsnano.8b02366 Publication Date (Web): July 5, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Mopping up that oil spill with a nanocellulose sponge and a segue into Canadian oil and politics

Empa (Swiss Federal Laboratories for Materials Science and Technology or ,in German, Eidgenössische Materialprüfungs- und Forschungsanstalt) has announced the development of a nanocellulose sponge useful for cleaning up oil spills in a May 5, 2014 news item on Nanowerk (Note: A link has been removed),

A new, absorbable material from Empa wood research could be of assistance in future oil spill accidents: a chemically modified nanocellulose sponge. The light material absorbs the oil spill, remains floating on the surface and can then be recovered. The absorbent can be produced in an environmentally-friendly manner from recycled paper, wood or agricultural by-products (“Ultralightweight and Flexible Silylated Nanocellulose Sponges for the Selective Removal of Oil from Water”).

A May 2, 2014 Empa news release (also on EurekAlert*}, which originated the news item, includes a description of the potential for oil spills due to transport issues, Empa’s proposed clean-up technology, and a request for investment,

All industrial nations need large volumes of oil which is normally delivered by ocean-going tankers or via inland waterways to its destination. The most environmentally-friendly way of cleaning up nature after an oil spill accident is to absorb and recover the floating film of oil. The Empa researchers Tanja Zimmermann and Philippe Tingaut, in collaboration with Gilles Sèbe from the University of Bordeaux, have now succeeded in developing a highly absorbent material which separates the oil film from the water and can then be easily recovered, “silylated” nanocellulose sponge. In laboratory tests the sponges absorbed up to 50 times their own weight of mineral oil or engine oil. They kept their shape to such an extent that they could be removed with pincers from the water. The next step is to fine tune the sponges so that they can be used not only on a laboratory scale but also in real disasters. To this end, a partner from industry is currently seeked.

Here’s what the nanocellulose sponge looks like (oil was dyed red and the sponge has absorbed it from the water),

The sponge remains afloat and can be pulled out easily. The oil phase is selectively removed from the surface of water. Image: Empa

The sponge remains afloat and can be pulled out easily. The oil phase is selectively removed from the surface of water.
Image: Empa

The news release describes the substance, nanofibrillated cellulose (NFC), and its advantages,

Nanofibrillated Cellulose (NFC), the basic material for the sponges, is extracted from cellulose-containing materials like wood pulp, agricultural by products (such as straw) or waste materials (such as recycled paper) by adding water to them and pressing the aqueous pulp through several narrow nozzles at high pressure. This produces a suspension with gel-like properties containing long and interconnected cellulose nanofibres .

When the water from the gel is replaced with air by freeze-drying, a nanocellulose sponge is formed which absorbs both water and oil. This pristine material sinks in water and is thus not useful for the envisaged purpose. The Empa researchers have succeeded in modifying the chemical properties of the nanocellulose in just one process step by admixing a reactive alkoxysilane molecule in the gel before freeze-drying. The nanocellulose sponge loses its hydrophilic properties, is no longer suffused with water and only binds with oily substances.

In the laboratory the “silylated” nanocellulose sponge absorbed test substances like engine oil, silicone oil, ethanol, acetone or chloroform within seconds. Nanofibrillated cellulose sponge, therefore, reconciles several desirable properties: it is absorbent, floats reliably on water even when fully saturated and is biodegradable.

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

Ultralightweight and Flexible Silylated Nanocellulose Sponges for the Selective Removal of Oil from Water by Zheng Zhang, Gilles Sèbe, Daniel Rentsch, Tanja Zimmermann, and Philippe Tingaut. Chem. Mater., 2014, 26 (8), pp 2659–2668 DOI: 10.1021/cm5004164 Publication Date (Web): April 10, 2014

Copyright © 2014 American Chemical Society

This article is behind a paywall.

I featured ‘nanocellulose and oil spills’ research at the University Wisconsin-Madison in a Feb. 26, 2014 post titled, Cleaning up oil* spills with cellulose nanofibril aerogels (Note: I corrected a typo in my headline hence the asterisk). I also have a Dec. 31, 2013 piece about a nanotechnology-enabled oil spill recovery technology project (Naimor) searching for funds via crowdfunding. Some major oil projects being considered in Canada and the lack of research on remediation are also mentioned in the post.

Segue Alert! As for the latest on Canada and its oil export situation, there’s a rather interesting May 2, 2014 Bloomberg.com article Canada Finds China Option No Easy Answer to Keystone Snub‘ by Edward Greenspon, Andrew Mayeda, Jeremy van Loon and Rebecca Penty describing two Canadian oil projects and offering a US perspective,

It was February 2012, three months since President Barack Obama had phoned the Canadian prime minister to say the Keystone XL pipeline designed to carry vast volumes of Canadian crude to American markets would be delayed.

Now Harper [Canadian Prime Minister Stephen Harper] found himself thousands of miles from Canada on the banks of the Pearl River promoting Plan B: a pipeline from Alberta’s landlocked oil sands to the Pacific Coast where it could be shipped in tankers to a place that would certainly have it — China. It was a country to which he had never warmed yet that served his current purposes. [China’s President at that time was Hu Jintao, 2002 – 2012; currently the President is Xi Jinping, 2013 – ]

The writers do a good job of describing a number of factors having an impact on one or both of the pipeline projects. However, no mention is made in the article that Harper is from the province of Alberta and represents that province’s Calgary Southwest riding. For those unfamiliar with Calgary, it is a city dominated by oil companies. I imagine Mr. Harper is under considerable pressure to resolve oil export and transport issues and I would expect they would prefer to resolve the US issues since many of those oil companies in Calgary have US headquarters.

Still, it seems simple, if the US is not interested as per the problems with the Keystone XL pipeline project, ship the oil to China via a pipeline through the province of British Columbia and onto a tanker. What the writers do not mention is yet another complicating factor, Trudeau, both Justin and, the deceased, Pierre.

As Prime Minister of Canada, Pierre Trudeau was unloved in Alberta, Harper’s home province, due to his energy policies and the formation of the National Energy Board. Harper appears, despite his denials, to have an antipathy towards Pierre Trudeau that goes beyond the political to the personal and it seems to extend beyond Pierre’s grave to his son, Justin. A March 21, 2014 article by Mark Kennedy for the National Post describes Harper’s response to Trudeau’s 2000 funeral this way,

Stephen Harper, then the 41-year-old president of the National Citizens Coalition (NCC), was a proud conservative who had spent three years as a Reform MP. He had entered politics in the mid-1980s, in part because of his disdain for how Pierre Trudeau’s “Just Society” had changed Canada.

So while others were celebrating Trudeau’s legacy, Harper hammered out a newspaper article eviscerating the former prime minister on everything from policy to personality.

Harper blasted Trudeau Sr. for creating “huge deficits, a mammoth national debt, high taxes, bloated bureaucracy, rising unemployment, record inflation, curtailed trade and declining competitiveness.”

On national unity, he wrote that Trudeau was a failure. “Only a bastardized version of his unity vision remains and his other policies have been rejected and repealed by even his own Liberal party.”

Trudeau had merely “embraced the fashionable causes of his time,” wrote Harper.

Getting personal, he took a jab at Trudeau over not joining the military during the Second World War: “He was also a member of the ‘greatest generation,’ the one that defeated the Nazis in war and resolutely stood down the Soviets in the decades that followed. In those battles however, the ones that truly defined his century, Mr. Trudeau took a pass.”

The article was published in the National Post Oct. 5, 2000 — two days after the funeral.

Kennedy’s article was occasioned by the campaign being led by Harper’;s Conservative party against the  leader (as of April 2013) of the Liberal Party, Justin Trudeau.

It’s hard to believe that Harper’s hesitation over China is solely due to human rights issues especially  since Harper has not been noted for consistent interest in those issues and, more particularly, since Prime Minister Pierre Trudeau was one of the first ‘Western’ leaders to visit communist China . Interestingly, Harper has been much more enthusiastic about the US than Pierre Trudeau who while addressing the Press Club in Washington, DC in March 1969, made this observation (from the Pierre Trudeau Wikiquote entry),

Living next to you [the US] is in some ways like sleeping with an elephant. No matter how friendly and even-tempered is the beast, if I can call it that, one is affected by every twitch and grunt.

On that note, I think Canada is always going to be sleeping with an elephant; the only question is, who’s the elephant now? In any event, perhaps Harper is more comfortable with the elephant he knows and that may explain why China’s offer to negotiate a free trade agreement has been left unanswered (this too was not noted in the Bloomberg article). The offer and lack of response were mentioned by Yuen Pau Woo, President and CEO of the Asia Pacific Foundation of Canada, who spoke at length about China, Canada, and their trade relations at a Jan. 31, 2014 MP breakfast (scroll down for video highlights of the Jan. 31, 2014 breakfast) held by Member of Parliament (MP) for Vancouver-Quadra, Joyce Murray.

Geopolitical tensions and Canadian sensitivities aside, I think Canadians in British Columbia (BC), at least, had best prepare for more oil being transported and the likelihood of spills. In fact, there are already more shipments according to a May 6, 2014 article by Larry Pynn for the Vancouver Sun,

B.C. municipalities work to prevent a disastrous accident as rail transport of oil skyrockets

The number of rail cars transporting crude oil and petroleum products through B.C. jumped almost 200 per cent last year, reinforcing the resolve of municipalities to prevent a disastrous accident similar to the derailment in Lac-Mégantic in Quebec last July [2013].

Transport Canada figures provided at The Vancouver Sun’s request show just under 3,400 oil and petroleum rail-car shipments in B.C. last year, compared with about 1,200 in 2012 and 50 in 2011.

The figures come a week after The Sun revealed that train derailments jumped 20 per cent to 110 incidents last year in B.C., the highest level in five years.

Between 2011 and 2012, there was an increase of 2400% (from 50 to 1200) of oil and petroleum rail-car shipments in BC. The almost 300% increase in shipments between 2012 and 2013 seems paltry in comparison.  Given the increase in shipments and the rise in the percentage of derailments, one assumes there’s an oil spill waiting to happen. Especially so, if the Canadian government manages to come to an agreement regarding the proposed pipeline for BC and frankly, I have concerns about the other pipeline too, since either will require more rail cars, trucks, and/or tankers for transport to major centres edging us all closer to a major oil spill.

All of this brings me back to Empa, its oil-absorbing nanocellulose sponges, and the researchers’ plea for investors and funds to further their research. I hope they and all the other researchers (e.g., Naimor) searching for ways to develop and bring their clean-up ideas to market find some support.

*EurekAlert link added May 7, 2014.

ETA May 8, 2014:  Some types of crude oil are more flammable than others according to a May 7, 2014 article by Lindsay Abrams for Salon.com (Note: Links have been removed),

Why oil-by-rail is an explosive disaster waiting to happen
A recent spate of fiery train accidents all have one thing in common: highly volatile cargo from North Dakota

In case the near continuous reports of fiery, deadly oil train accidents hasn’t been enough to convince you, Earth Island Journal is out with a startling investigative piece on North Dakota’s oil boom and the dire need for regulations governing that oil’s transport by rail.

The article is pegged to the train that derailed and exploded last summer in  [Lac-Mégantic] Quebec, killing 47 people, although it just as well could have been the story of the train that derailed and exploded in Alabama last November, the train that derailed and exploded in North Dakota last December, the train that derailed and exploded in Virginia last week or — let’s face it — any future accidents that many see as an inevitability.

The Bakken oil fields in North Dakota are producing over a million barrels of crude oil a day, more than 60 percent of which is shipped by rail. All that greenhouse gas-emitting fossil fuel is bad enough; that more oil spilled in rail accidents last year than the past 35 years combined is also no small thing. But the particular chemical composition of Bakken oil lends an extra weight to these concerns: according to the Pipeline and Hazardous Materials Safety Administration, it may be more flammable and explosive than traditional crude.

While Abrams’ piece is not focused on oil cleanups, it does raise some interesting questions about crude oil transport and whether or not the oil from Alberta might also be more than usually dangerous.