Category Archives: coatings

Cellulose- and chitin-based biomaterial to replace plastics?

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

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

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

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

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

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

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

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

crab shells

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

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

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

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

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

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

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

lab vials

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

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

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

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

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

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

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

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

Historic and other buildings get protection from pollution?

This Sept. 15, 2017 news item on Nanowerk announces a new product for protecting buildings from pollution,

The organic pollution decomposing properties of titanium dioxide (TiO2 ) have been known for about half a century. However, practical applications have been few and hard to develop, but now a Greek paint producer claims to have found a solution

A Sept. 11, 2017 Youris (European Research Media Center) press release by Koen Mortelmans which originated the news item expands on the theme,

The photocatalytic properties of anatase, one of the three naturally occurring forms of titanium dioxide, were discovered in Japan in the late 1960s. Under the influence of the UV-radiation in sunlight, it can decompose organic pollutants such as bacteria, fungi and nicotine, and some inorganic materials into carbon dioxide. The catalytic effect is caused by the nanostructure of its crystals.

Applied outdoors, this affordable and widely available material could represent an efficient self-cleaning solution for buildings. This is due to the chemical reaction, which leaves a residue on building façades, a residue then washed away when it rains. Applying it to monuments in urban areas may save our cultural heritage, which is threatened by pollutants.

However, “photocatalytic paints and additives have long been a challenge for the coating industry, because the catalytic action affects the durability of resin binders and oxidizes the paint components,” explains Ioannis Arabatzis, founder and managing director of NanoPhos, based in the Greek town of Lavrio, in one of the countries home to some of the most important monuments of human history. The Greek company is testing a paint called Kirei, inspired by a Japanese word meaning both clean and beautiful.

According to Arabatzis, it’s an innovative product because it combines the self-cleaning action of photocatalytic nanoparticles and the reflective properties of cool wall paints. “When applied on exterior surfaces this paint can reflect more than 94% of the incident InfraRed radiation (IR), saving energy and reducing costs for heating and cooling”, he says. “The reflection values are enhanced by the self-cleaning ability. Compared to conventional paints, they remain unchanged for longer.”

The development of Kirei has been included in the European project BRESAER (BREakthrough Solutions for Adaptable Envelopes in building Refurbishment) which is studying a sustainable and adaptable “envelope system” to renovate buildings. The new paint was tested and subjected to quality controls following ISO standard procedures at the company’s own facilities and in other independent laboratories. “The lab results from testing in artificial, accelerated weathering conditions are reliable,” Arabatzis claims. “There was no sign of discolouration, chalking, cracking or any other paint defect during 2,000 hours of exposure to the simulated environmental conditions. We expect the coating’s service lifetime to be at least ten years.”

Many studies are being conducted to exploit the properties of titanium dioxide. Jan Duyzer, researcher at the Netherlands Organisation for Applied Scientific Research (TNO) in Utrecht, focused on depollution: “There is no doubt about the ability of anatase to decrease the levels of nitrogen oxides in the air. But in real situations, there are many differences in pollution, wind, light, and temperature. We were commissioned by the Dutch government specifically to find a way to take nitrogen oxides out of the air on roads and in traffic tunnels. We used anatase coated panels. Our results were disappointing, so the government decided to discontinue the research. Furthermore, we still don’t know what caused the difference between lab and life. Our best current hypothesis is that the total surface of the coated panels is very small compared to the large volumes of polluted air passing over them,” he tells youris.com.

Experimental deployment of titanium dioxide panels on an acoustic wall along a Dutch highway – Courtesy of Netherlands Organisation for Applied Scientific Research (TNO)

“In laboratory conditions the air is blown over the photocatalytic surface with a certain degree of turbulence. This results in the NOx-particles and the photocatalytic material coming into full contact with one another,” says engineer Anne Beeldens, visiting professor at KU Leuven, Belgium. Her experience with photocatalytic TiO2 is also limited to nitrogen dioxide (NOx) pollution.

In real applications, the air stream at the contact surface becomes laminar. This results in a lower velocity of the air at the surface and a lower depollution rate. Additionally, not all the air will be in contact with the photocatalytic surfaces. To ensure a good working application, the photocatalytic material needs to be positioned so that all the air is in contact with the surface and flows over it in a turbulent manner. This would allow as much of the NOx as possible to be in contact with photocatalytic material. In view of this, a good working application could lead to a reduction of 5 to 10 percent of NOx in the air, which is significant compared to other measures to reduce pollutants.”

The depollution capacity of TiO2 is undisputed, but most applications and tests have only involved specific kinds of substances. More research and measurements are required if we are to benefit more from the precious features of this material.

I think the most recent piece here on protecting buildings, i.e., the historic type, from pollution is an Oct. 21, 2014 posting: Heart of stone.

Korean researchers extend food shelf *life* with nanomicrobial coating

These Korean scientists have applied their new coating to food and to shoe insoles as they test various uses for their technology. From an Aug. 11, 2017 news item on Nanowerk,

The edible coating on produce has drawn a great deal of attention in the food and agricultural industry. It could not only prolong postharvest shelf life of produce against external changes in the environment but also provide additional nutrients to be useful for human health. However, most versions of the coating have had intrinsic limitations in their practical application.

First, highly specific interactions between coating materials and target surfaces are required for a stable and durable coating. Even further, the coating of bulk substrates, such as fruits, is time consuming or is not achievable in the conventional solution-based coating. In this respect, material-independent and rapid coating strategies are highly demanded.

The research team led by Professor Insung Choi of the Department of Chemistry developed a sprayable nanocoating technique using plant-derived polyphenol that can be applied to any surface.

An Aug. 10, 2017 KAIST (Korea Advanced Institute of Science and Technology) press release, which originated the news item, expands on the theme,

Polyphenols, a metabolite of photosynthesis, possess several hydroxyl groups and are found in a large number of plants showing excellent antioxidant properties. They have been widely used as a nontoxic food additive and are known to exhibit antibacterial, as well as potential anti-carcinogenic capabilities. Polyphenols can also be used with iron ions, which are naturally found in the body, to form an adhesive complex, which has been used in leather tanning, ink, etc.

The research team combined these chemical properties of polyphenol-iron complexes with spray techniques to develop their nanocoating technology. Compared to conventional immersion coating methods, which dip substrates in specialized coating solutions, this spray technique can coat the select areas more quickly. The spray also prevents cross contamination, which is a big concern for immersion methods. The research team has showcased the spray’s ability to coat a variety of different materials, including metals, plastics, glass, as well as textile fabrics. The polyphenol complex has been used to form antifogging films on corrective lenses, as well as antifungal treatments for shoe soles, demonstrating the versatility of their technique.

Furthermore, the spray has been used to coat produce with a naturally antibacterial, edible film. The coatings significantly improved the shelf life of tangerines and strawberries, preserving freshness beyond 28 days and 58 hours, respectively. (Uncoated fruit decomposed and became moldy under the same conditions). See the image below.

 

a –I, II: Uncoated and coated tangerines incubated for 14 and 28 days in daily-life settings

b –I: Uncoated and coated strawberries incubated for 58 hours in daily-life settings

b –II: Statistical investigation of the resulting edibility.

Professor Choi said, “Nanocoating technologies are still in their infancy, but they have untapped potential for exciting applications. As we have shown, nanocoatings can be easily adapted for several different uses, and the creative combination of existing nanomaterials and coating methods can synergize to unlock this potential.”

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

Antimicrobial spray nanocoating of supramolecular Fe(III)-tannic acid metal-organic coordination complex: applications to shoe insoles and fruits by Ji Park, Sohee Choi, Hee Moon, Hyelin Seo, Ji Kim, Seok-Pyo Hong, Bong Lee, Eunhye Kang, Jinho Lee, Dong Ryu, & Insung S. Choi. Scientific Reports 7, Article number: 6980 (2017) doi:10.1038/s41598-017-07257-x Published online: 01 August 2017

This paper is open access.

*’life’ added to correct headline on Sept. 4, 2017.

Material that sheds like a snake when it’s damaged

Truly water-repellent materials are on the horizon. Or, they would be if one tiny problem was solved. According to a May  3, 2017 news item on ScienceDaily, scientists may have come up with that solution,

Imagine a raincoat that heals a scratch by shedding the part of the outer layer that’s damaged. To create such a material, scientists have turned to nature for inspiration. They report in ACS’ journal Langmuir a water-repellant material that molts like a snake’s skin when damaged to reveal another hydrophobic [water-repellent] layer beneath it.

A May 3, 2017 American Chemical Society (ACS) press release (also on EurekAlert), which originated the news item, expands on the theme,

Lotus leaves, water striders and other superhydrophobic examples from nature have inspired scientists to copy their water-repelling architecture to develop new materials. Such materials are often made by coating a substrate with nanostructures, which can be shored up by adding microstructures to the mix. Superhydrophobic surfaces could be useful in a range of applications including rain gear, medical instruments and self-cleaning car windows. But most of the prototypes so far haven’t been strong enough to stand up to damage by sharp objects. To address this shortcoming, Jürgen Rühe and colleagues again found a potential solution in nature — in snake and lizard skins.

The researchers stacked three layers to create their material: a water-repellant film made with poly-1H,1H,2H,2H-perfluorodecyl acrylate (PFA) “nanograss” on the top, a water-soluble polymer in the middle and a superhydrophobic silicon nanograss film on the bottom. Nanograss consists of tiny needle-like projections sticking straight up. The team scratched the coating and submerged the material in water, which then seeped into the cut and dissolved the polymer. The top layer then peeled off like molted skin and floated away, exposing the bottom, water-repellant film. Although further work is needed to strengthen the top coating so that a scratch won’t be able to penetrate all three layers, the researchers say it offers a new approach to creating self-cleaning and water-repellant materials.

The authors acknowledge support from the German Federal Ministry of Education and Research (BMBF) and VDI/VDE/IT GmbH through project NanoTau.

Here’s a video demonstrating the concept,

Published on May 2, 2017

Scientists turn to snakes and lizards for inspiration to create a new material that sheds its outer layer when scratched.

Finally, a link to and a citation for the paper,

Molting Materials: Restoring Superhydrophobicity after Severe Damage via Snakeskin-like Shedding by Roland Hönes, Vitaliy Kondrashov, and Jürgen Rühe. Langmuir, Article ASAP DOI: 10.1021/acs.langmuir.7b00814 Publication Date (Web): April 14, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

Adding melanin to make foams and fabrics stronger

Melanin does not have a reputation as a strengthening agent so why these scientists tested it for that purpose is a mystery. From a Nov. 9, 2016 news item on phys.org,

Melanin is the natural molecule in animals’ skin, hair and the iris of eyes that gives them color and helps protect them from ultraviolet light. Someday soon, the pigment could be found in unexpected places such as sofa cushions or clothing—but not for its hue. Scientists have found that adding a small amount of melanin to polyurethane makes it far stronger than the material by itself. …

A Nov. 9, 2016 American Chemical Society (ACS) press release (also on EurekAlert), which originated the news item, expands on the theme,

From durable foam seating and insulation to glossy coatings and stretchy textiles, polyurethane is used in a huge range of products. Although already fairly versatile, polyurethane still has room for improvement. To make it more durable, scientists have tried adding fillers, including silica, carbon nanotubes and graphene oxide. But these efforts have often led to the enhancement of only one physical property at a time, such as tensile strength — how hard a material can be pulled before it snaps — but not toughness — how much energy it can absorb without breaking. Mingqing Chen, Weifu Dong and colleagues wanted to try a new approach: adding melanin, a biomolecule increasingly used in various other materials.

The researchers found that polyurethane containing just 2 percent melanin, extracted from the ink sacs of cuttlefish, had improved tensile strength and toughness. These properties were enhanced about 10 fold, increasing from 5.6 megapascals and 33 megajoules per cubic meter in plain polyurethane to 51.5 MPa and 413 MJ/m3, respectively. Polyurethane by itself could stretch 770 percent before breaking, whereas the melanin-infused version stretched 1,880 percent before rupturing.

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

Superior Performance of Polyurethane Based on Natural Melanin Nanoparticles by Yang Wang, Ting Li, Xuefei Wang, Piming Ma, Huiyu Bai, Weifu Dong, Yi Xie, and Mingqing Chen. Biomacromolecules, DOI: 10.1021/acs.biomac.6b01298 Publication Date (Web): October 17, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Nanofiber coating for artificial joints and implants

The researchers have a great image to accompany their research, which fit well with Hallowe’en and the Day of the Dead celebrations taking place around the same time as the research was published.

 A titanium implant (blue) without a nanofiber coating in the femur of a mouse. Bacteria are shown in red and responding immune cells in yellow. Credit: Lloyd Miller/Johns Hopkins Medicine

A titanium implant (blue) without a nanofiber coating in the femur of a mouse. Bacteria are shown in red and responding immune cells in yellow.
Credit: Lloyd Miller/Johns Hopkins Medicine

An Oct. 24, 2016 news item on ScienceDaily announces the research on nanofibers,

In a proof-of-concept study with mice, scientists at The Johns Hopkins University show that a novel coating they made with antibiotic-releasing nanofibers has the potential to better prevent at least some serious bacterial infections related to total joint replacement surgery.

An Oct. 24, 2016 Johns Hopkins Medicine news release (also on EurekAlert), provides further details (Note: Links have been removed),

A report on the study, published online the week of Oct. 24 [2016] in Proceedings of the National Academy of Sciences, was conducted on the rodents’ knee joints, but, the researchers say, the technology would have “broad applicability” in the use of orthopaedic prostheses, such as hip and knee total joint replacements, as well pacemakers, stents and other implantable medical devices. In contrast to other coatings in development, the researchers report the new material can release multiple antibiotics in a strategically timed way for an optimal effect.

“We can potentially coat any metallic implant that we put into patients, from prosthetic joints, rods, screws and plates to pacemakers, implantable defibrillators and dental hardware,” says co-senior study author Lloyd S. Miller, M.D., Ph.D., an associate professor of dermatology and orthopaedic surgery at the Johns Hopkins University School of Medicine.

Surgeons and biomedical engineers have for years looked for better ways —including antibiotic coatings — to reduce the risk of infections that are a known complication of implanting artificial hip, knee and shoulder joints.

Every year in the U.S., an estimated 1 to 2 percent of the more than 1 million hip and knee replacement surgeries are followed by infections linked to the formation of biofilms — layers of bacteria that adhere to a surface, forming a dense, impenetrable matrix of proteins, sugars and DNA. Immediately after surgery, an acute infection causes swelling and redness that can often be treated with intravenous antibiotics. But in some people, low-grade chronic infections can last for months, causing bone loss that leads to implant loosening and ultimately failure of the new prosthesis. These infections are very difficult to treat and, in many cases of chronic infection, prostheses must be removed and patients placed on long courses of antibiotics before a new prosthesis can be implanted. The cost per patient often exceeds $100,000 to treat a biofilm-associated prosthesis infection, Miller says.

Major downsides to existing options for local antibiotic delivery, such as antibiotic-loaded cement, beads, spacers or powder, during the implantation of medical devices are that they can typically only deliver one antibiotic at a time and the release rate is not well-controlled. To develop a better approach that addresses those problems, Miller teamed up with Hai-Quan Mao, Ph.D., a professor of materials science and engineering at the Johns Hopkins University Whiting School of Engineering, and a member of the Institute for NanoBioTechnology, Whitaker Biomedical Engineering Institute and Translational Tissue Engineering Center.

Over three years, the team focused on designing a thin, biodegradable plastic coating that could release multiple antibiotics at desired rates. This coating is composed of a nanofiber mesh embedded in a thin film; both components are made of polymers used for degradable sutures.

To test the technology’s ability to prevent infection, the researchers loaded the nanofiber coating with the antibiotic rifampin in combination with one of three other antibiotics: vancomycin, daptomycin or linezolid. “Rifampin has excellent anti-biofilm activity but cannot be used alone because bacteria would rapidly develop resistance,” says Miller. The coatings released vancomycin, daptomycin or linezolid for seven to 14 days and rifampin over three to five days. “We were able to deploy two antibiotics against potential infection while ensuring rifampin was never present as a single agent,” Miller says.

The team then used each combination to coat titanium Kirschner wires — a type of pin used in orthopaedic surgery to fix bone in place after wrist fractures — inserted them into the knee joints of anesthetized mice and introduced a strain of Staphylococcus aureus, a bacterium that commonly causes biofilm-associated infections in orthopaedic surgeries. The bacteria were engineered to give off light, allowing the researchers to noninvasively track infection over time.

Miller says that after 14 days of infection in mice that received an antibiotic-free coating on the pins, all of the mice had abundant bacteria in the infected tissue around the knee joint, and 80 percent had bacteria on the surface of the implant. In contrast, after the same time period in mice that received pins with either linezolid-rifampin or daptomycin-rifampin coating, none of the mice had detectable bacteria either on the implants or in the surrounding tissue.

“We were able to completely eradicate infection with this coating,” says Miller. “Most other approaches only decrease the number of bacteria but don’t generally or reliably prevent infections.”

After the two-week test, each of the rodents’ joints and adjacent bones were removed for further study. Miller and Mao found that not only had infection been prevented, but the bone loss often seen near infected joints — which creates the prosthetic loosening in patients — had also been completely avoided in animals that received pins with the antibiotic-loaded coating.

Miller emphasized that further research is needed to test the efficacy and safety of the coating in humans, and in sorting out which patients would best benefit from the coating — people with a previous prosthesis joint infection receiving a new replacement joint, for example.

The polymers they used to generate the nanofiber coating have already been used in many approved devices by the U.S. Food and Drug Administration, such as degradable sutures, bone plates and drug delivery systems.

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

Polymeric nanofiber coating with tunable combinatorial antibiotic delivery prevents biofilm-associated infection in vivo by Alyssa G. Ashbaugh, Xuesong Jiang, Jesse Zheng, Andrew S. Tsai, Woo-Shin Kim, John M. Thompson, Robert J. Miller, Jonathan H. Shahbazian, Yu Wang, Carly A. Dillen, Alvaro A. Ordonez, Yong S. Chang, Sanjay K. Jain, Lynne C. Jones, Robert S. Sterling, Hai-Quan Mao, and Lloyd S. Miller. PNAS [Proceedings of the National Academy of Sciences] 2016 doi: 10.1073/pnas.1613722113 Published ahead of print October 24, 2016

This paper is behind a paywall.

Ocean-inspired coatings for organic electronics

An Oct. 19, 2016 news item on phys.org describes the advantages a new coating offers and the specific source of inspiration,

In a development beneficial for both industry and environment, UC Santa Barbara [University of California at Santa Barbara] researchers have created a high-quality coating for organic electronics that promises to decrease processing time as well as energy requirements.

“It’s faster, and it’s nontoxic,” said Kollbe Ahn, a research faculty member at UCSB’s Marine Science Institute and corresponding author of a paper published in Nano Letters.

In the manufacture of polymer (also known as “organic”) electronics—the technology behind flexible displays and solar cells—the material used to direct and move current is of supreme importance. Since defects reduce efficiency and functionality, special attention must be paid to quality, even down to the molecular level.

Often that can mean long processing times, or relatively inefficient processes. It can also mean the use of toxic substances. Alternatively, manufacturers can choose to speed up the process, which could cost energy or quality.

Fortunately, as it turns out, efficiency, performance and sustainability don’t always have to be traded against each other in the manufacture of these electronics. Looking no further than the campus beach, the UCSB researchers have found inspiration in the mollusks that live there. Mussels, which have perfected the art of clinging to virtually any surface in the intertidal zone, serve as the model for a molecularly smooth, self-assembled monolayer for high-mobility polymer field-effect transistors—in essence, a surface coating that can be used in the manufacture and processing of the conductive polymer that maintains its efficiency.

An Oct. 18, 2016 UCSB news release by Sonia Fernandez, which originated the news item, provides greater technical detail,

More specifically, according to Ahn, it was the mussel’s adhesion mechanism that stirred the researchers’ interest. “We’re inspired by the proteins at the interface between the plaque and substrate,” he said.

Before mussels attach themselves to the surfaces of rocks, pilings or other structures found in the inhospitable intertidal zone, they secrete proteins through the ventral grove of their feet, in an incremental fashion. In a step that enhances bonding performance, a thin priming layer of protein molecules is first generated as a bridge between the substrate and other adhesive proteins in the plaques that tip the byssus threads of their feet to overcome the barrier of water and other impurities.

That type of zwitterionic molecule — with both positive and negative charges — inspired by the mussel’s native proteins (polyampholytes), can self-assemble and form a sub-nano thin layer in water at ambient temperature in a few seconds. The defect-free monolayer provides a platform for conductive polymers in the appropriate direction on various dielectric surfaces.

Current methods to treat silicon surfaces (the most common dielectric surface), for the production of organic field-effect transistors, requires a batch processing method that is relatively impractical, said Ahn. Although heat can hasten this step, it involves the use of energy and increases the risk of defects.

With this bio-inspired coating mechanism, a continuous roll-to-roll dip coating method of producing organic electronic devices is possible, according to the researchers. It also avoids the use of toxic chemicals and their disposal, by replacing them with water.

“The environmental significance of this work is that these new bio-inspired primers allow for nanofabrication on silicone dioxide surfaces in the absence of organic solvents, high reaction temperatures and toxic reagents,” said co-author Roscoe Lindstadt, a graduate student researcher in UCSB chemistry professor Bruce Lipshutz’s lab. “In order for practitioners to switch to newer, more environmentally benign protocols, they need to be competitive with existing ones, and thankfully device performance is improved by using this ‘greener’ method.”

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

Molecularly Smooth Self-Assembled Monolayer for High-Mobility Organic Field-Effect Transistors by Saurabh Das, Byoung Hoon Lee, Roscoe T. H. Linstadt, Keila Cunha, Youli Li, Yair Kaufman, Zachary A. Levine, Bruce H. Lipshutz, Roberto D. Lins, Joan-Emma Shea, Alan J. Heeger, and B. Kollbe Ahn. Nano Lett., 2016, 16 (10), pp 6709–6715
DOI: 10.1021/acs.nanolett.6b03860 Publication Date (Web): September 27, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall but the scientists have made an illustration available,

An artist's concept of a zwitterionic molecule of the type secreted by mussels to prime surfaces for adhesion Photo Credit: Peter Allen

An artist’s concept of a zwitterionic molecule of the type secreted by mussels to prime surfaces for adhesion Photo Credit: Peter Allen

Achieving ultra-low friction without oil

Oiled gears as small parts of large mechanism Courtesy: Georgia Institute of Technology

Oiled gears as small parts of large mechanism Courtesy: Georgia Institute of Technology

Those gears are gorgeous, especially in full size; I will be giving a link to a full size version in a bit. Meanwhile, an Oct. 11, 2016 news item on Nanowerk makes an announcement about ultra-low friction without oil,

Researchers at Georgia Institute of Technology [Georgia Tech; US] have developed a new process for treating metal surfaces that has the potential to improve efficiency in piston engines and a range of other equipment.

The method improves the ability of metal surfaces to bond with oil, significantly reducing friction without special oil additives.

“About 50 percent of the mechanical energy losses in an internal combustion engine result from piston assembly friction. So if we can reduce the friction, we can save energy and reduce fuel and oil consumption,” said Michael Varenberg, an assistant professor in Georgia Tech’s George W. Woodruff School of Mechanical Engineering.

An Oct. 5, 2016 Georgia Tech news release (also on EurekAlert but dated Oct. 11, 2016), which originated the news item, describes the research in more detail,

In the study, which was published Oct. 5 [2016] in the journal Tribology Letters, the researchers at Georgia Tech and Technion – Israel Institute of Technology tested treating the surface of cast iron blocks by blasting it with mixture of copper sulfide and aluminum oxide. The shot peening modified the surface chemically that changed how oil molecules bonded with the metal and led to a superior surface lubricity.

“We want oil molecules to be connected strongly to the surface. Traditionally this connection is created by putting additives in the oil,” Varenberg said. “In this specific case, we shot peen the surface with a blend of alumina and copper sulfide particles.  Making the surface more active chemically by deforming it allows for replacement reaction to form iron sulfide on top of the iron. And iron sulfides are known for very strong bonds with oil molecules.”

Oil is the primary tool used to reduce the friction that occurs when two surfaces slide in contact. The new surface treatment results in an ultra-low friction coefficient of about 0.01 in a base oil environment, which is about 10 times less than a friction coefficient obtained on a reference untreated surface, the researchers reported.

“The reported result surpasses the performance of the best current commercial oils and is similar to the performance of lubricants formulated with tungsten disulfide-based nanoparticles, but critically, our process does not use any expensive nanostructured media,” Varenberg said.

The method for reducing surface friction is flexible and similar results can be achieved using a variety of processes other than shot peening, such as lapping, honing, burnishing, laser shock peening, the researchers suggest. That would make the process even easier to adapt to a range of uses and industries. The researchers plan to continue to examine that fundamental functional principles and physicochemical mechanisms that caused the treatment to be so successful.

“This straightforward, scalable pathway to ultra-low friction opens new horizons for surface engineering, and it could significantly reduce energy losses on an industrial scale,” Varenberg said. “Moreover, our finding may result in a paradigm shift in the art of lubrication and initiate a whole new direction in surface science and engineering due to the generality of the idea and a broad range of potential applications.”

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

Mechano-Chemical Surface Modification with Cu2S: Inducing Superior Lubricity by Michael Varenberg, Grigory Ryk, Alexander Yakhnis, Yuri Kligerman, Neha Kondekar, & Matthew T. McDowell. Tribol Lett (2016) 64: 28. doi:10.1007/s11249-016-0758-8 First online: Oct. 5, 2016

This paper is behind a paywall.

Nanotechnology-enhanced roads in South Africa and in Kerala, India

It’s all about road infrastructure in these two news bits.

Road building and maintenance in sub-Saharan Africa

A July 7, 2016 news item on mybroadband.co.za describes hopes that nanotechnology-enabled products will make roads easier to build and maintain,

The solution for affordable road infrastructure development could lie in the use of nanotechnology, according to a paper presented at the 35th annual Southern African Transport Conference in Pretoria.

The cost of upgrading, maintaining and rehabilitating road infrastructure with limited funds makes it impossible for sub-Saharan Africa to become competitive in the world market, according to Professor Gerrit Jordaan of the University of Pretoria, a speaker at the conference.

The affordability of road infrastructure depends on the materials used, the environment in which the road will be built and the traffic that will be using the road, explained Professor James Maina of the department of civil engineering at the University of Pretoria.

Hauling materials to a construction site contributes hugely to costs, which planners try to minimise by getting materials closer to the site. But if there aren’t good quality materials near the site, another option is to modify poor quality materials for construction purposes. This is where nanotechnology comes in, he explained.

For example, if the material is clay soil, it has a high affinity to water so when it absorbs water it expands, and when it dries out it contracts. Nanotechnology can make the soil water repellent. “Essentially, nanotechnology changes the properties to work for the construction process,” he said.

These nanotechnology-based products have been used successfully in many parts of the world, including India, the USA and in the West African region.

There have also been concerns about road building and maintenance in Kerala, India.

Nanotechnology for city roads in Kochi

A March 23, 2015 news item in the Times of India describes an upcoming test of a nanotechnology-enabled all weather road,

Citizens can now look forward to better roads with the local self-government department planning to use nanotechnology to construct all-weather roads.

For the district trial run, the department has selected a 300-metre stretch of a panchayat road in Edakkattuvayal panchayat. The trial would experiment with nanotechnology to build moisture resistant, long-lasting and maintenance-free roads.

“Like the public, the department is also fed up with the poor condition of roads in the state. Crores of rupees are spent every year for repairing and resurfacing the roads. This is because of heavy rains in the state that weakens the soil base of roads, resulting in potholes that affect the ride-quality of the road surface,” said KT Sajan, assistant executive engineer, LSGD, who is supervising the work.

The nanotechnology has been developed by Zydex Technologies, a Gujarat-headquartered firm. The company’s technology has already been used by major private contract firms that build national highways in India and in other major projects in European and African countries.

Oddly, you can’t find out more about the Zydex products mentioned in the article on its Roads Solution webpage , where you are provided a general description of the technology,

Revolutionary nanotechnology for building moisture resistant, long lasting & maintenance free roads through innovative adaptation of Organosilane chemistry.

Zydex Nanotechnology: A Game Changer

Zydex Nanotechnology has a value propositions for all layers of the road

SOIL LAYERS
Zydex Nanotechnology makes the soil moisture resistant, reduces expansiveness and stabilizes the soil to improve its bearing strength manifold. If used with 1% cement, it can stabilize almost any type of soil, by improving the California Bearing Ratio (CBR) to even 100 or above.

Here is the real change in game, as stronger soil bases would now allow optimization of road section thicknesses, potentially saving 10-15% road construction cost.

BOND COATS
Prime & Tack coats become 100 % waterproofed, due to penetration and chemical bonding. This also ensures uniform load transfer. And all this at lower residual bitumen.

ASPHALTIC LAYERS
Chemical bonding between aggregates and asphalt eliminates moisture induced damage of asphaltic layers.

Final comment

I hadn’t meant to wait so long to publish the bit about Kerala’s road but serendipity has allowed me to link it to a piece about South Africa ‘s roads and to note a resemblance to the problems encountered in both regions.