Tag Archives: Nicola Pugno

Making spider silk stronger by feeding graphene and carbon nanotubes to spiders

Spider silk is already considered a strong and tough material but now scientists have found a way to enhance those properties. From an August 15, 2017 Institute of Physics Publishing press release (also on EurekAlert),

…  researchers in Italy and the UK have found a way to make Spidey’s silk a lot stronger, using various different spider species and carbon nanotubes or graphene.

The research team, led by Professor Nicola Pugno at the University of Trento, Italy, succeeded in having their spiders produce silk with up to three times the strength and ten times the toughness of the regular material.

Their discovery, published today in the journal 2D Materials, could pave the way for a new class of bionicomposites, with a wide variety of uses.

Professor Pugno said: “Humans have used silkworm silks widely for thousands of years, but recently research has focussed on spider silk, as it has extremely promising mechanical properties. It is among the best spun polymer fibres in terms of tensile strength, ultimate strain, and especially toughness, even when compared to synthetic fibres such as Kevlar.

“We already know that there are biominerals present in in the protein matrices and hard tissues of insects, which gives them high strength and hardness in their jaws, mandibles and teeth, for example. So our study looked at whether spider silk’s properties could be ‘enhanced’ by artificially incorporating various different nanomaterials into the silk’s biological protein structures.”

To do this, the team exposed three different spider species to water dispersions containing carbon nanotubes or graphene.

After collecting the spiders’ silk, the team tested its tensile strength and toughness.

Professor Pugno said: “We found that the strongest silk the spiders spun had a fracture strength up to 5.4 gigapascals (GPa), and a toughness modulus up to 1,570 joules per gram (J/g). Normal spider silk, by comparison, has a fracture strength of around 1.5 GPa and a toughness modulus of around 150 J/g.

“This is the highest fibre toughness discovered to date, and a strength comparable to that of the strongest carbon fibres or limpet teeth. These are still early days, but our results are a proof of concept that paves the way to exploiting the naturally efficient spider spinning process to produce reinforced bionic silk fibres, thus further improving one of the most promising strong materials.

“These silks’ high toughness and resistance to ultimate strain could have applications such as parachutes.”

“Furthermore, this process of the natural integration of reinforcements in biological structural materials could also be applied to other animals and plants, leading to a new class of “bionicomposites” for innovative applications.”

Remember this? “You are what you eat.” If you’ve ever had doubts about that saying, these spiders should be laying them to rest.

Sadly, this news release doesn’t explain much about the decision to feed the spiders graphene or carbon nanotubes, which are identical other than in their respective shapes (sheet vs tube)  and whether those shapes did or did not affect the strength of the silk.

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

Spider silk reinforced by graphene or carbon nanotubes by Emiliano Lepore, Federico Bosia, Francesco Bonaccorso, Matteo Bruna, Simone Taioli, Giovanni Garberoglio, Andrea C Ferrari, and Nicola Maria Pugno. 2D Materials, Volume 4, Number 3 DOI: https://doi.org/10.1088/2053-1583/aa7cd3 Published 14 August 2017

© 2017 IOP Publishing Ltd

This paper is behind a paywall.

Pugno was most recently mentioned here in a May 29, 2015 posting where he was listed as an author for a paper on synthesizing spider silk. Prior to 2015 I was familiar with Pugno’s name due to his work on adhesiveness in geckos.

A 2nd European roadmap for graphene

About 2.5 years ago there was an article titled, “A roadmap for graphene” (behind a paywall) which Nature magazine published online in Oct. 2012. I see at least two of the 2012 authors, Konstantin (Kostya) Novoselov and Vladimir Fal’ko,, are party to this second, more comprehensive roadmap featured in a Feb. 24, 2015 news item on Nanowerk,

In October 2013, academia and industry came together to form the Graphene Flagship. Now with 142 partners in 23 countries, and a growing number of associate members, the Graphene Flagship was established following a call from the European Commission to address big science and technology challenges of the day through long-term, multidisciplinary R&D efforts.

A Feb.  24, 2015 University of Cambridge news release, which originated the news item, describes the roadmap in more detail,

In an open-access paper published in the Royal Society of Chemistry journal Nanoscale, more than 60 academics and industrialists lay out a science and technology roadmap for graphene, related two-dimensional crystals, other 2D materials, and hybrid systems based on a combination of different 2D crystals and other nanomaterials. The roadmap covers the next ten years and beyond, and its objective is to guide the research community and industry toward the development of products based on graphene and related materials.

The roadmap highlights three broad areas of activity. The first task is to identify new layered materials, assess their potential, and develop reliable, reproducible and safe means of producing them on an industrial scale. Identification of new device concepts enabled by 2D materials is also called for, along with the development of component technologies. The ultimate goal is to integrate components and structures based on 2D materials into systems capable of providing new functionalities and application areas.

Eleven science and technology themes are identified in the roadmap. These are: fundamental science, health and environment, production, electronic devices, spintronics, photonics and optoelectronics, sensors, flexible electronics, energy conversion and storage, composite materials, and biomedical devices. The roadmap addresses each of these areas in turn, with timelines.

Research areas outlined in the roadmap correspond broadly with current flagship work packages, with the addition of a work package devoted to the growing area of biomedical applications, to be included in the next phase of the flagship. A recent independent assessment has confirmed that the Graphene Flagship is firmly on course, with hundreds of research papers, numerous patents and marketable products to its name.

Roadmap timelines predict that, before the end of the ten-year period of the flagship, products will be close to market in the areas of flexible electronics, composites, and energy, as well as advanced prototypes of silicon-integrated photonic devices, sensors, high-speed electronics, and biomedical devices.

“This publication concludes a four-year effort to collect and coordinate state-of-the-art science and technology of graphene and related materials,” says Andrea Ferrari, director of the Cambridge Graphene Centre, and chairman of the Executive Board of the Graphene Flagship. “We hope that this open-access roadmap will serve as the starting point for academia and industry in their efforts to take layered materials and composites from laboratory to market.” Ferrari led the roadmap effort with Italian Institute of Technology physicist Francesco Bonaccorso, who is a Royal Society Newton Fellow of the University of Cambridge, and a Fellow of Hughes Hall.

“We are very proud of the joint effort of the many authors who have produced this roadmap,” says Jari Kinaret, director of the Graphene Flagship. “The roadmap forms a solid foundation for the graphene community in Europe to plan its activities for the coming years. It is not a static document, but will evolve to reflect progress in the field, and new applications identified and pursued by industry.”

I have skimmed through the report briefly (wish I had more time) and have a couple of comments. First, there’s an excellent glossary of terms for anyone who might stumble over chemical abbreviations and/or more technical terminology. Second, they present a very interesting analysis of the intellectual property (patents) landscape (Note: Links have been removed. Incidental numbers are footnote references),

In the graphene area, there has been a particularly rapid increase in patent activity from around 2007.45 Much of this is driven by patent applications made by major corporations and universities in South Korea and USA.53 Additionally, a high level of graphene patent activity in China is also observed.54 These features have led some commentators to conclude that graphene innovations arising in Europe are being mainly exploited elsewhere.55 Nonetheless, an analysis of the Intellectual Property (IP) provides evidence that Europe already has a significant foothold in the graphene patent landscape and significant opportunities to secure future value. As the underlying graphene technology space develops, and the GRM [graphene and related materials] patent landscape matures, re-distribution of the patent landscape seems inevitable and Europe is well positioned to benefit from patent-based commercialisation of GRM research.

Overall, the graphene patent landscape is growing rapidly and already resembles that of sub-segments of the semiconductor and biotechnology industries,56 which experience high levels of patent activity. The patent strategies of the businesses active in such sub-sectors frequently include ‘portfolio maximization’56 and ‘portfolio optimization’56 strategies, and the sub-sectors experience the development of what commentators term ‘patent thickets’56, or multiple overlapping granted patent rights.56 A range of policies, regulatory and business strategies have been developed to limit such patent practices.57 In such circumstances, accurate patent landscaping may provide critical information to policy-makers, investors and individual industry participants, underpinning the development of sound policies, business strategies and research commercialisation plans.

It sounds like a patent thicket is developing (Note: Links have been removed. Incidental numbers are footnote references),,

Fig. 13 provides evidence of a relative increase in graphene patent filings in South Korea from 2007 to 2009 compared to 2004–2006. This could indicate increased commercial interest in graphene technology from around 2007. The period 2010 to 2012 shows a marked relative increase in graphene patent filings in China. It should be noted that a general increase in Chinese patent filings across many ST domains in this period is observed.76 Notwithstanding this general increase in Chinese patent activity, there does appear to be increased commercial interest in graphene in China. It is notable that the European Patent Office contribution as a percentage of all graphene patent filings globally falls from a 8% in the period 2007 to 2009 to 4% in the period 2010 to 2012.

The importance of the US, China and South Korea is emphasised by the top assignees, shown in Fig. 14. The corporation with most graphene patent applications is the Korean multinational Samsung, with over three times as many filings as its nearest rival. It has also patented an unrivalled range of graphene-technology applications, including synthesis procedures,77 transparent display devices,78 composite materials,79 transistors,80 batteries and solar cells.81 Samsung’s patent applications indicate a sustained and heavy investment in graphene R&D, as well as collaboration (co-assignment of patents) with a wide range of academic institutions.82,83

 

image file: c4nr01600a-f14.tif
Fig. 14 Top 10 graphene patent assignees by number and cumulative over all time as of end-July 2014. Number of patents are indicated in the red histograms referred to the left Y axis, while the cumulative percentage is the blue line, referred to the right Y axis.

It is also interesting to note that patent filings by universities and research institutions make up a significant proportion ([similar]50%) of total patent filings: the other half comprises contributions from small and medium-sized enterprises (SMEs) and multinationals.

Europe’s position is shown in Fig. 10, 12 and 14. While Europe makes a good showing in the geographical distribution of publications, it lags behind in patent applications, with only 7% of patent filings as compared to 30% in the US, 25% in China, and 13% in South Korea (Fig. 13) and only 9% of filings by academic institutions assigned in Europe (Fig. 15).

 

image file: c4nr01600a-f15.tif
Fig. 15 Geographical breakdown of academic patent holders as of July 2014.

While Europe is trailing other regions in terms of number of patent filings, it nevertheless has a significant foothold in the patent landscape. Currently, the top European patent holder is Finland’s Nokia, primarily around incorporation of graphene into electrical devices, including resonators and electrodes.72,84,85

This may sound like Europe is trailing behind but that’s not the case according to the roadmap (Note: Links have been removed. Incidental numbers are footnote references),

European Universities also show promise in the graphene patent landscape. We also find evidence of corporate-academic collaborations in Europe, including e.g. co-assignments filed with European research institutions and Germany’s AMO GmbH,86 and chemical giant BASF.87,88 Finally, Europe sees significant patent filings from a number of international corporate and university players including Samsung,77 Vorbeck Materials,89 Princeton University,90–92 and Rice University,93–95 perhaps reflecting the quality of the European ST base around graphene, and its importance as a market for graphene technologies.

There are a number of features in the graphene patent landscape which may lead to a risk of patent thickets96 or ‘multiple overlapping granted patents’ existing around aspects of graphene technology systems. [emphasis mine] There is a relatively high volume of patent activity around graphene, which is an early stage technology space, with applications in patent intensive industry sectors. Often patents claim carbon nano structures other than graphene in graphene patent landscapes, illustrating difficulties around defining ‘graphene’ and mapping the graphene patent landscape. Additionally, the graphene patent nomenclature is not entirely settled. Different patent examiners might grant patents over the same components which the different experts and industry players call by different names.

For anyone new to this blog, I am not a big fan of current patent regimes as they seem to be stifling rather encouraging innovation. Sadly, patents and copyright were originally developed to encourage creativity and innovation by allowing the creators to profit from their ideas. Over time a system designed to encourage innovation has devolved into one that does the opposite. (My Oct. 31, 2011 post titled Patents as weapons and obstacles, details my take on this matter.) I’m not arguing against patents and copyright but suggesting that the system be fixed or replaced with something that delivers on the original intention.

Getting back to the matter at hand, here’s a link to and a citation for the 200 pp. 2015 European Graphene roadmap,

Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems by Andrea C. Ferrari, Francesco Bonaccorso, Vladimir Fal’ko, Konstantin S. Novoselov, Stephan Roche, Peter Bøggild, Stefano Borini, Frank H. L. Koppens, Vincenzo Palermo, Nicola Pugno, José A. Garrido, Roman Sordan, Alberto Bianco, Laura Ballerini, Maurizio Prato, Elefterios Lidorikis, Jani Kivioja, Claudio Marinelli, Tapani Ryhänen, Alberto Morpurgo, Jonathan N. Coleman, Valeria Nicolosi, Luigi Colombo, Albert Fert, Mar Garcia-Hernandez, Adrian Bachtold, Grégory F. Schneider, Francisco Guinea, Cees Dekker, Matteo Barbone, Zhipei Sun, Costas Galiotis,  Alexander N. Grigorenko, Gerasimos Konstantatos, Andras Kis, Mikhail Katsnelson, Lieven Vandersypen, Annick Loiseau, Vittorio Morandi, Daniel Neumaier, Emanuele Treossi, Vittorio Pellegrini, Marco Polini, Alessandro Tredicucci, Gareth M. Williams, Byung Hee Hong, Jong-Hyun Ahn, Jong Min Kim, Herbert Zirath, Bart J. van Wees, Herre van der Zant, Luigi Occhipinti, Andrea Di Matteo, Ian A. Kinloch, Thomas Seyller, Etienne Quesnel, Xinliang Feng,  Ken Teo, Nalin Rupesinghe, Pertti Hakonen, Simon R. T. Neil, Quentin Tannock, Tomas Löfwander and Jari Kinaret. Nanoscale, 2015, Advance Article DOI: 10.1039/C4NR01600A First published online 22 Sep 2014

Here’s a diagram illustrating the roadmap process,

Fig. 122 The STRs [science and technology roadmaps] follow a hierarchical structure where the strategic level in a) is connected to the more detailed roadmap shown in b). These general roadmaps are the condensed form of the topical roadmaps presented in the previous sections, and give technological targets for key applications to become commercially competitive and the forecasts for when the targets are predicted to be met.  Courtesy: Researchers and  the Royal Society's journal, Nanoscale

Fig. 122 The STRs [science and technology roadmaps] follow a hierarchical structure where the strategic level in a) is connected to the more detailed roadmap shown in b). These general roadmaps are the condensed form of the topical roadmaps presented in the previous sections, and give technological targets for key applications to become commercially competitive and the forecasts for when the targets are predicted to be met.
Courtesy: Researchers and the Royal Society’s journal, Nanoscale

The image here is not the best quality; the one embedded in the relevant Nanowerk news item is better.

As for the earlier roadmap, here’s my Oct. 11, 2012 post on the topic.

Biomimicry book focusses on adhesive and non-adhesive properties

While I’m not familiar with Emiliano Lepore’s work, his co-author’s name, Nicola Pugno, rang a bell; he’s mentioned in my Feb. 3, 2012 posting about spiderwebs and strength and in my Nanotech Mysteries wiki entry, ‘Scientists read comics, watch tv, and more‘ about adhesive properties at the nanoscale. The two men have authored a book, ‘An Experimental Study on Adhesive or Anti-Adhesive, Bio-Inspired Experimental Nanomaterials‘ (print version) according to an April 2, 2014 news item on Nanowerk (Note: A link has been removed),

While recognising that bio-inspiration for technological development is already an established concept, “An Experimental Study on Adhesive or Anti-Adhesive, Bio-Inspired Experimental Nanomaterials” by Italian scientists Emiliano Lepore and Nicola Pugno, released in Open Access by De Gruyter Open, sets out to explore the potential of three categories of bio-inspired materials, namely, adhesives, anti-adhesives, and materials designed to offer exceptional characteristics – particularly in terms of their strength-to-weight ratio. In each of these areas, the technologies, which are currently at the forefront of scientific research, are described in relation to how they have been inspired by nature in an attempt to optimise their physical characteristics and performance in operation, with an aim to design and develop new innovative products.

Lepore and Pugno investigate a wide range of natural systems and employ original experimental procedures, the book additionally stands out for its rigorous and innovative approach to biomaterials. For example, the challenge of creating strong, reliable and affordable adhesives appears in numerous areas of engineering, such as the development of aircrafts, and all types of vehicles for transportation on land or water, where the need to save energy consumption by reducing weight is of paramount importance. There is also a specific interest in bonding dissimilar materials, which due to their physical properties prohibit the application of more conventional joining techniques. In this field, inspiration has been sought by investigating the adhesive abilities of insects, spiders, and reptiles.

The book published by De Gruyter is available in a free PDF format in addition to the print version which can be purchased through Amazon.

Gossamer silk that withstands hurricane force winds

I’ve written about spiderwebs before (mostly recently in my Dec. 9, 2011 posting titled, Music, math, and spiderwebs. Researcher, Markus J. Buehler, was featured in the Dec. 2011 posting and he is featured in this one too. I imagine he’s the ‘go to’ spiderweb researcher at MIT (Massachusetts Institute of Technology).

The most discussed characteristic of spiderwebs is their strength, a topic of endless fascination. The Feb. 1, 2012 news item on physorg.com offers a new take on this phenomenon,

While researchers have long known of the incredible strength of spider silk, the robust nature of the tiny filaments cannot alone explain how webs survive multiple tears and winds that exceed hurricane strength.

Now, a study that combines experimental observations of spider webs with complex computer simulations has shown that web durability depends not only on silk strength, but on how the overall web design compensates for damage and the response of individual strands to continuously varying stresses.

Reporting in the cover story of the Feb. 2, 2012, issue of Nature, researchers from the Massachusetts Institute of Technology (MIT) [team leader Markus Buehler, associate professor of civil and environmental engineering at MIT] and the Politecnico di Torino [team leader Nicola Pugno, Professor of Solid and Structural Mechanics at the Politecnico di Torino] in Italy show how spider web-design localizes strain and damage, preserving the web as a whole.

Very simply, two of the types of spider silk that give the webs their strength were examined separately and together. From the news item,

Viscid silk is stretchy, wet and sticky, and it is the silk that winds out in increasing spirals from the web center. Its primary function is to capture prey. Dragline silk is stiff and dry, and it serves as the threads that radiate out from a web’s center, providing structural support. Dragline silk is crucial to the mechanical behavior of the web.

If you’re a weaver, that description will like remind you of warp and weft. The warp threads provide the strength and remain immobile while the the weft threads are the ones you weave in and out and use to create patterns, etc. if you are so inclined.

These observations about viscid and dragline silk have practical applications (from the news item),

The concept of selective, localized failure for spider webs is interesting since it is a distinct departure from the structural principles that seem to be in play for many biological materials and components,” adds Dennis Carter, the NSF program director for biomechanics and mechanobiology who helped support the study. [emphasis mine]

“For example, the distributed material components in bone spread stress broadly, adding strength. There is no ‘wasted’ material, minimizing the weight of the structure. While all of the bone is being used to resist force, bone everywhere along the structure tends to be damaged prior to failure.”

In contrast, a spider’s web is organized to sacrifice local areas so that failure will not prevent the remaining web from functioning, even if in a diminished capacity, says Carter. “This is a clever strategy when the alternative is having to make an entire, new web!,” he adds. “As Buehler suggests, engineers can learn from nature and adapt the design strategies that are most appropriate for specific applications.”

According to David Kaplan’s Feb. 2, 2012 article for MIT News, the spiderweb’s localized failure was a considered a sign of weakness,

It turns out that a key property of spider silk that helps make webs robust is something previously considered a weakness: the way it can stretch and soften at first when pulled, and then stiffen again as the force of the pulling increases.

This stiffening response is crucial to the way spider silk resists damage. Buehler and his team analyzed how materials with different properties, arranged in the same web pattern, respond to localized stresses. They found that materials with other responses — those that either behave as a simple linear spring as they’re pulled, or start out stretchy and then become more “plastic” — perform much less effectively.

Spider webs, it turns out, can take quite a beating without failing. Damage tends to be localized, affecting just a few threads — the place where a bug got caught in the web and flailed around, for example. This localized damage can simply be repaired, rather than replaced, or even left alone if the web continues to function as before. “Even if it has a lot of defects, the web actually still functions mechanically virtually the same way,” Buehler says. “It’s a very flaw-tolerant system.”

Here’s an image that illustrates how spiderwebs react to stress,

Images show the successive deformation states as loading is increased on a spider web, with red marking high stresses. Simulation picture by S. Cranford & M.J. Buehler/MIT, photographic image by Francesco Tomasinelli & Emanuele Biggi.

The researchers’ article in Nature, Nonlinear material behaviour of spider silk yields robust webs by Steven W. Cranford, Anna Tarakanova, Nicola M. Pugno & Markus J. Buehler is available behind a paywall.

Note: I’m pretty sure I searched to find out if it should be spiderwebs or spider webs. I will investigate further but do not have time now. Meanwhile, I committed to spiderwebs in Dec. 2011.