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Graphene: You Don’t Get What You Pay For

Since I was going on yesterday about the need to validate tool reagents, I wanted to note that this problem is not confined to biochemical applications. Here’s an article looking at commercial sources of graphene, the carbon monolayer material that’s been the subject of so much research the last few years. There are a number of ways to produce it, starting with the famous tape-peeling method, which doesn’t exactly scale to commercial production. And there are quite a few commercial suppliers, with the usual footnote that it can be hard to tell who might be reselling material from someone else.

And as the paper shows, the commercial graphene supply is a mess. The first problem apparently is that a number of things labeled as graphene are actually graphene oxide or its reduced form. That’s a brute-force way of exfoliating graphene sheets by absolutely oxidizing the crap out of the bulk material with a hot mixture of potassium permanganate, sodium nitrate, and sulfuric acid (which will indeed oxidize the crap out of most anything you toss into it). The graphene sheets get riddled with epoxides, hydroxys, and COOH groups, breaking the layers away from each other, and graphene oxide itself is its own field of study. But it sure isn’t graphene. You can partially reduce the material back toward graphene (rGO, reduced graphene oxide) but this is yet another amorphous material, full of random defects, that is also not graphene. But there are plenty of labeled vials for sale that claim otherwise.

Once you’ve hacked your way past that stuff, there are plenty of quality control issues with graphene itself. The real thing is a single carbon atom layer thick, and has very interesting properties. But all the methods for its production (including the tape) give you mixtures of multilayer species that have to be purified. The properties of these get progressive less unusual, and by the time you’re up to 10 layers thick it’s basically indistinguishable from bulk graphite, which needless to say is a heck of a lot cheaper than graphene. Guess what you’re buying, though. The authors of this paper analyzed material from 60 different suppliers worldwide:

The lack of standards for graphene has been stalling the development of graphene applications due to the bad quality of the material sold in the open market. There is a lot of confusion and misinformation in the graphene application’s market leading to unreliability and senseless pricing schemes. . .

. . .As one can clearly see, the majority of the companies are producing less than 10% graphene content and no company is currently producing above 50% graphene content. This result may come as a surprise given the widely advertised graphene “fever” of the last decade. However, it also helps to understand why graphene applications are not commonplace yet.

Yeah, I’ll bet it does. It also leads to the immediate conclusion that a great deal of the graphene literature, the part from people that didn’t carefully produce and purify their own graphene and chose to believe what was on the label instead, must be close to worthless. It appears that the majority of companies are producing what would be better named “finely divided graphite particles”, thick three-dimensional chunks on the nanoscale that have little or nothing to do with graphene.

Furthermore, it is worrisome that producers are labeling black powders as graphene and selling for top dollar, while in reality they contain mostly cheap graphite. This kind of activity gives a bad reputation to the whole industry and has a negative impact on serious developers of graphene applications.

Indeed. It’s not so worrisome for the producers, though – the less ethical ones might consider switching to carbon black as an even cheaper alternative, since it’s not going to perform any worse than the crap they’re selling now. I should note, though, that there are a couple of companies whose material apparently consists of only 30 to 40% carbon at all, which is really impressive, although not in the good way. What the hell the rest of it might be is a good question. As is often the case in these sorts of papers, suppliers do not appear to be named. But at some level, it hardly matters: not one single supplier, in case you’re wondering, manages to sell anything near pure monolayer graphene. The average of even the better end of the scale is four-layer material.

So in case it’s needed, here’s yet another warning. If you’re buying any material/reagent/chemical tool that’s the least bit interesting, unusual, crucial to your research in any way, or (especially) that is for some reason difficult to produce, don’t just take their word for it. Characterize it. Assay it. Make sure it’s what it’s supposed to be. Unless you’re really into wasting your time and everyone else’s.

Update: here’s Nature on the same topic.

27 comments on “Graphene: You Don’t Get What You Pay For”

  1. Peter Kenny says:

    Sounds like the PAINS filters may need to be updated?

  2. Red Agent says:

    Interesting. This blog and yesterday’s frame a significant (and unfortunate) difference between academic and industrial work. In academics there is substantial reward for supplementing the literature with experimental results. If the results are invalid because of lousy tools or reagents, you can still publish in good faith and get your promotion / speaking invitations / whatever. In industry there is no equivalent upside. Doing dead-end work that can’t produce a commercial product because of bad tools will waste your time and your employer’s resources. No good can come of that.

    1. Ivory Tower SWAT team says:

      The idea that industry is above these perverse incentives is directly contradicted by the article, since commercial suppliers are making off like bandits selling sub-par material.

      1. loupgarous says:

        Anyone who’s read Max Gergel’s memoirs knows that chemical (and other technical suppliers) exist on an whole other plane of ethical existence than most researchers. Derek’s latest article illustrates that when you’re on the frontier of science, your suppliers are on the frontier of how fast they can turn profitable product out, and how high they can get their profit margin. If you’re making reagents for other folks in a couple of sheds in South Carolina with cheap labor, that margin can pay a lot of alimony.

        And so it seems to be in nanotech. The difficulty in finding suppliers of graphene good enough to exhibit the behavior which is creating the buzz points to scalability not being good enough even to support the kind and quantity of research to get Moore’s Law-caliber progress in developing graphene applications.

        By comparison, people working in rare earths for high-temp superconductivity have it easy – well-capitalized suppliers, most of whom make ton lots of what you’re working with and assay in-house because they’re mining companies and that’s what they do.

        Maybe Elon Musk can spend all that spare time from not chairing the board at Tesla on inventing a scalable process for making true graphene in quantity. Might come in handy down the road for making maglev for that Hyperloop of his. In any case, just a pilot plant for mass-produced graphene would, if its product was reliably good, cover some of its own expenses.

      2. Ken says:

        The point I got from Red Agent’s post is that the market provided by academia is supporting these sub-standard materials, and the lack of any commercial products means no market means no improved suppliers.

        1. loupgarous says:

          There are commercial products, just preponderantly in structural applications. Structural graphene, unfortunately, isn’t monolayer and doesn’t exhibit all those splendid electronic and chemical properties at any scale, much less nanoscale. It’s great for making what you might call nanofiberglass, and that’s a big market.

          My hope is that the market for “structural grade graphene” gets large enough to spur a fabrication technology usable for making monolayer graphene at high scale/low cost.

          It took 7 years from the invention of the transistor in 1947 to the mass-production and sale of the first portable transistor radio in 1954. From the isolation of graphene in 2004 to its first commercial application in the Siren anti-theft packaging device took 7 years.

          Moore’s Law ought to shorten the time between truly world-changing applications of graphenes from 1947 to the IBM-PC’s rollout in 1981 (34 years) dramatically.

    2. loupgarous says:

      Is Bell Labs industrial enough for you?
      I only ask because the prolific Jan Hendrik Schön‘s career there from 1997 to 2002 provoked 28 retractions from major journals such as Science, Physical Review and Nature, and a small but still impressive list of “concerns” about more papers from his time at Bell Labs, when he was publishing on a new (and irreproducible) experimental result about every eight days. Eventually the University of Konstanz, Schön’s alma mater, revoked his PhD.
      So tell me how comparatively pure industry is compared to academia, again?

      1. The Lunatic says:

        Well, was Jan Hendrik Schön developing products for commercial sale, or was he publishing papers in academic journals?

        So, by Red Agent’s provided definitions he was doing academic work ( “supplementing the literature with experimental results”), not industrial work (“produce a commercial product”), even if he was employed by Bell Labs. Which means, no, Bell Labs wasn’t remotely “industrial enough”.

        1. loupgarous says:

          Schön reported making fundamental discoveries which would have immense technological value to Bell Labs and its parent company (at the time, Lucent Technologies). Had they not been irreproducible by others and led to patentable devices or concepts, the patent rights would probably have gone to Bell Labs. So, Schön was an industrial researcher. Reproducible work or not, his purported discoveries and innovations would have been incredibly valuable to his employer, which was in the right business to exploit them commercially or license them to other firms.

          1. Ren Hoeg says:

            Just as a side note – I seem to recall that at the time of the scandal Bell Labs was quick to emphasize that basically all of Schön’s questionable/faked work was from his time at the University of Konstanz in Germany. The investigation there demonstrated some interesting facts like e.g. that while his PI toured the world presenting the data and lauding the man as a future Noble Prize winner he later had to admit that he never bothered to look at the actual raw data produced by him.

          2. The Lunatic says:

            No, sorry, “could have led to valuable patents” doesn’t make academic research the same thing as product development in industry, or else huge numbers of researchers in the hard sciences at universities that license patents is engaged in industry.

            I’m not saying Red Agent is correct, but Schön is not a refutation of what he said. Schön makes a dandy refutation of, say, profit vs. non-profit, or corporate vs. non-corporate, or private vs. public, but not of Red Agent’s actual argument as presented in his post.

          3. Hap says:

            Example?
            http://blogs.sciencemag.org/pipeline/archives/2016/10/12/pfizer-fires-for-fakery

            Industry used to do fundamental research – it didn’t immediately lead to products but might in the future (either because it helped support their monopoly status or because good internal knowledge of fundamental discoveries might make it easier for them to incorporate those discoveries in products). Industrial research used to be where the research was, not what it was.

    3. Snorelax PhD says:

      Can’t you just assume? What else could it be? Hurry up time to publish no time to run the controls! Hooray! Papers for everyone!

  3. Uncle Al says:

    absolutely oxidizing the crap out of the bulk material” pfft. Piranha solution! 3:1 conc. sulfuric acid / 30% hydrogen peroxide (Caro’s acid). Disposal is no problem, for short of air dropping vented friable glass containers into the Drake Passage, there is none (that your boss would personally attempt).

    As for vendor SOP…if a levied penalty is less than profit in hand, it’s not a deterrent – it’s a business plan.

    1. loupgarous says:

      ” …if a levied penalty is less than profit in hand, it’s not a deterrent – it’s a business plan.”

      Or, in Elizabeth Holmes’ or Martin Shkreli’s cases, “…if a levied penalty is less than other folks’ venture capital in hand… “

  4. loupgarous says:

    The really scary part of the post, Derek, is “The average of even the better end of the scale is four-layer material.”

    What’s to do, then? If one takes your good advice and analyzes every bit of graphene out of the container for monolayer-ness, and finds one’s not getting it no matter who one buys from, it’s not unreasonable to think it’s not much more work to make one’s own graphene and assay that instead. But then, reproducibility gets wild and woolly – much better to be able to just give a supplier’s name in “Methods and Materials” than say “we prepared our own graphene, samples available on request…. “

  5. Passerby says:

    I want to seriously ask a question to graphene-oriented folks here: was the Nobel Prize for graphene justified? Sure it’s a very interesting material, but given the paucity of real-world applications, the prize seems premature at the very least.

    1. loupgarous says:

      Graphene’s got so many technically, medically, structurally and electronically important properties that, yet, that Nobel was justified and then some. Even the stuff that ‘s crap for actual nanotechnoiogy research and development works as a structural basis for new resin goods, and those goods are selling now.

      My son sends me new and increasingly cool drones, one of which is the thickness and width of a five-cent coin (if I said “nickel” people here would think I’d jumped topics), and with decent battery life given the battery has to coexist in that space with the other parts. Yep, graphene parts make that possible.

      I’ll leave Googling other current publications on more electronically functional graphene’s applications (as a replacement for metal electrodes in batteries, frex) as an exercise for the reader.

    2. loupgarous says:

      Wikipedia hasn’t covered but all things graphene can do which other chemical structures cannot do as well, but it’s worth a look, anyway.

      My high-tech group in Second Life discusses at least one or two new innovative and incredibly useful uses for graphene a week, among other things. It’s the path toward “green” batteries and very small but charge-dense capacitors, unprecedentedly light and usefully strong small structural parts (and again, “green” compared to structural alloys that strong at the same dimensional scale), it’s biocompatible in many medical applications, and one paper reports superconductive behavior in a graphene cylinder wetted by heptane.

  6. Anonymous says:

    As has been mentioned previously in Pipeline, other carbon nanomaterials are also problematical. I had to buy materials from one supplier whose catalog had TEMs of the nanotube materials offered. Single wall, double wall, multiwall, … crude, oxidized, purified, … short, long, … It was all the same TEM! I got EMs of the materials delivered and they were crap. They sent less terrible replacements. I pointed out the problems – garbage in – but the project went forward anyway. There are more than 15 publications – garbage out – from that group and it is confounding the literature.

  7. nonchemist says:

    Seems to me that the whole nanotechnology business has gotten too big (ha!) for its own good. Its genuine discoveries easily deserve the recognition, so far as I can judge, and I don’t think anyone will contest that. But on the other side of that scale, you’ve the unreliable starting materials, poorly documented synthesis protocols that have proper chemists hanging their heads in shame, an alarming number of get-high-impact-quick schemes that involve tossing nanoparticles into whatever you were working on (my own PhD was full of this, unfortunately), and crowning achievements like nanochopsticks.

    But it’s good that the field is getting this kind of fire, since there’s a lot of room to do respectable research in it.

    1. loupgarous says:

      It’s also already commercially useful, which is the path toward getting graphene good enough to do research with (as both demand and competition in the market increase enough to drive better and more powerful fabrication methods).

      I hadn’t realized just how much graphene production is scaling up until I researched some of my replies here to make sure of my facts. Now that commercial-grade graphene’s getting cheap enough for consumer goods, it’s showing up in that space, mainly as a structural matrix for small, durable resin parts, where it’s important in really small drones and medical devices.

  8. glassveins says:

    Guess I’ll just stick to synthisizing my own ClF3O2 and assorted tetrazole compounds, then.
    (kidding, kidding.)

  9. JG4 says:

    https://www.nakedcapitalism.com/2018/10/200pm-water-cooler-10-12-2018.html

    Commodities: “The war on fake graphene” [Nature]. “Imagine a world in which antibiotics could be sold by anybody, and were not subject to quality standards and regulations. Many people would be afraid to use them because of the potential side effects, or because they had no faith that they would work, with potentially fatal consequences. For emerging nanomaterials such as graphene, a lack of standards is creating a situation that, although not deadly, is similarly unacceptable…. Writing in Advanced Materials, Kauling et al.1 report a systematic study of graphene from 60 producers, and find that many highly priced graphene products consist mostly of graphite powder.”

  10. a. nonymaus says:

    It seems like the other problem is the lateral extent of the graphenic domain. Can I sputter a monolayer of pyrene and call it a day? What about coronene? Where is my 1 m x 1 m x 1 monolayer sheet of carbon atoms?

  11. Brett Goldsmith says:

    I actually make a graphene product, a sensor system we manufacture and sell to biotech and pharma researchers. It is a real product that uses single layer graphene, with actual customers outside the nanotech community.

    We make our own graphene via CVD, and only recently started seeing vendors make an attempt to match quality and cost of what we do internally.

    To develop a real industry, we do have to do our own basic research decoupled from the granting system, which strongly shifts priorities away from commercial realities. We also have to set high material standards. This is not a hypothetical, it’s something that we have done.

    However, we cannot change the overall culture in nanotechnology that rewards hero devices, outliers, and a continual re-hashing of the same issues. For the field to move forward, we need to look for rigor and standards outside of the graphene community. For example, “manufacturability” should be demonstrated in a competitive manufacturing environment, yields should be reported completely not just for the few times that things work out, and material testing should be appropriate for the end application instead of dictated by material producers. The standards in use right now encourage bad behavior, hype, and create barriers to commercialization.

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