Category Archives: coatings

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.

First textile to automatically trap or release heat, depending on conditions

A revolutionary fabric created at UMD reacts to environmental conditions to either trap heat or release it. (Photo by Faye Levine) Courtesy: University of Maryland

This may look like just another gauzy fabric but it has some special properties according to a February 7, 2019 news item on ScienceDaily,

Despite decades of innovation in fabrics with high-tech thermal properties that keep marathon runners cool or alpine hikers warm, there has never been a material that changes its insulating properties in response to the environment. Until now.

University of Maryland researchers have created a fabric that can automatically regulate the amount of heat that passes through it. When conditions are warm and moist, such as those near a sweating body, the fabric allows infrared radiation (heat) to pass through. When conditions become cooler and drier, the fabric reduces the heat that escapes. The development was reported in the February 8, 2019 issue of the journal Science.

A February 8, 2019 University of Maryland news release (also on EurekAlert [published Feb.7, 2019]) by Kimbra Cutlip delves further into the research,

The researchers created the fabric from specially engineered yarn coated with a conductive metal. Under hot, humid conditions, the strands of yarn compact and activate the coating, while cool, dry conditions reverse the action. The researchers refer to this as “gating”—essentially a tunable blind that transmits or blocks heat.

“This is the first technology that allows us to dynamically gate infrared radiation,” said YuHuang Wang, a professor of chemistry and biochemistry and one of the paper’s corresponding authors who directed the studies.

The base yarn for this new textile is created with fibers made of two different synthetic materials—one absorbs water and the other repels it. The strands are coated with carbon nanotubes, a special class of lightweight, carbon-based, conductive metal.

Because materials in the fibers both resist and absorb water, the fibers warp when exposed to humidity such as that surrounding a sweating body. That distortion brings the strands of yarn closer together, opening the pores in the fabric and creating a minor cooling effect by allowing heat to escape. More importantly, it modifies the electromagnetic coupling between the carbon nanotubes in the coating.

“You can think of this coupling effect like the bending of a radio antenna to change the wavelength or frequency it resonates with,” Wang said. “Imagine bringing two antennae close together to regulate the kind of electromagnetic wave they pick up. When the fabric fibers are brought closer together, the radiation they interact with changes. In clothing, that means the fabric interacts with the heat radiating from the human body.

”Depending on the tuning, the fabric either blocks infrared radiation or allows it to pass through. The reaction is almost instant, so before people realize it, the dynamic gating mechanism is either cooling them down or working in reverse to trap heat.
 
“The human body is a perfect radiator. It gives off heat quickly,” said Min Ouyang, a professor of physics at UMD and the paper’s other corresponding author. “For all of history, the only way to regulate the radiator has been to take clothes off or put clothes on. But this fabric is a true bidirectional regulator.

More work is needed before the fabric can be commercialized, but according to the researchers, materials used for the base fiber are readily available and the carbon coating can be easily added during the standard dyeing process.

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

Dynamic gating of infrared radiation in a textile by Xu A. Zhang, Shangjie Yu, Beibei Xu, Min Li, Zhiwei Peng, Yongxin Wang, Shunliu Deng, Xiaojian Wu, Zupeng Wu, Min Ouyang, YuHuang Wang. Science 08 Feb 2019: Vol. 363, Issue 6427, pp. 619-623 DOI: 10.1126/science.aau1217

This paper is behind a paywall.

The van Gogh-Roosegaarde path, a solar powered bike path

From YouTube, Heijmans NV Published on Nov 12, 2014 Inspired by Vincent van Gogh’s work, the cycle path combines innovation and design with cultural heritage and tourism. The Van Gogh-Roosegaarde cycle path is being constructed by Heijmans from a design by Daan Roosegaarde and forms part of the Van Gogh cycle route in Brabant.

According to other sources, the path was inspired by van Gogh’s ‘Starry Night’. From a November 21, 2014 article by Elizabeth Montalbano for Design News (Note: A link has been removed),

The Dutch are known for their love of bicycling, and they’ve also long been early adopters of green-energy and smart-city technologies. So it seems fitting that a town in which painter Vincent van Gogh once lived has given him a very Dutch-like tribute — a bike path lit by a special smart paint in the style of the artist’s “Starry Night” painting.

Designed by artist Daan Roosegaarde of Studio Roosegaarde, the van Gogh-Roosegaarde bike path — in the Dutch town of Nuenen en Eindhoven, where van Gogh lived from 1883-1885 — is a kilometer long and features technologies developed as part of the Smart Highway project, a joint venture of the studio and Dutch infrastructure company Heijmans.

A team of 12 designers and engineers worked on the project for eight months, while site production took 10 days. The opening of the path marked the official launch of the international van Gogh 2015 year.

The path uses stones painted with a smart coating that charges by the heat of the sun during the day and then glow at night for up to eight hours. When there is not enough sunlight during the day to charge the stones, the path can draw electricity from a solar panel installed nearby. There are also LEDs in the path that provides lighting.

How does the technology work?

Despite my best efforts, I never did unearth a good technical explanation. There is some sort of photoluminescent powder or paint. I vote for a powder that’s been emulsified in a paint/coating. material. Somehow, this material is charged by sunlight and then at night glows with the help of a solar panel and light-emitting diodes (LEDs).

Here’s the clearest explanation I found; it’s from Dan Howarth’s November 12, 2014 article for dezeen.com (Note: A link has been removed), ,

The surface of the Van Gogh-Roosegaarde Bicycle Path is coated with a special paint that uses energy gathered during the day to glow after dark.


[Daan] Roosegaarde told Dezeen that this method of illumination is “more gentle to the eye and surrounding nature” that other lighting infrastructure, and creates a “connection with cultural history”.

A nearby solar panel is used to generate power to illuminate the coated surface, which was developed with infrastructure firm Heijmans. LEDs along the side of certain curves in the path cast extra light, meaning the path will still be partially lit if the weather has been too cloudy for the panel to charge the surface to its full brightness.

“It’s a new total system that is self-sufficient and practical, and just incredibly poetic,” said Roosegaarde.

Lily Hay Newman’s November 14, 2014 article for Slate.com succinctly sums up the technical aspects,

The path is coated in photoluminescent paint that’s also embedded with small LEDs powered by nearby solar panels. The path essentially charges all day so that it can glow during the night, and it also has backup power in case it’s overcast.

This October 30, 2012 article by Liat Clark for Wired.com provides a bit more detail about the powder/paint as Clark delves into the Roosegaarde Studo’s Smart Highway project (the cycle path made use of the same technology) ,

The studio has developed a photo-luminising powder that will replace road markings – it charges up in sunlight, giving it up to 10 hours of glow-in-the-dark time come nightfall. “It’s like the glow in the dark paint you and I had when we were children,” designer Roosegaarde explained, “but we teamed up with a paint manufacturer and pushed the development. Now, it’s almost radioactive“. [perhaps not the wisest choice of hyperbole]

Special paint will also be used to paint markers like snowflakes across the road’s surface – when temperatures fall to a certain point, these images will become visible, indicating that the surface will likely be slippery. Roosegaarde says this technology has been around for years, on things like baby food – the studio has just upscaled it.

Not everyone is in love

Shaunacy Ferro’s July 26, 2017 article for dentalfloss.com highlights a glow-in-the-dark path project for Singapore and a little criticism (Note: Links have been removed),

Glow-in-the-dark materials are no longer for toys. Photoluminescence can help cities feel safer at night, whether it’s part of a mural, a bike lane, or a highway. Glow-in-the-dark paths have been tested in several European cities (the above is a Van Gogh-inspired bike path by the Dutch artist Daan Roosegaarde) and in Texas, but now, the technology may be coming to Singapore. The city-state is currently developing a 15-mile greenway called the Rail Corridor, and it now has a glow-in-the-dark path, as Mashable reports.

The 328-foot stretch of glowing path is part of a test of multiple surface materials that might eventually be used throughout the park, depending on public opinion. In addition to the strontium aluminate-beaded [emphasis mine] path that glows at night, there are also three other 328-foot stretches of the path that are paved with fine gravel, cement aggregate, and part-grass/part-gravel. The glow-in-the-dark material embedded in the walkway absorbs UV light from the sun during the day and can emit light for up to eight hours once the sun goes down.

However, in practice, glow-in-the-dark paths can be less dazzling than they seem. [emphasis mine] Mashable’s reporter called the glowing effect on Singapore’s path “disappointingly feeble.” [emphasis mine] In 2014, a glowing highway-markings pilot by Studio Roosegaarde in the Netherlands revealed that the first road markings faded after exposure to heavy rains. [emphases mine] When it comes to glowing roads, the renderings tend to look better than the actual result, [emphasis mine] and there are still kinks to work out. (The studio worked the issue out eventually.) While a person walking or biking down Singapore’s glowing path might be able to tell that they were staying on the path better than if they were fumbling along dark pavement, it’s not the equivalent of a streetlight, for sure.

Ferro had reported earlier on Studio Roosegaarde’s Smart Highway project in an October 23, 2014 article for Fast Company where Ferro first mentioned the rain problem (Note: Links have been removed),

Glowing Lanes is a collaboration between Dutch engineering company Heijmans and Daan Roosegaarde, a tech-loving artist and designer whose previous work includes Intimacy 2.0, a dress that becomes transparent when the wearer gets aroused. The glow-in-the-dark lane markers are intended to increase road visibility in a more energy-efficient way than traditional street lighting. Photoluminescent paint charges during the day and slowly emits light over the course of eight hours during the evening.

After a few technical challenges (an early version of the markers didn’t fare so well in the rain), the final system has been installed, and according to Studio Roosegaarde, the kinks have been worked out, and initial reports of the paint fading were “overstated.” [emphases mine]

“This was part of any normal learning process,” according to an email from the studio’s PR, and “now the project is ‘matured.’”

But not to the point where it’s no longer a novelty. According to the email from Studio Roosegaarde, the glowing highway caused a minor traffic jam last night as people rushed to look at it.

… Roosegaarde has also been asked to create a smart highway design for Afsluitdijk–an almost 20-mile-long dike that connects North Holland to the province of Friesland across the water–and according to his studio, there are plans in the works to launch the glowing lanes in China and Japan as well.

Comments

In the following excerpt, there’s a reference to strontium aluminate-coated materials, given the interview which follows this section, the project in Singapore did not use the photoluminescent paint developed by Roosegaarde Studio. I found this paint reference in a July 26, 2017 article by Yi Shu Ng for Mashable (h/t Ferro’s July 26, 2017 article) which notes the product’s ubiquity,

The track glows because it’s got strontium aluminate compounds embedded in it — the chemical is commonly found in glow-in-the-dark products, which absorb ultraviolet light in the day, to emit luminescence at night.

There are some inconsistencies in the reporting about the number of hours, eight hours or 10 hours, the bicycle path or smart highway remains lit after being charged. Given that this was a newish technology being used in a new application, the rain problem and other technical glitches were to be expected. I wish the writer had been a little less dismissive and that the studio had been a little more forthcoming about how they solved the problems. In any case, I dug further and this is what I got.

Interview

I’m not sure who answered the questions but this comes direct from Studio Roosegaarde,

  • Could you give me a capsule description of what’s happened since the path was opened in 2014/15? For example, How does the bike path look these days? Does it still glow? Don’t the bicycles on the path destroy the ‘Starry Night’ pattern over time? Do the stones have to be coated over and over again to maintain their solar charging capacities? 

    The Van Gogh Path is still working perfectly and is visited every night by couples, tourists and local people. The stones are inside the concrete so are still in place and will work for a minimum of 10 years. It is great to see we have created a place of wonder. It is the most published bicycle path in the world. We have even had children books published about it.
  • Are there more bike paths like the Van Gogh Path in other parts of Holland and/or elsewhere?

    No, this is the only one. There have been some copycats in other countries.The Smart Highway project is still growing, and our recent Gates of Light is the next step of poetic and energy-neutral landscapes like the Van Gogh Path:  https://www.studioroosegaarde.net/project/gates-of-light
  • How has your project evolved? And, have there been any unanticipated benefits and/or setbacks? Is there a change in the technology, I noticed you were investigating bioluminscence.

    Yes, we are still developing new landscapes of the future. What we have learned from Van Gogh Path we have applied in new projects such as Glowing Nature: https://www.studioroosegaarde.net/project/glowing-nature We also do something new.
  • I was struck by how gentle the lighting is. I understand there has been some criticism about how much light the path radiates and I’m wondering about your thoughts on that.

    Yes, since the path is a nature protected environment, normal LED lighting was not allowed. So the light is gentle but still visible, and sustainable.There are some bad copy-cats using cheap materials which don’t work well, like the one in Singapore. But we are happy that our path is still working.

Thank you to the folks at Studio Roosegaarde for taking the time to provide this interview. Here are links to Studio Roosegaarde and their industrial partner, Heijmans.

Graphene-gilded artifacts (or artefacts)

Caption: L: An artist rendering of graphene gilding on Tutankhamun’s middle coffin (original photograph copyright: Griffith Institute, University of Oxford). R: Microscope image of a graphene crystal is shown on the palladium leaf. Although graphene is only a single atom thick, it can be observed in the scanning electron microscope. Here, a small crystal of graphene is shown to observe its edges. The team produces leaves where the graphene fully cover the metal surface. Credit: Original photograph copyright: Griffith Institute, University of Oxford

As icons go, Tutankhamun’s middle coffin ranks highly and it’s a great image to use as an example of what might be accomplished with graphene gilding. From a Sept. 10, 2018 news item on Nanowerk,

Gilding is the process of coating intricate artifacts with precious metals. Ancient Egyptians and Chinese coated their sculptures with thin metal films using gilding—and these golden sculptures have resisted corrosion, wear, and environmental degradation for thousands of years. The middle and outer coffins of Tutankhamun, for instance, are gold leaf gilded, as are many other ancient treasures.

In a new study, Illinois’ Sameh Tawfick, from the Department of Mechanical Science & Engineering (MechSE) and the Beckman Institute, inspired by this ancient process, has added a single layer of carbon atoms, known as graphene, on top of metal leaves—doubling the protective quality of gilding against wear and tear.

A Sept. 10, 2018 University of Illinois news release (also on EurekAlert), which originated the news item, offers more details,

Metal leaves, or foils, offer many advantages as a scalable coating material, including their commercial availability in large rolls and their comparatively low price. By bonding a single layer of graphene to the leaves, Tawfick and his team demonstrated unexpected benefits, including enhanced mechanical resistance. Their work presents exciting opportunities for protective coating applications on large structures like buildings or ship hulls, metal surfaces of consumer electronics, and small precious artifacts or jewelry.

“Adding one more layer of graphene atoms onto the palladium made it twice as resistant to indents than the bare leaves alone,” said Tawfick. “It’s also very attractive from a cost perspective. The amount of graphene needed to cover the gilded structures of the Carbide & Carbon Building in Chicago, for example, would be the size of the head of a pin.”

Additionally, the team developed a new technology to grow high-quality graphene directly on the surface of 150 nanometer-thin palladium leaves—in just 30 seconds. Using a process called chemical vapor deposition, in which the metal leaf is processed in a 1,100°C furnace, the bare palladium leaf acts as a catalyst, allowing the gases to react quickly.

“Chemical vapor deposition of graphene requires a very high temperature, which could melt the leaves or cause them to bead up by a process called solid state dewetting,” said Kaihao Zhang, PhD candidate in MechSE and lead author of the study. “The process we developed deposits the graphene quickly enough to avoid high-temperature degradation, it’s scalable, and it produces graphene of very high quality.”

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

Gilding with Graphene: Rapid Chemical Vapor Deposition Synthesis of Graphene on Thin Metal Leaves by Kaihao Zhang, Charalampos Androulidakis, Mingze Chen, Sameh Tawfick. Advanced Functional Materials DOI: https://doi.org/10.1002/adfm.201804068 First published: 06 September 2018

This paper is behind  a paywall.

Colo(u)ring your carbon nanotubes

Finnish research is highlighted in an August 28, 2018 news item on phys.org,

A method developed at Aalto University, Finland, can produce large quantities of pristine single-walled carbon nanotubes in select shades of the rainbow. The secret is a fine-tuned fabrication process—and a small dose of carbon dioxide. The films could find applications in touch screen technologies or as coating agents for new types of solar cells.

An August 28, 2018 Aalto University press release (also on EurekAlert), which originated the news item, provides more detail,

Samples of the colourful carbon nanotube thin films, as produced in the fabrication reactor. Image: Aalto University.
 

Single-walled carbon nanotubes, or sheets of one atom-thick layers of graphene rolled up into different sizes and shapes, have found many uses in electronics and new touch screen devices. By nature, carbon nanotubes are typically black or a dark grey.

In their new study published in the Journal of the American Chemical Society (JACS), Aalto University researchers present a way to control the fabrication of carbon nanotube thin films so that they display a variety of different colours—for instance, green, brown, or a silvery grey.

The researchers believe this is the first time that coloured carbon nanotubes have been produced by direct synthesis. Using their invention, the colour is induced straight away in the fabrication process, not by employing a range of purifying techniques on finished, synthesized tubes.

With direct synthesis, large quantities of clean sample materials can be produced while also avoiding damage to the product in the purifying process—which makes it the most attractive approach for applications.

‘In theory, these coloured thin films could be used to make touch screens with many different colours, or solar cells that display completely new types of optical properties,’ says Esko Kauppinen, Professor at Aalto University.

To get carbon structures to display colours is a feat in itself. The underlying techniques needed to enable the colouration also imply finely detailed control of the structure of the nanotube structures. Kauppinen and his team’s unique method, which uses aerosols of metal and carbon, allows them to carefully manipulate and control the nanotube structure directly from the fabrication process.

‘Growing carbon nanotubes is, in a way, like planting trees: we need seeds, feeds, and solar heat. For us, aerosol nanoparticles of iron work as a catalyst or seed, carbon monoxide as the source for carbon, so feed, and a reactor gives heat at a temperature more than 850 degrees Celsius,’ says Dr. Hua Jiang, Senior Scientist at Aalto University.

Professor Kauppinen’s group has a long history of using these very resources in their singular production method. To add to their repertoire, they have recently experimented with administering small doses of carbon dioxide into the fabrication process.

‘Carbon dioxide acts as a kind of graft material that we can use to tune the growth of carbon nanotubes of various colors,’ explains Jiang.

With an advanced electron diffraction technique, the researchers were able to find out the precise atomic scale structure of their thin films. They found that they have very narrow chirality distributions, meaning that the orientation of the honeycomb-lattice of the tubes’ walls is almost uniform throughout the sample. The chirality more or less dictates the electrical properties carbon nanotubes can have, as well as their colour.

The method developed at Aalto University promises a simple and highly scalable way to fabricate carbon nanotube thin films in high yields.

‘Usually you have to choose between mass production or having good control over the structure of carbon nanotubes. With our breakthrough, we can do both,’ trusts Dr. Qiang Zhang, a postdoctoral researcher in the group.

Follow-up work is already underway.

‘We want to understand the science of how the addition of carbon dioxide tunes the structure of the nanotubes and creates colours. Our aim is to achieve full control of the growing process so that single-walled carbon nanotubes could be used as building blocks for the next generation of nanoelectronics devices,’ says professor Kauppinen.

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

Direct Synthesis of Colorful Single-Walled Carbon Nanotube Thin Films by Yongping Liao, Hua Jiang, Nan Wei, Patrik Laiho, Qiang Zhang, Sabbir A. Khan, and Esko I. Kauppinen. J. Am. Chem. Soc., 2018, 140 (31), pp 9797–9800 DOI: 10.1021/jacs.8b05151 Publication Date (Web): July 26, 2018

Copyright © 2018 American Chemical Society

This paper appears to be open access.

For the curious, here’s a peek at the coloured carbon nanotube films,

 

Caption: Samples of the colorful carbon nanotube thin films, as produced in the fabrication reactor. Credit: Authors / Aalto University

It’s a very ‘carbony’ time: graphene jacket, graphene-skinned airplane, and schwarzite

In August 2018, I been stumbled across several stories about graphene-based products and a new form of carbon.

Graphene jacket

The company producing this jacket has as its goal “… creating bionic clothing that is both bulletproof and intelligent.” Well, ‘bionic‘ means biologically-inspired engineering and ‘intelligent‘ usually means there’s some kind of computing capability in the product. This jacket, which is the first step towards the company’s goal, is not bionic, bulletproof, or intelligent. Nonetheless, it represents a very interesting science experiment in which you, the consumer, are part of step two in the company’s R&D (research and development).

Onto Vollebak’s graphene jacket,

Courtesy: Vollebak

From an August 14, 2018 article by Jesus Diaz for Fast Company,

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that have long threatened to revolutionize everything from aerospace engineering to medicine. …

Despite its immense promise, graphene still hasn’t found much use in consumer products, thanks to the fact that it’s hard to manipulate and manufacture in industrial quantities. The process of developing Vollebak’s jacket, according to the company’s cofounders, brothers Steve and Nick Tidball, took years of intensive research, during which the company worked with the same material scientists who built Michael Phelps’ 2008 Olympic Speedo swimsuit (which was famously banned for shattering records at the event).

The jacket is made out of a two-sided material, which the company invented during the extensive R&D process. The graphene side looks gunmetal gray, while the flipside appears matte black. To create it, the scientists turned raw graphite into something called graphene “nanoplatelets,” which are stacks of graphene that were then blended with polyurethane to create a membrane. That, in turn, is bonded to nylon to form the other side of the material, which Vollebak says alters the properties of the nylon itself. “Adding graphene to the nylon fundamentally changes its mechanical and chemical properties–a nylon fabric that couldn’t naturally conduct heat or energy, for instance, now can,” the company claims.

The company says that it’s reversible so you can enjoy graphene’s properties in different ways as the material interacts with either your skin or the world around you. “As physicists at the Max Planck Institute revealed, graphene challenges the fundamental laws of heat conduction, which means your jacket will not only conduct the heat from your body around itself to equalize your skin temperature and increase it, but the jacket can also theoretically store an unlimited amount of heat, which means it can work like a radiator,” Tidball explains.

He means it literally. You can leave the jacket out in the sun, or on another source of warmth, as it absorbs heat. Then, the company explains on its website, “If you then turn it inside out and wear the graphene next to your skin, it acts like a radiator, retaining its heat and spreading it around your body. The effect can be visibly demonstrated by placing your hand on the fabric, taking it away and then shooting the jacket with a thermal imaging camera. The heat of the handprint stays long after the hand has left.”

There’s a lot more to the article although it does feature some hype and I’m not sure I believe Diaz’s claim (August 14, 2018 article) that ‘graphene-based’ hair dye is perfectly safe ( Note: A link has been removed),

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that will one day revolutionize everything from aerospace engineering to medicine. Its diverse uses are seemingly endless: It can stop a bullet if you add enough layers. It can change the color of your hair with no adverse effects. [emphasis mine] It can turn the walls of your home into a giant fire detector. “It’s so strong and so stretchy that the fibers of a spider web coated in graphene could catch a falling plane,” as Vollebak puts it in its marketing materials.

Not unless things have changed greatly since March 2018. My August 2, 2018 posting featured the graphene-based hair dye announcement from March 2018 and a cautionary note from Dr. Andrew Maynard (scroll down ab out 50% of the way for a longer excerpt of Maynard’s comments),

Northwestern University’s press release proudly announced, “Graphene finds new application as nontoxic, anti-static hair dye.” The announcement spawned headlines like “Enough with the toxic hair dyes. We could use graphene instead,” and “’Miracle material’ graphene used to create the ultimate hair dye.”

From these headlines, you might be forgiven for getting the idea that the safety of graphene-based hair dyes is a done deal. Yet having studied the potential health and environmental impacts of engineered nanomaterials for more years than I care to remember, I find such overly optimistic pronouncements worrying – especially when they’re not backed up by clear evidence.

These studies need to be approached with care, as the precise risks of graphene exposure will depend on how the material is used, how exposure occurs and how much of it is encountered. Yet there’s sufficient evidence to suggest that this substance should be used with caution – especially where there’s a high chance of exposure or that it could be released into the environment.

The full text of Dr. Maynard’s comments about graphene hair dyes and risk can be found here.

Bearing in mind  that graphene-based hair dye is an entirely different class of product from the jacket, I wouldn’t necessarily dismiss risks; I would like to know what kind of risk assessment and safety testing has been done. Due to their understandable enthusiasm, the brothers Tidball have focused all their marketing on the benefits and the opportunity for the consumer to test their product (from graphene jacket product webpage),

While it’s completely invisible and only a single atom thick, graphene is the lightest, strongest, most conductive material ever discovered, and has the same potential to change life on Earth as stone, bronze and iron once did. But it remains difficult to work with, extremely expensive to produce at scale, and lives mostly in pioneering research labs. So following in the footsteps of the scientists who discovered it through their own highly speculative experiments, we’re releasing graphene-coated jackets into the world as experimental prototypes. Our aim is to open up our R&D and accelerate discovery by getting graphene out of the lab and into the field so that we can harness the collective power of early adopters as a test group. No-one yet knows the true limits of what graphene can do, so the first edition of the Graphene Jacket is fully reversible with one side coated in graphene and the other side not. If you’d like to take part in the next stage of this supermaterial’s history, the experiment is now open. You can now buy it, test it and tell us about it. [emphasis mine]

How maverick experiments won the Nobel Prize

While graphene’s existence was first theorised in the 1940s, it wasn’t until 2004 that two maverick scientists, Andre Geim and Konstantin Novoselov, were able to isolate and test it. Through highly speculative and unfunded experimentation known as their ‘Friday night experiments,’ they peeled layer after layer off a shaving of graphite using Scotch tape until they produced a sample of graphene just one atom thick. After similarly leftfield thinking won Geim the 2000 Ig Nobel prize for levitating frogs using magnets, the pair won the Nobel prize in 2010 for the isolation of graphene.

Should you be interested, in beta-testing the jacket, it will cost you $695 (presumably USD); order here. One last thing, Vollebak is based in the UK.

Graphene skinned plane

An August 14, 2018 news item (also published as an August 1, 2018 Haydale press release) by Sue Keighley on Azonano heralds a new technology for airplans,

Haydale, (AIM: HAYD), the global advanced materials group, notes the announcement made yesterday from the University of Central Lancashire (UCLAN) about the recent unveiling of the world’s first graphene skinned plane at the internationally renowned Farnborough air show.

The prepreg material, developed by Haydale, has potential value for fuselage and wing surfaces in larger scale aero and space applications especially for the rapidly expanding drone market and, in the longer term, the commercial aerospace sector. By incorporating functionalised nanoparticles into epoxy resins, the electrical conductivity of fibre-reinforced composites has been significantly improved for lightning-strike protection, thereby achieving substantial weight saving and removing some manufacturing complexities.

Before getting to the photo, here’s a definition for pre-preg from its Wikipedia entry (Note: Links have been removed),

Pre-preg is “pre-impregnated” composite fibers where a thermoset polymer matrix material, such as epoxy, or a thermoplastic resin is already present. The fibers often take the form of a weave and the matrix is used to bond them together and to other components during manufacture.

Haydale has supplied graphene enhanced prepreg material for Juno, a three-metre wide graphene-enhanced composite skinned aircraft, that was revealed as part of the ‘Futures Day’ at Farnborough Air Show 2018. [downloaded from https://www.azonano.com/news.aspx?newsID=36298]

A July 31, 2018 University of Central Lancashire (UCLan) press release provides a tiny bit more (pun intended) detail,

The University of Central Lancashire (UCLan) has unveiled the world’s first graphene skinned plane at an internationally renowned air show.

Juno, a three-and-a-half-metre wide graphene skinned aircraft, was revealed on the North West Aerospace Alliance (NWAA) stand as part of the ‘Futures Day’ at Farnborough Air Show 2018.

The University’s aerospace engineering team has worked in partnership with the Sheffield Advanced Manufacturing Research Centre (AMRC), the University of Manchester’s National Graphene Institute (NGI), Haydale Graphene Industries (Haydale) and a range of other businesses to develop the unmanned aerial vehicle (UAV), which also includes graphene batteries and 3D printed parts.

Billy Beggs, UCLan’s Engineering Innovation Manager, said: “The industry reaction to Juno at Farnborough was superb with many positive comments about the work we’re doing. Having Juno at one the world’s biggest air shows demonstrates the great strides we’re making in leading a programme to accelerate the uptake of graphene and other nano-materials into industry.

“The programme supports the objectives of the UK Industrial Strategy and the University’s Engineering Innovation Centre (EIC) to increase industry relevant research and applications linked to key local specialisms. Given that Lancashire represents the fourth largest aerospace cluster in the world, there is perhaps no better place to be developing next generation technologies for the UK aerospace industry.”

Previous graphene developments at UCLan have included the world’s first flight of a graphene skinned wing and the launch of a specially designed graphene-enhanced capsule into near space using high altitude balloons.

UCLan engineering students have been involved in the hands-on project, helping build Juno on the Preston Campus.

Haydale supplied much of the material and all the graphene used in the aircraft. Ray Gibbs, Chief Executive Officer, said: “We are delighted to be part of the project team. Juno has highlighted the capability and benefit of using graphene to meet key issues faced by the market, such as reducing weight to increase range and payload, defeating lightning strike and protecting aircraft skins against ice build-up.”

David Bailey Chief Executive of the North West Aerospace Alliance added: “The North West aerospace cluster contributes over £7 billion to the UK economy, accounting for one quarter of the UK aerospace turnover. It is essential that the sector continues to develop next generation technologies so that it can help the UK retain its competitive advantage. It has been a pleasure to support the Engineering Innovation Centre team at the University in developing the world’s first full graphene skinned aircraft.”

The Juno project team represents the latest phase in a long-term strategic partnership between the University and a range of organisations. The partnership is expected to go from strength to strength following the opening of the £32m EIC facility in February 2019.

The next step is to fly Juno and conduct further tests over the next two months.

Next item, a new carbon material.

Schwarzite

I love watching this gif of a schwarzite,

The three-dimensional cage structure of a schwarzite that was formed inside the pores of a zeolite. (Graphics by Yongjin Lee and Efrem Braun)

An August 13, 2018 news item on Nanowerk announces the new carbon structure,

The discovery of buckyballs [also known as fullerenes, C60, or buckminsterfullerenes] surprised and delighted chemists in the 1980s, nanotubes jazzed physicists in the 1990s, and graphene charged up materials scientists in the 2000s, but one nanoscale carbon structure – a negatively curved surface called a schwarzite – has eluded everyone. Until now.

University of California, Berkeley [UC Berkeley], chemists have proved that three carbon structures recently created by scientists in South Korea and Japan are in fact the long-sought schwarzites, which researchers predict will have unique electrical and storage properties like those now being discovered in buckminsterfullerenes (buckyballs or fullerenes for short), nanotubes and graphene.

An August 13, 2018 UC Berkeley news release by Robert Sanders, which originated the news item, describes how the Berkeley scientists and the members of their international  collaboration from Germany, Switzerland, Russia, and Italy, have contributed to the current state of schwarzite research,

The new structures were built inside the pores of zeolites, crystalline forms of silicon dioxide – sand – more commonly used as water softeners in laundry detergents and to catalytically crack petroleum into gasoline. Called zeolite-templated carbons (ZTC), the structures were being investigated for possible interesting properties, though the creators were unaware of their identity as schwarzites, which theoretical chemists have worked on for decades.

Based on this theoretical work, chemists predict that schwarzites will have unique electronic, magnetic and optical properties that would make them useful as supercapacitors, battery electrodes and catalysts, and with large internal spaces ideal for gas storage and separation.

UC Berkeley postdoctoral fellow Efrem Braun and his colleagues identified these ZTC materials as schwarzites based of their negative curvature, and developed a way to predict which zeolites can be used to make schwarzites and which can’t.

“We now have the recipe for how to make these structures, which is important because, if we can make them, we can explore their behavior, which we are working hard to do now,” said Berend Smit, an adjunct professor of chemical and biomolecular engineering at UC Berkeley and an expert on porous materials such as zeolites and metal-organic frameworks.

Smit, the paper’s corresponding author, Braun and their colleagues in Switzerland, China, Germany, Italy and Russia will report their discovery this week in the journal Proceedings of the National Academy of Sciences. Smit is also a faculty scientist at Lawrence Berkeley National Laboratory.

Playing with carbon

Diamond and graphite are well-known three-dimensional crystalline arrangements of pure carbon, but carbon atoms can also form two-dimensional “crystals” — hexagonal arrangements patterned like chicken wire. Graphene is one such arrangement: a flat sheet of carbon atoms that is not only the strongest material on Earth, but also has a high electrical conductivity that makes it a promising component of electronic devices.

schwarzite carbon cage

The cage structure of a schwarzite that was formed inside the pores of a zeolite. The zeolite is subsequently dissolved to release the new material. (Graphics by Yongjin Lee and Efrem Braun)

Graphene sheets can be wadded up to form soccer ball-shaped fullerenes – spherical carbon cages that can store molecules and are being used today to deliver drugs and genes into the body. Rolling graphene into a cylinder yields fullerenes called nanotubes, which are being explored today as highly conductive wires in electronics and storage vessels for gases like hydrogen and carbon dioxide. All of these are submicroscopic, 10,000 times smaller than the width of a human hair.

To date, however, only positively curved fullerenes and graphene, which has zero curvature, have been synthesized, feats rewarded by Nobel Prizes in 1996 and 2010, respectively.

In the 1880s, German physicist Hermann Schwarz investigated negatively curved structures that resemble soap-bubble surfaces, and when theoretical work on carbon cage molecules ramped up in the 1990s, Schwarz’s name became attached to the hypothetical negatively curved carbon sheets.

“The experimental validation of schwarzites thus completes the triumvirate of possible curvatures to graphene; positively curved, flat, and now negatively curved,” Braun added.

Minimize me

Like soap bubbles on wire frames, schwarzites are topologically minimal surfaces. When made inside a zeolite, a vapor of carbon-containing molecules is injected, allowing the carbon to assemble into a two-dimensional graphene-like sheet lining the walls of the pores in the zeolite. The surface is stretched tautly to minimize its area, which makes all the surfaces curve negatively, like a saddle. The zeolite is then dissolved, leaving behind the schwarzite.

soap bubble schwarzite structure

A computer-rendered negatively curved soap bubble that exhibits the geometry of a carbon schwarzite. (Felix Knöppel image)

“These negatively-curved carbons have been very hard to synthesize on their own, but it turns out that you can grow the carbon film catalytically at the surface of a zeolite,” Braun said. “But the schwarzites synthesized to date have been made by choosing zeolite templates through trial and error. We provide very simple instructions you can follow to rationally make schwarzites and we show that, by choosing the right zeolite, you can tune schwarzites to optimize the properties you want.”

Researchers should be able to pack unusually large amounts of electrical charge into schwarzites, which would make them better capacitors than conventional ones used today in electronics. Their large interior volume would also allow storage of atoms and molecules, which is also being explored with fullerenes and nanotubes. And their large surface area, equivalent to the surface areas of the zeolites they’re grown in, could make them as versatile as zeolites for catalyzing reactions in the petroleum and natural gas industries.

Braun modeled ZTC structures computationally using the known structures of zeolites, and worked with topological mathematician Senja Barthel of the École Polytechnique Fédérale de Lausanne in Sion, Switzerland, to determine which of the minimal surfaces the structures resembled.

The team determined that, of the approximately 200 zeolites created to date, only 15 can be used as a template to make schwarzites, and only three of them have been used to date to produce schwarzite ZTCs. Over a million zeolite structures have been predicted, however, so there could be many more possible schwarzite carbon structures made using the zeolite-templating method.

Other co-authors of the paper are Yongjin Lee, Seyed Mohamad Moosavi and Barthel of the École Polytechnique Fédérale de Lausanne, Rocio Mercado of UC Berkeley, Igor Baburin of the Technische Universität Dresden in Germany and Davide Proserpio of the Università degli Studi di Milano in Italy and Samara State Technical University in Russia.

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

Generating carbon schwarzites via zeolite-templating by Efrem Braun, Yongjin Lee, Seyed Mohamad Moosavi, Senja Barthel, Rocio Mercado, Igor A. Baburin, Davide M. Proserpio, and Berend Smit. PNAS August 14, 2018. 201805062; published ahead of print August 14, 2018. https://doi.org/10.1073/pnas.1805062115

This paper appears to be open access.

An artistic feud over the blackest black (a coating material)

This artistic feud has its roots in a nanotechnology-enabled coating material known as Vantablack. Surrey Nanosystems in the UK sent me an announcement which I featured here in a March 14, 2016 posting. About one month later (in an April 16, 2016 posting regarding risks and an artistic controversy), I recounted the story of the controversy, which resulted from the company’s exclusive deal with artist, Sir Anish Kapoor (scroll down the post about 60% of the way to ‘Anish Kapoor and his exclusive rights to Vantablack’.

Apparently, the controversy led to an artistic feud between artists Stuart Semple and Kapoor. Outraged by the notion that only Kapoor could have access to the world’s blackest black, Semple created the world’s pinkest pink and stipulated that any artist in the world could have access to this colour—except Anish Kapoor.

Kapoor’s response can seen in a January 30,2019 article by Sarah Cascone for artnet.com,

… Semple started selling what he called “the world’s pinkest pink, available to anyone who wasn’t Kapoor.”

“I wanted to make a point about elitism and self-expression and the fact that everybody should be able to make art,” Semple said. But within weeks, “tragedy struck. Anish Kapoor got our pink! And he dipped his middle finger in it and put a picture on Instagram!”

[downloaded from http://www.artlyst.com/wp-content/uploads/2016/10/anish-kapoor-pink-1200x600_c.jpg]

Cascone’s article, which explores the history of the feud in greater detail also announces the latest installment (Note: Links have been removed),

In the battle over artistic access to the world’s blackest blacks, Stuart Semple isn’t backing down. The British artist, who took exception to Anish Kapoor’s exclusive contract to use Vantablack, the world’s blackest black substance, just launched a Kickstarter to produce a super dark paint of his own—and it has now been fully funded.

Jesus Diaz’s February 1, 2019 article for Fast Company provides some general technical details (Note: A link has been removed),

… Semple decided to team up with paint makers and about 1,000 artists to develop and test a competitor to Vantablack. His first version, Black 2.0, wasn’t quite as black as Vantablack, since it only absorbed 95% of the visible light (Vantablack absorbs about 99%).

Now, Black 3.0 is out and available on Kickstarter for about $32 per 150ml tube. According to Semple, it is the blackest, mattest, flattest acrylic paint available on the planet, capturing up to 99% of all the visible spectrum radiation. The paint is based on a new pigment called Black Magick, whose exact composition they aren’t disclosing. Black 3.0 is made up of this pigment, combined with a custom acrylic polymer. Semple and his colleagues claim that the polymer “is special because it has more available bonds than any other acrylic polymer being used in paints,” allowing more pigment density. The paint is then finished with what they claim are new “nano-mattifiers,” which remove any shine from the paint. Unlike Vantablack, the resulting paint is soluble in water and nontoxic. [emphasis mine]

I wonder what a ‘nano-mattifier’ might be. Regardless, I’m glad to see this new black is (with a nod to my April 16, 2016 posting about risks and this artistic controversy) nontoxic.

Semple’s ‘blackest black paint’ Kickstarter campaign can be found here. It ends on March 22, 2019 at 1:01 am PDT. The goal is $42,755 in Canadian dollars (CAD) and, as Iwrite this, they currently have $473,062 CAD in pledges.

I don’t usually embed videos that run over 5 mins. but Stuart Semple is very appealing in at least two senses of the word,

Spider glue

Caption: An orb spider, glue-maker extraordinaire, at work on a web. Credit: The University of Akron

Scientists are taking inspiration from spiders in their quest to develop better adhesives. (Are they abandoning the gecko? Usually when scientists study adhesiveness, there’s talk of geckos. From a June 5, 2018 news item on ScienceDaily,

Ever wonder why paint peels off the wall during summer’s high humidity? It’s the same reason that bandages separate from skin when we bathe or swim.

Interfacial water, as it’s known, forms a slippery and non-adhesive layer between the glue and the surface to which it is meant to stick, interfering with the formation of adhesive bonds between the two.

Overcoming the effects of interfacial water is one of the challenges facing developers of commercial adhesives.

To find a solution, researchers at The University of Akron (UA) are looking to one of the strongest materials found in nature: spider silk.

The sticky glue that coats the silk threads of spider webs is a hydrogel, meaning it is full of water. One would think, then, that spiders would have difficulty catching prey, especially in humid conditions — but they do not. In fact, their sticky glue, which has been a subject of intensive research for years, is one of the most effective biological glues in all of nature.

A June 4, 2018 University of Akron news release (also on EurekAlert published on June 5, 2018), which originated the news item, provides more detail,

So how is spider glue able to stick in highly humid conditions?

That question was the subject of investigation by UA graduate students Saranshu Singla, Gaurav Amarpuri and Nishad Dhopatkar, who have been working with Dr. Ali Dhinojwala, interim dean of the College of Polymer Science and Polymer Engineering, and Dr. Todd Blackledge, professor of biology in the Integrated Bioscience program. Both professors are principal investigators in UA’s Biomimicry Research Innovation Center [BRIC], which specializes in emulating biological forms, processes, patterns and systems to solve technical challenges.

The team’s findings, which may provide the clue to developing stronger commercial adhesives, can be read in a paper recently published in the journal Nature Communications.

Singla and her colleagues set out to examine the secret behind the success of the common orb spider (Larinioides cornutus) glue and uncover how it overcomes the primary obstacle of achieving good adhesion in the humid conditions where water could be present between the glue and the target surface.

To investigate the processes involved, the team took orb spider glue, set it on sapphire substrate, then examined it using a combination of interface-sensitive spectroscopy and infrared spectroscopy.

Spider glue is made of three elements: two specialized glycoproteins, a collection of low molecular mass organic and inorganic compounds (LMMCs), and water. The LMMCs are hygroscopic (water-attracting), which keeps the glue soft and tacky to stick.

Singla and her team discovered that these glycoproteins act as primary binding agents to the surface. Glycoprotein-based glues have been identified in several other biological glues, such as fungi, algae, diatoms, sea stars, sticklebacks and English ivy.

But why doesn’t the water present in the spider glue interfere with the adhesive contact the way it does with most synthetic adhesives?

The LMMCs, the team concluded, perform a previously unknown function of sequestering interfacial water, preventing adhesive failure.

Singla and colleagues determined that it is the interaction of glycoproteins and LMMCs that governs the adhesive quality of the glue produced, with the respective proportions varying across species, thus optimizing adhesive strength to match the relative humidity of spider habitat.

“The hygroscopic compounds – known as water-absorbers – in spider glue play a previously unknown role in moving water away from the boundary, thereby preventing failure of spider glue at high humidity,” explained Singla.

The ability of the spider glue to overcome the problem of interfacial water by effectively absorbing it is the key finding of the research, and the one with perhaps the strongest prospect for commercial development.

“Imagine a paint that is guaranteed for life, come rain or shine,” Singla remarked.

All thanks to your friendly neighborhood spider glue.

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

Hygroscopic compounds in spider aggregate glue remove interfacial water to maintain adhesion in humid conditions by Saranshu Singla, Gaurav Amarpuri, Nishad Dhopatkar, Todd A. Blackledge, & Ali Dhinojwala. Nature Communicationsvolume 9, Article number: 1890 (2018) Published 22 May 2018 DOI: https://doi.org/10.1038/s41467-018-04263-z

This paper is open access.

Killing bacteria on contact with dragonfly-inspired nanocoating

Scientists in Singapore were inspired by dragonflies and cicadas according to a March 28, 2018 news item on Nanowerk (Note: A link has been removed),

Studies have shown that the wings of dragonflies and cicadas prevent bacterial growth due to their natural structure. The surfaces of their wings are covered in nanopillars making them look like a bed of nails. When bacteria come into contact with these surfaces, their cell membranes get ripped apart immediately and they are killed. This inspired researchers from the Institute of Bioengineering and Nanotechnology (IBN) of A*STAR to invent an anti-bacterial nano coating for disinfecting frequently touched surfaces such as door handles, tables and lift buttons.

This technology will prove particularly useful in creating bacteria-free surfaces in places like hospitals and clinics, where sterilization is important to help control the spread of infections. Their new research was recently published in the journal Small (“ZnO Nanopillar Coated Surfaces with Substrate-Dependent Superbactericidal Property”)

Image 1: Zinc oxide nanopillars that looked like a bed of nails can kill a broad range of germs when used as a coating on frequently-touched surfaces. Courtesy: A*STAR

A March 28, 2018 Agency for Science Technology and Research (A*STAR) press release, which originated the news item, describes the work further,

80% of common infections are spread by hands, according to the B.C. [province of Canada] Centre for Disease Control1. Disinfecting commonly touched surfaces helps to reduce the spread of harmful germs by our hands, but would require manual and repeated disinfection because germs grow rapidly. Current disinfectants may also contain chemicals like triclosan which are not recognized as safe and effective 2, and may lead to bacterial resistance and environmental contamination if used extensively.

“There is an urgent need for a better way to disinfect surfaces without causing bacterial resistance or harm to the environment. This will help us to prevent the transmission of infectious diseases from contact with surfaces,” said IBN Executive Director Professor Jackie Y. Ying.

To tackle this problem, a team of researchers led by IBN Group Leader Dr Yugen Zhang created a novel nano coating that can spontaneously kill bacteria upon contact. Inspired by studies on dragonflies and cicadas, the IBN scientists grew nanopilllars of zinc oxide, a compound known for its anti-bacterial and non-toxic properties. The zinc oxide nanopillars can kill a broad range of germs like E. coli and S. aureus that are commonly transmitted from surface contact.

Tests on ceramic, glass, titanium and zinc surfaces showed that the coating effectively killed up to 99.9% of germs found on the surfaces. As the bacteria are killed mechanically rather than chemically, the use of the nano coating would not contribute to environmental pollution. Also, the bacteria will not be able to develop resistance as they are completely destroyed when their cell walls are pierced by the nanopillars upon contact.

Further studies revealed that the nano coating demonstrated the best bacteria killing power when it is applied on zinc surfaces, compared with other surfaces. This is because the zinc oxide nanopillars catalyzed the release of superoxides (or reactive oxygen species), which could even kill nearby free floating bacteria that were not in direct contact with the surface. This super bacteria killing power from the combination of nanopillars and zinc broadens the scope of applications of the coating beyond hard surfaces.

Subsequently, the researchers studied the effect of placing a piece of zinc that had been coated with zinc oxide nanopillars into water containing E. coli. All the bacteria were killed, suggesting that this material could potentially be used for water purification.

Dr Zhang said, “Our nano coating is designed to disinfect surfaces in a novel yet practical way. This study demonstrated that our coating can effectively kill germs on different types of surfaces, and also in water. We were also able to achieve super bacteria killing power when the coating was used on zinc surfaces because of its dual mechanism of action. We hope to use this technology to create bacteria-free surfaces in a safe, inexpensive and effective manner, especially in places where germs tend to accumulate.”

IBN has recently received a grant from the National Research Foundation, Prime Minister’s Office, Singapore, under its Competitive Research Programme to further develop this coating technology in collaboration with Tan Tock Seng Hospital for commercial application over the next 5 years.

1 B.C. Centre for Disease Control

2 U.S. Food & Drug Administration

(I wasn’t expecting to see a reference to my home province [BC Centre for Disease Control].) Back to the usual, here’s a link to and a citation for the paper,

ZnO Nanopillar Coated Surfaces with Substrate‐Dependent Superbactericidal Property by Guangshun Yi, Yuan Yuan, Xiukai Li, Yugen Zhang. Small https://doi.org/10.1002/smll.201703159 First published: 22 February 2018

This paper is behind a paywall.

One final comment, this research reminds me of research into simulating shark skin because that too has bacteria-killing nanostructures. My latest about the sharkskin research is a Sept, 18, 2014 posting.

Better hair dyes with graphene and a cautionary note

Beauty products aren’t usually the first applications that come to mind when discussing graphene or any other research and development (R&D) as I learned when teaching a course a few years ago. But research and development  in that field are imperative as every company is scrambling for a short-lived competitive advantage for a truly new products or a perceived competitive advantage in a field where a lot of products are pretty much the same.

This March 15, 2018 news item on ScienceDaily describes graphene as a potential hair dye,

Graphene, a naturally black material, could provide a new strategy for dyeing hair in difficult-to-create dark shades. And because it’s a conductive material, hair dyed with graphene might also be less prone to staticky flyaways. Now, researchers have put it to the test. In an article published March 15 [2018] in the journal Chem, they used sheets of graphene to make a dye that adheres to the surface of hair, forming a coating that is resistant to at least 30 washes without the need for chemicals that open up and damage the hair cuticle.

Courtesy: Northwestern University

A March 15, 2018 Cell Press news release on EurekAlert, which originated the news item, fills in more the of the story,

Most permanent hair dyes used today are harmful to hair. “Your hair is covered in these cuticle scales like the scales of a fish, and people have to use ammonia or organic amines to lift the scales and allow dye molecules to get inside a lot quicker,” says senior author Jiaxing Huang, a materials scientist at Northwestern University. But lifting the cuticle makes the strands of the hair more brittle, and the damage is only exacerbated by the hydrogen peroxide that is used to trigger the reaction that synthesizes the dye once the pigment molecules are inside the hair.

These problems could theoretically be solved by a dye that coats rather than penetrates the hair. “However, the obvious problem of coating-based dyes is that they tend to wash out very easily,” says Huang. But when he and his team coated samples of human hair with a solution of graphene sheets, they were able to turn platinum blond hair black and keep it that way for at least 30 washes–the number necessary for a hair dye to be considered “permanent.”

This effectiveness has to do with the structure of graphene: it’s made of up thin, flexible sheets that can adapt to uneven surfaces. “Imagine a piece of paper. A business card is very rigid and doesn’t flex by itself. But if you take a much bigger sheet of newspaper–if you still can find one nowadays–it can bend easily. This makes graphene sheets a good coating material,” he says. And once the coating is formed, the graphene sheets are particularly good at keeping out water during washes, which keeps the water from eroding both the graphene and the polymer binder that the team also added to the dye solution to help with adhesion.

The graphene dye has additional advantages. Each coated hair is like a little wire in that it is able to conduct heat and electricity. This means that it’s easy for graphene-dyed hair to dissipate static electricity, eliminating the problem of flyaways on dry winter days. The graphene flakes are large enough that they won’t absorb through the skin like other dye molecules. And although graphene is typically black, its precursor, graphene oxide, is light brown. But the color of graphene oxide can be gradually darkened with heat or chemical reactions, meaning that this dye could be used for a variety of shades or even for an ombre effect.

What Huang thinks is particularly striking about this application of graphene is that it takes advantage of graphene’s most obvious property. “In many potential graphene applications, the black color of graphene is somewhat undesirable and something of a sore point,” he says. Here, though, it’s applied to a field where creating dark colors has historically been a problem.

The graphene used for hair dye also doesn’t need to be of the same high quality as it does for other applications. “For hair dye, the most important property is graphene being black. You can have graphene that is too lousy for higher-end electronic applications, but it’s perfectly okay for this. So I think this application can leverage the current graphene product as is, and that’s why I think that this could happen a lot sooner than many of the other proposed applications,” he says.

Making it happen is his next goal. He hopes to get funding to continue the research and make these dyes a reality for the people whose lives they would improve. “This is an idea that was inspired by curiosity. It was very fun to do, but it didn’t sound very big and noble when we started working on it,” he says. “But after we deep-dived into studying hair dyes, we realized that, wow, this is actually not at all a small problem. And it’s one that graphene could really help to solve.”

Northwestern University’s Amanda Morris also wrote a March 15, 2018 news release (it’s repetitive but there are some interesting new details; Note: Links have been removed),

It’s an issue that has plagued the beauty industry for more than a century: Dying hair too often can irreparably damage your silky strands.

Now a Northwestern University team has used materials science to solve this age-old problem. The team has leveraged super material graphene to develop a new hair dye that is less harmful [emphasis mine], non-damaging and lasts through many washes without fading. Graphene’s conductive nature also opens up new opportunities for hair, such as turning it into in situ electrodes or integrating it with wearable electronic devices.

Dying hair might seem simple and ordinary, but it’s actually a sophisticated chemical process. Called the cuticle, the outermost layer of a hair is made of cells that overlap in a scale-like pattern. Commercial dyes work by using harsh chemicals, such as ammonia and bleach, to first pry open the cuticle scales to allow colorant molecules inside and then trigger a reaction inside the hair to produce more color. Not only does this process cause hair to become more fragile, some of the small molecules are also quite toxic.

Huang and his team bypassed harmful chemicals altogether by leveraging the natural geometry of graphene sheets. While current hair dyes use a cocktail of small molecules that work by chemically altering the hair, graphene sheets are soft and flexible, so they wrap around each hair for an even coat. Huang’s ink formula also incorporates edible, non-toxic polymer binders to ensure that the graphene sticks — and lasts through at least 30 washes, which is the commercial requirement for permanent hair dye. An added bonus: graphene is anti-static, so it keeps winter-weather flyaways to a minimum.

“It’s similar to the difference between a wet paper towel and a tennis ball,” Huang explained, comparing the geometry of graphene to that of other black pigment particles, such as carbon black or iron oxide, which can only be used in temporary hair dyes. “The paper towel is going to wrap and stick much better. The ball-like particles are much more easily removed with shampoo.”

This geometry also contributes to why graphene is a safer alternative. Whereas small molecules can easily be inhaled or pass through the skin barrier, graphene is too big to enter the body. “Compared to those small molecules used in current hair dyes, graphene flakes are humongous,” said Huang, who is a member of Northwestern’s International Institute of Nanotechnology.

Ever since graphene — the two-dimensional network of carbon atoms — burst onto the science scene in 2004, the possibilities for the promising material have seemed nearly endless. With its ultra-strong and lightweight structure, graphene has potential for many applications in high-performance electronics, high-strength materials and energy devices. But development of those applications often require graphene materials to be as structurally perfect as possible in order to achieve extraordinary electrical, mechanical or thermal properties.

The most important graphene property for Huang’s hair dye, however, is simply its color: black. So Huang’s team used graphene oxide, an imperfect version of graphene that is a cheaper, more available oxidized derivative.

“Our hair dye solves a real-world problem without relying on very high-quality graphene, which is not easy to make,” Huang said. “Obviously more work needs to be done, but I feel optimistic about this application.”

Still, future versions of the dye could someday potentially leverage graphene’s notable properties, including its highly conductive nature.

“People could apply this dye to make hair conductive on the surface,” Huang said. “It could then be integrated with wearable electronics or become a conductive probe. We are only limited by our imagination.”

So far, Huang has developed graphene-based hair dyes in multiple shades of brown and black. Next, he plans to experiment with more colors.

Interestingly, the tiny note of caution”less harmful” doesn’t appear in the Cell Press news release. Never fear, Dr. Andrew Maynard (Director Risk Innovation Lab at Arizona State University) has written a March 20, 2018 essay on The Conversation suggesting a little further investigation (Note: Links have been removed),

Northwestern University’s press release proudly announced, “Graphene finds new application as nontoxic, anti-static hair dye.” The announcement spawned headlines like “Enough with the toxic hair dyes. We could use graphene instead,” and “’Miracle material’ graphene used to create the ultimate hair dye.”

From these headlines, you might be forgiven for getting the idea that the safety of graphene-based hair dyes is a done deal. Yet having studied the potential health and environmental impacts of engineered nanomaterials for more years than I care to remember, I find such overly optimistic pronouncements worrying – especially when they’re not backed up by clear evidence.

Tiny materials, potentially bigger problems

Engineered nanomaterials like graphene and graphene oxide (the particular form used in the dye experiments) aren’t necessarily harmful. But nanomaterials can behave in unusual ways that depend on particle size, shape, chemistry and application. Because of this, researchers have long been cautious about giving them a clean bill of health without first testing them extensively. And while a large body of research to date doesn’t indicate graphene is particularly dangerous, neither does it suggest it’s completely safe.

A quick search of scientific papers over the past few years shows that, since 2004, over 2,000 studies have been published that mention graphene toxicity; nearly 500 were published in 2017 alone.

This growing body of research suggests that if graphene gets into your body or the environment in sufficient quantities, it could cause harm. A 2016 review, for instance, indicated that graphene oxide particles could result in lung damage at high doses (equivalent to around 0.7 grams of inhaled material). Another review published in 2017 suggested that these materials could affect the biology of some plants and algae, as well as invertebrates and vertebrates toward the lower end of the ecological pyramid. The authors of the 2017 study concluded that research “unequivocally confirms that graphene in any of its numerous forms and derivatives must be approached as a potentially hazardous material.”

These studies need to be approached with care, as the precise risks of graphene exposure will depend on how the material is used, how exposure occurs and how much of it is encountered. Yet there’s sufficient evidence to suggest that this substance should be used with caution – especially where there’s a high chance of exposure or that it could be released into the environment.

Unfortunately, graphene-based hair dyes tick both of these boxes. Used in this way, the substance is potentially inhalable (especially with spray-on products) and ingestible through careless use. It’s also almost guaranteed that excess graphene-containing dye will wash down the drain and into the environment.

Undermining other efforts?

I was alerted to just how counterproductive such headlines can be by my colleague Tim Harper, founder of G2O Water Technologies – a company that uses graphene oxide-coated membranes to treat wastewater. Like many companies in this area, G2O has been working to use graphene responsibly by minimizing the amount of graphene that ends up released to the environment.

Yet as Tim pointed out to me, if people are led to believe “that bunging a few grams of graphene down the drain every time you dye your hair is OK, this invalidates all the work we are doing making sure the few nanograms of graphene on our membranes stay put.” Many companies that use nanomaterials are trying to do the right thing, but it’s hard to justify the time and expense of being responsible when someone else’s more cavalier actions undercut your efforts.

Overpromising results and overlooking risk

This is where researchers and their institutions need to move beyond an “economy of promises” that spurs on hyperbole and discourages caution, and think more critically about how their statements may ultimately undermine responsible and beneficial development of a technology. They may even want to consider using guidelines, such as the Principles for Responsible Innovation developed by the organization Society Inside, for instance, to guide what they do and say.

If you have time, I encourage you to read Andrew’s piece in its entirety.

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

Multifunctional Graphene Hair Dye by Chong Luo, Lingye Zhou, Kevin Chiou, and Jiaxing Huang. Chem DOI: https://doi.org/10.1016/j.chempr.2018.02.02 Publication stage: In Press Corrected Proof

This paper appears to be open access.

*Two paragraphs (repetitions) were deleted from the excerpt of Dr. Andrew Maynard’s essay on August 14, 2018