Graphene: The good and the great

By Laura Syrett, Kasia Patel
Published: Friday, 18 March 2016

The nanocarbon is gradually beginning to appear in consumer products, but as Laura Syrett, Acting Editor and Kasia Patel, North American Editor, discover, there is a tension between getting graphene commercialised quickly into useful but ordinary items and the more time consuming business of realising the material’s game-changing potential.

Since its discovery in 2004, there has been a running joke that graphene can do anything, except get out of the lab. 

The 2D material, described in simple terms as a single layer of carbon atoms that can be derived from a number of precursors, including natural graphite, has been credited with a multitude of applications, with cancer cures and invisible aircraft being among the most eye-catching.

Palpable commercial achievements for graphene, which include security packaging for store goods and coatings for light bulbs, generally haven’t caught the public’s imagination in quite the same way.

Graphene’s development has been hampered by a nagging feeling that the world was led to expect too much from the nanocarbon "wonder material", meaning that many of its early fans, and investors, lost interest when transparent phones and superfast-charging batteries didn’t start rolling off production lines within a matter of months.

Yet graphene’s marketing power is still strong and some of the most successful attempts to keep the material in the public eye have been by major brands, dexterously turning its geekiness into glamour. 

Austrian sports equipment maker, Head, has successfully enlisted tennis stars like Andy Murray and Maria Sharapova to promote is range of graphene-enhanced tennis rackets and, in 2013, the Parisian beauty house, Yves Saint Laurent, launched a "graphene inspired" mascara, which was modelled by Cara Delevingne. The cosmetic’s formula, which consists of three polymers, soft waxes and a pigment distribution agent, doesn’t actually contain graphene but "mimics its structure and properties".

Although many "serious" graphene developers deplore such promotional stunts on the grounds that they detract from graphene’s true importance and potential, others argue that the wall of secrecy screening graphene intellectual property (IP) from the public eye doesn’t do the science much good either.

"The main problem facing the graphene market is the lack of clear knowledge and understanding about the material, processes and specific propositions of graphene producers," Giulio Cesareo, CEO of Directa Plus, an Italian company specialising in graphene-enhanced materials such as textiles and rubber, told IM.

Established in 2005, Directa Plus makes graphene from natural graphite using a patented process, which begins with plasma super expansion, heating the raw material to "the temperature of the surface of the sun" (5,505°C) to produce carbon flakes, in what is known as a "top-down" approach to producing graphene. This is the opposite of "bottom-up" methods, which make small precursor particles grow in size, as in the chemical vapour deposition (CVD) technique – the way most graphene is made. According to Cesareo, the Directa Plus method is low-cost but retains a high quality graphene. 

The company wants to change the perception that graphene will never live up to expectations by getting its material swiftly into existing products and brands. It opened its graphene factory in Lomazzo, near Milan, in 2014, where it currently produces 30 tpa graphene and has signed collaboration agreements with Swiss performance tyre manufacturer, Vittoria Industries Ltd and Italian sportswear brand, Colmar, to develop and sell products containing Directa Plus’ Graphene Plus (G+) material. 

Aside from sports materials, Directa Plus is also targeting electronics, composites and environmental applications and has signed more than 300 non-disclosure agreements in the last three years, with more products containing G+ expected to be launched in 2016.

Cesareo insists that using its graphene offers genuine improvements to materials, rather than just a marketing story. Vittoria’s G+ range includes the Corsa Speed bicycle tyre, which, Directa Plus claims, is the fastest tyre of its kind to be independently tested and sits at the premium end of the market. "Yet is still affordable, which is incredible when you look at the potential advantages it gives the cyclist," Cesareo said.

International model Cara Delevingne was
used to launch Yves Saint Laurent’s "graphene inspired" mascara.  (crizeel ong, via Flickr)

Need for speed

Ray Gibbs, CEO of UK-based Haydale Graphene Industries Plc, thinks that the sportswear and equipment market is a good route for graphene to gain commercial traction, because it isn’t as highly regulated as some of the other markets graphene is targeting, such as electronics and healthcare.

Longer term, however, Gibbs believes that graphene developers need to set their sights on bigger prizes and actively pursue commercial goals, rather than waiting to receive funding from government-backed programmes.

"Industry has got to pick up the baton and get on with it," Gibbs told IM. Haydale’s strategy, which is based on producing graphene from a graphitic source, rather than CVD, rests on being able to control its whole supply chain and using this as a springboard to get its products to market as quickly as possible.

In March this year, the company announced a collaboration with Switzerland-based Hunstman Advanced Materials GmbH, part of US-headquartered Huntsman Corp., to develop graphene-enhanced epoxy resins for Huntman’s range of ARALDITE adhesives for use in carbon fibre composites.

Prior to signing the cooperation agreement, Haydale self-funded a number of trials on incorporating its graphene nanoplatelets into epoxy resins. "We paid for these ourselves because, if we had just sat and waited, the market would probably have moved on, but also because we wanted to hold onto the IP," Gibbs explained.

Alongside epoxy resins, Haydale is working on adding graphene to carbon nanotubes (CNTs) and inks for screen printing – applications for which Asia is the world’s fastest growing market.

The Asian graphene scene, while representing a large potential customer base for graphene products, is becoming something of a sensitive topic for "Western" companies looking to cash in on the material as paranoia about industrial espionage takes hold.

In mid-March, the UK’s Sunday Times claimed that academics were "boycotting" the UK’s £61m ($86.4m*) National Graphene Institute (NGI), after one of the research centre’s partners, Taiwan-based BGT Materials, subsequently agreed to work with a Chinse manufacturer and university on graphene technology.

According to the article, academics at the NGI have voiced concerns about the protection of IP and the British government is reported to be considering opening an enquiry into the issue.

A spokesperson for the NGI, which is attached to the University of Manchester, told the paper that it had investigated the allegations and found no evidence that BGT Materials "had access, outside of any confidentiality undertaking, to confidential research programmes or that there were insufficient safeguards to protect the university’s intellectual property." It also refuted the allegation that the NGI was being boycotted by researchers.

Gibbs told IM that he felt the article had dealt with the issue unfairly, but conceded that Asian competition over graphene IP is always a background concern for companies like Haydale.

"There is risk but also opportunity in working with Asia," he said. "If you want to be in step with Asian companies, you need to set yourself up to move quickly. That’s not something the UK has traditionally been well placed to do."

For its part, Haydale is working with tier one suppliers to major Asian electronics like Samsung and LG. "These are our route to market," Gibbs explained.

Italian graphene company Directa Plus has successfully enhanced tyres made
by Vittoria Industries for racing bikes. (Directa Plus)

Top down

For producers of natural graphite, one of the contenders to be the raw material of choice for the graphene industry, the graphene tide rose and ebbed back in the early 2010s, leaving many washed up after it became apparent that demand for the nanocarbon would not emerge soon enough or require enough graphite to support entire mining operations.

There is, however, plenty of credible research to suggest that exfoliation of natural graphite is a viable way of producing graphene of higher quality and at a lower cost compared to forms of the nanocarbon produced via other methods. Most graphite companies are therefore keeping one eye on the technology as a potential future market.

One such business is Canada-listed Flinders Resources Ltd, which owns the mothballed Woxna graphite mine in Sweden. In September last year, Flinders announced that its Swedish subsidiary, Woxna Graphite AB, had been chosen as an industry partner by Swedish Graphene, a government-funded programme to research and commercialise graphene produced from Sweden-sourced graphite. 

Flinders’ CEO, Blair Way, is realistic about the share graphene could take of the natural graphite market. "I don’t know if the commercialisation of graphene is really going to have a huge impact on graphite," he told IM

To put this in context, Mikael Ranggard, chairman of Woxna Graphite, pointed out that: "If we were to make a new graphene-based display for every mobile in the world, we would need less than 100kg of graphene".

But small can still be valuable. There a few meaningful estimates available for the price of graphene derived from natural graphite, but according to Spanish nanomaterials graphene company, Graphenea, the retail price of its CVD-produced graphene oxide today is around €24.85/g ($27.58/g), or $27,580/tonne. This is compares to current prices of around $1,100/tonne for large flake natural graphite.

Even though the price of graphene is going down (Graphenea’s material is 99.9% cheaper than it was in 2010), if companies like Flinders can secure even a modest outlet for Woxna graphite into the graphene industry, then this could be an added lucrative bonus to business models primarily geared to supply larger volume markets.

With the backing of Swedish Graphene, Flinders and its partner, 2D Fab AB, will seek support from Swedish industry to evaluate graphene’s potential for use in printing, energy and surface treatment applications.

Way told IM that buildings coated with graphene for capturing energy could be "a huge thing", but that this kind of technology would need to be complemented by electricity storage devices for it to become a viable proposition. 

"The concept pf all this technology converging will be a point where you can capture the energy, but it’s a while away," he said.

One of the other graphene projects Flinders is looking into is nanocarbon paints for paper. "If you coat the paper with graphene, then it has electrical conductivity and you can track where it is, so the paper mills can value add to what they’re selling," Ranggard told IM. "But realistically, this technology is probably still five years away, maybe even 10 – it’s frightening how long it takes technology to get into the mainstream," Way added.

Out of the lab rat race

One of the chief complaints frequently sounded by many in the graphene industry is that the sector has become too crowded and that the quality of research and products is wildly inconstant.

"Because of the high volume and variety of graphene products on the market, there is little in the way of regulations and standards in Europe. In Asia, it has been hard to get a clear idea of what is actually going on," Directa Plus’ Cesareo told IM

Cesareo believes that if an independent body was established to regulate graphene production, it would help boost the market and also help coordinate efforts to establish health and safety legislation relating to graphene – issues which have to be ironed out before the material can be used in certain applications.

Along with Haydale’s Gibbs, Cesareo holds the view that while state-backed research initiatives such as the European Graphene Flagship programme, are welcome sources of support for graphene developers, they are unlikely to deliver immediate commercial returns.

"Real innovation requires an unexpected combination of knowledge, market awareness and technology," Cesareo said.  

"As we’ve demonstrated, graphene is already ’out of the lab. It is undeniable that applications for graphene which currently seem futuristic will eventually reach the market, but ultimately, the graphene industry is still young." 

"It is essential that the companies pioneering graphene research now have the support they need to facilitate the research which has been the backbone of the industry and will be crucial to its future," he added.

*Conversions made March 2016