EDITOR: | March 6th, 2016 | 13 Comments

Understanding Graphene – Part 2

| March 06, 2016 | 13 Comments
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Graphene can be made by separating the stacked layers in graphite or by self-assembly of the structure atom by atom. Separating the layers is called exfoliation.

That’s the short version, dear Investorintel reader, for more detail please read on…

Graphene is the new wonder material, which promises to revolutionise everything from batteries to bulletproof vests. It is a superb conductor of electricity and heat, 200 times stronger than steel and can form a transparent and flexible layer just 1 atom thick. Small wonder then that this has attracted a lot of attention from investors.

A Google search shows 327,000 hits for graphene manufacturers. There is a lot of content out there associated with making this material. At Investorintel, we have been analysing the global graphene supply market and the report will be available soon. In creating this report we have looked at who is making graphene by what method to understand the current state of the art. This column contains some of the background information.

So, how is this material made?

There are two basic methods to make graphene, they are classed as the top down and bottom up approach. This column will focus on the top down approach, and we will look in detail at the bottom up approach in the next column.

The Top down approach to make graphene:

The starting material is graphite, which is made of layers of graphene rather like a pack of playing cards as described in part 1of this series.

The scotch tape method:

Place a thin sample of graphite on to sticky tape then place another piece of sticky tape on top of the exposed part of the graphite sample. Press the sticky tape together and peel the tape apart. This will cleave the layers. Take one of the pieces of sticky tape and repeat the process. This will eventually leave a single layer of true graphene stuck to the tape. At this point stick the tape to a suitable surface such as silicon glass. Solvents can then be used to remove the adhesive and tape leaving the graphene layer transferred to the substrate of your choice.

Exfoliation of graphite

This hand-prepared method can produce very high quality pieces of true graphene. This is the prime source universities use for research quality samples. The leading producers of this type of product are based in the UK at the University of Manchester where the Nobel prizewinning work was originally performed.

The size of the graphene monolayer is determined by the flake size in the original sample. Typical flake sizes are around 2000 micrometres (µm or micron) the largest graphene monolayer flake size found so far is 1,500,000 square micrometres. If that sounds big then consider this character in the brackets:

 (o)

This is about the size of that largest piece of graphene found in graphite so far.

This artisan graphene is not cheap; prices are typically 0.5 GBP per micrometre. So expect to pay at least $750.00 USD for a piece of flake monolayer graphene transferred to SiO2 glass.

Industrial exfoliation methods

It will not surprise you to know that people have been looking for cheaper ways to make graphene in industrial quantities. The main alternative method is to tear apart the layers in graphite using a shear mixer.

The basic science has been worked out  and graphite can be sheared down to create a suspension of individual flakes of graphene in various liquids. A 1mg/L suspension of monolayer graphene in ethanol will cost approximately $1000.00 USD per litre.

Organisations are competing against one another to develop patent protected methods for creating exfoliated graphene from graphite. These include electrochemical methods where graphite is put in suspension in water with a conducting chemical additive such as acrylonitrile.

Other industrial processes use a stabilizing solvent such as N-Methyl-2-pyrrolidinone (NMP). This works because the surface energy of the solvent matches that of graphene. So once the graphene platelets are broken apart the solvent keeps them dispersed. The solvent can then be evaporated to create a graphene powder that contains pieces of graphene up to 2 micrometres in size.

Another common route to making graphene is to subject graphite to chemical oxidation creating graphene oxide. The most common route is Hummer’s method. This is then reduced back to graphene again using an oxygen scavenger such as hydrazine hydrate.  Graphene Oxide is a fascinating material in its own right and has quite different properties to graphene which we will explore in a future column.

The market overview

The market for graphene suspensions and powders has become rather crowded and the market shakeout had started. Our first survey found 55 organisations making graphene by the top down method. The latest update has found 48 manufacturers around the world.

All these industrial methods produce tiny particles of graphene. If anyone knows of a process that can reconnect these small pieces into large sheets of continuous defect free graphene, please let me know as I have not found any credible evidence for this yet.

The size of the sheet of graphene is important. To fully realise the amazing properties of graphene in the promised new products requires the use of continuous defect free sheets of graphene of the sort of scale where you could take a single sheet and hold it between your hands.

No matter how graphene is made from graphite it is worth noting that all these methods produce very small pieces of graphene, some call these graphene sheets. Look at the full stop (period) at the end of this sentence; it is 100,000 times bigger than the graphene sheets produced by these industrial exfoliation methods.

Using the term sheets to describe graphene gives the casual observer the impression we are dealing with something of the scale of copier paper when in fact these ‘sheets’ are a hundred thousand times smaller than a small dot. This is not to say the exfoliated graphene products are no good, they do have uses, which we will look at in another column. This tells you more about the power of marketing hype surrounding the current state of graphene manufacturing.

So, making graphene by the top down route from graphite can produce industrial scale quantities of the wonder material, just in very, very tiny pieces. Larger sheets of graphene are required to realise its full potential. We need to look at other ways of making the stuff and that, dear Investorintel reader, is the subject of the next column…


Editor:

Adrian Nixon is a Senior Editor at InvestorIntel. He began his career as a scientist and is a Chartered Chemist and Member of the Royal ... <Read more about Adrian Nixon>


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Comments

  • Adrian Nixon

    Thanks John, Glad you liked it. Thanks also for being patient too, it takes a little time to check the facts and make sure everything is verifiable.

    I can quite understand the 20 year development of diamond deposition technology. I’ve managed an R&D lab in the past and quite a lot of the research never works. R&D is as much an exercise in failure management as in creativity. Knowing when to pull the plug on projects is a tricky decision but one that’s vital for a healthy R&D portfolio because no one has unlimited resources. Looking back from a successful product-to-market, everyone sees the success and quickly forgets all the failures and dead ends.

    I agree entirely that graphene is a tremendously exciting material. It will change all our lives in the future and the key to that will be making graphene in large area quantities. I’m working on the next column at the moment that will show the current state of the art. There are lots of organisations in the race to make this stuff. The race is as fascinating as the end product will be. However, you will know much better than most that this race is more a marathon than a sprint.

    March 7, 2016 - 7:03 AM

  • Adrian Nixon

    Ah, so they got lost in many rabbit holes and ended up losing their focus. That can happen so easily in the excitement pursuing sexy applications rather than the seemingly less exciting things that would bring in the money like the drills. It’s easy to spread one-selves too thinly.

    I too am hearing wonderful things about adding graphene powders and dispersions to all sorts of things such as clothing and bike tyres. Many of these applications are building evidence of their benefits so I’m still watching and listening at the moment.

    March 7, 2016 - 10:10 AM

  • Peter marshall

    Superb article Mr Nixon, and especially including John Petersen’s follow up comment interactions. A terrific, understandable of the key issue to Graphene’s wonder material success story of the century:– > cost effective very high volume Graphene manufacturing.
    Will your next article provide your market analysis of current progress in this regard, including names (lab, company and likely timelines).
    Am I hoping for too much?

    Keep it coming…..a happy reader.
    Peter, from Ottawa.

    March 7, 2016 - 12:56 PM

  • Adrian Nixon

    Thank you very much for your kind words Peter. You are on to something when you note the interaction between us is as interesting as the column itself.
    The next column is about the bottom up manufacturing method for making graphene from carbon containing sources other than graphite. This series will run to at least 6 column entries. If you are interested in the market analysis you’ll find that in this previous column: http://investorintel.wpengine.com/technology-metals-intel/who-is-making-graphene-and-where-examining-a-secretive-market/
    More to come…
    Adrian

    March 7, 2016 - 5:12 PM

  • Sam Amamoo

    Adrian, a highly useful follow-up to Part 1 of “Understanding Graphene”. You deserve credit for clarifying the production processes associated with graphene without lessening the scientific fundamentals including the basic chemistry. I don’t recall reading anywhere a distinction being made so well between graphene powders and graphene “sheets”, the physical scale of current products and their significance in various manufacturing end uses.

    In this regard I wonder whether it is a case of graphene powders for coatings etc and the almost mythical A4 size monolayer of graphene for the near miraculous future applications which have made graphene so famous. I say “almost” because science and technology can move in quick and mysterious ways. Lets think “disruption” but that can’t be right because there is no existing graphene sheet production technology to knock of the pedestal! No, we have to wait patiently for the ‘miracle” sheet.

    Bottom line, You have handed investors in the graphite/graphene space invaluable information that will guide them in managing risks related to their investment decisions.

    No doubt about it, there is more to the term “graphene” than I suspect many realised. Many thanks.

    March 9, 2016 - 4:31 AM

  • Adrian Nixon

    Thanks Sam, You’ve grasped the intent of this column instantly.
    I’ll be writing about the commercial uses of graphene powder and dispersions in a future column. At the moment I’m taking a long hard look at the promise of other methods to produce larger scale graphene.

    I think you are right that technology moves in quick and mysterious ways. I do a lot of work looking at trends in future technologies. Everyone assumes that progress is a smoothly improving line upwards, in fact it commonly occurs in rapid advances interspersed with long periods of seeming inactivity.
    It makes for an interesting world. back in touch shortly with another column.
    Adrian

    March 9, 2016 - 4:54 AM

  • Understanding Graphene – Part 3 | InvestorIntel

    […] a previous column we looked at the top down method of making graphene from graphite. This can be scaled to produce […]

    March 25, 2016 - 12:44 PM

  • New faster method for making large scale, high quality graphene

    […] commercial quantities (kilogrammes and tonnes) of graphene are made from graphite usually by the top down method. These are available as powders and liquids that can be used as additives in other products such as […]

    July 31, 2017 - 9:29 AM

  • DON KRESS

    Adrian, thanks for a great series of articles and graphics explaining graphene. You asked to be informed of systems and methods that may be capable of producing larger sheets of graphene. We have a published patent application in which is described a vortex based system which utilizes an interfacial trapping method patented by the University of Connecticut. Here is our application:
    https://patentscope.wipo.int/search/en/detail.jsf?docId=WO2018100552&redirectedID=true
    We are currently seeking interested parties that can assist in critiquing and if worthy, developing a prototype to explore the possibilities of this invention.
    I have more information, so contact me directly if you wish.
    Thanks
    Don

    September 6, 2018 - 10:18 AM

  • Adrian Nixon

    Hello Don, Glad you find the series interesting, there is more to come. I have had a look at your patent. Would I be right in assuming the following:
    1) Input is graphite powder and two immiscible liquids.
    2) Graphene nanoplates exfoliated from graphite inside your cavitation reactor using ultrasound.
    3) Graphene nanoplates gather at the interface between the two liquids
    4) A graphene tube emerges from the reactor.
    If this is broadly how the reactor works, I’m curious to know how the graphene nanoplates stick together and what are the physical characteristics of the product you create.
    Thanks, Adrian

    September 6, 2018 - 11:52 AM

    • DON KRESS

      Thanks for the quick response Adrian…
      For items 1,2, and 3… correct.
      For item 4, a modified embodiment which I believe would work just as well or better, is similar to the graphene foam embodiment. (I can send you a graphic showing this embodiment) The tube shape of graphene would form as the fluids advance up the reactor and once they reach the guide cone, another ultrasound horn would produce an unstable emulsion of water in oil with the graphene reporting to the interface. This emulsion would then be ejected from the reactor and sent to a suitable vessel allowing the two immiscible fluids to separate. The graphene would/should spread out and report to the interface and the quality of the graphene would likely depend on the design and how the system is operated.
      As I am not an expert on graphene, so as for how the nanoplates stick together, I would refer you to the dissertation by one of the UConn inventors, Steve Woltornist…
      https://opencommons.uconn.edu/cgi/viewcontent.cgi?article=7251&context=dissertations
      His explanations and data are excellent and his photos are better than the UConn patent documents.
      I emphasize that our patent pending is conceptual at this point and has not been prototyped. We have several patents pending with vortex fluid motion being a central theme. As I was curious about graphene and doing some research on the subject, I came across the UConn methods and devised a vortex system which should produce graphene products in some quantity using their methods.
      I am of the opinion that some ‘lower end’ applications of graphene foam might have less stringent market entry barriers…
      For example, I was intrigued by the foam’s ability to absorb hydrocarbons whilst being hydrophobic. This would make a good spill absorbent for oil, diesel, gasoline spills.
      Another possibility would be to shred the foam (once it has cured) into a fine powder and admix with asphalt for pothole filling. A suitable foam could absorb the asphaltenes into a strong matrix and the strength of the filled pothole might be increased. The barrier to entry here is low… you could fill a few potholes in a private parking lot at a mall for example, off the back of a half ton truck and observe what happens.
      Other low barrier products might be imagined. The idea is ship product, establish cash flow and get fancy later.
      You can email me directly if you like as I have more in the way of block diagrams and sketches to share.
      donkress0123318480@gmail.com

      Cheers
      Don

      September 6, 2018 - 12:17 PM

    • DON KRESS

      Hi Adrian. Correct.
      I had a previous more lengthy response but not sure it went through.

      As to how the nanoplates stick together, search for
      “Steve Woltornist dissertation”
      Steve is one of the inventors of the UConn methods that our vortex system invention is based on.
      He has great explanations and the photos are better than the patent document.

      I put my email address in the previous posted response so maybe it got rejected?
      You can contact me directly as I have more graphics and sketches I can share.
      donkress0123318480
      The “at” symbol
      gmail dot com

      thanks
      Don

      September 6, 2018 - 12:28 PM

  • Adrian Nixon

    Hi Don, I’ll send you an email so you have mine and we can continue the conversation. Regards, Adrian

    September 6, 2018 - 12:33 PM

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