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Method for manufacture of Graphene

Large swathes of the new wonder material produced cheaply.
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Graphene is the most amazing new material to be identified for decades. It is the world's thinnest and strongest material, the best conductor of heat and electricity, combines brittleness and ductililty as well acting as a total barrier to gases but one which still lets water vapour through as if the graphene barrier wasn't there. [links]

The current favoured method to produce graphene is to basically pull off a single-molecule-thick layer from a block of highly ordered graphite with a scotch-tape like material then dissolve the substrate. This works, but is very fiddly and only produces very tiny samples of this essentially 2-dimensional material. Others are trying many different methods such as vapour deposition and chemical growth on substrates but none have really taken off.

My proposed method is to emulate the technique used to manufacture float glass. Graphene has a very high melting point which hasn't even been accurately determined as yet but I've seen a figure of ~3400 K . I would find a metal with a high, but still lower than graphene's, melting point such as tantalum ~3290 K and heat it to around 3350 K then pour it into a tray. A tiny quantity of melted graphite is then poured onto the liquid substrate where it disperses into a molecule-thick layer before slowly cooling to solidity. Bung the whole mechanism into a large centrifuge if you like to aid the graphene's dispersal to molecular thickness process then, when the sheets of graphene have solidified, pick them up carefully (*HOT* - use oven gloves) and hang'em on the clothesline to cool.

There you go. Sheets of graphene as big as you like with very little energy cost other than the heat required to melt new batches of graphite and to maintain the tray at a baking temperature which is above the melting point of the metal substrate but below that of graphene. The "half-baking" temperature in other words.

I shall mention all bun-givers by name during my Nobel acceptance speech.

AusCan531, Jan 31 2012

Graphene superpermeable to water http://www.gizmag.c...ble-to-water/21240/
Another amazing property of graphene discovered [AusCan531, Jan 31 2012]

Wikipedia http://en.wikipedia.org/wiki/Graphene
Good description of many different methodologies being tried to manufacture graphene. [AusCan531, Jan 31 2012]

Czochralski process http://en.wikipedia...Czochralski_process
I'd try this process to form graphene [xaviergisz, Feb 01 2012]

New use for graphene and carbon nanotube hybrid http://www.popsci.c...tougher-than-kevlar
[AusCan531, Feb 06 2012]

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       Bun bribery [+]
pocmloc, Jan 31 2012
  

       You're most likely going to need to run the process in an atmosphere of Argon, which you failed to mention.   

       Bun [+]
8th of 7, Jan 31 2012
  

       Yes, but would it work? I can think of two possible problems:   

       (a) carbon is very soluble in molten iron; what's its solubility in other metals? Even a trace of solubility would be very bad.   

       (b) Would the molten graphite form single- molecule-thick layers? For instance, if you pour oil on water, it forms relatively thick puddles rather than a uniform thin layer, because of surface tension.
MaxwellBuchanan, Jan 31 2012
  

       //run the process in an atmosphere of Argon//. I'm embarrassed to say that I don't even know where the planet Argon is located let alone how to get there. Sorry.   

       [MB] raises good questions to which I don't pretend to know the answers. For what it's worth, no one has ever specifically mentioned to me in my entire lifetime that carbon is soluble in molten tantalum. Presumably solubility of metals reaches a saturation point, so does it make sense to dissolve carbon into the molten substrate to the point of insolubility then proceed as specified? Would the large differences in Specific Gravities of carbon and the saturated substrate be enough to separate the layers or would one simply end up with a non- delineated mess? How does the fact that the substrate metal is kept below the melting point of carbon affect the whole solubility issue anyway? (I ask a lot of questions for a potential Nobel Laureate, I know, but that is how one learns.)   

       Different oils have different viscoscities and I have no idea as to the viscosity of molten carbon but I'm sure temperature would be a large factor. The centrifuge would also play a part in spreading the layers. A tray of 4000 degree molten metal spinning at high speed - what could go wrong?   

       If the aforementioned difficulties are surmountable I'm sure large sheets of graphene would be a valuable enough commodity to make it worthwhile. There are thousands of potential uses if a viable manufacturing technique can be found. It is vast project but I've already got half-vast plans.   

       My second method would be to further pursue the 'drawing' method mentioned in the Wikipedia article by intercalating the graphite between sheets of gold then drawing and pounding them to extreme thinness before melting the gold away for reuse. I've already got the graphite so would appreciate as many donations of gold as you can all spare.   

       [pocmloc], you get first mention in Stockhom - subject to how the gold donations come in, obviously.
AusCan531, Jan 31 2012
  

       You could have a problem with the container that is supposed to hold that molten metal. As for possibilities regarding that molten metal, you might consider rhodium. I don't know how it reacts to carbon, but rhodium is able to ignore oxygen at almost 2000 degrees Celsius.   

       Anyway, it seems to me there is probably a simpler way. If they can grow large diamonds from a "seed" in a vacuum-deposition chamber, I assume they can grow sheets of graphene that way, too.
Vernon, Jan 31 2012
  

       Isn't rhodium extremely expensive?
nineteenthly, Jan 31 2012
  

       It's not used up by this process.
pocmloc, Jan 31 2012
  

       Cool links. I like the dry ice method, very mad-scientisty.   

       Graphene mines can be established on demolished grade schools that have been producing graphene in a systematic way for a century or more.
rcarty, Jan 31 2012
  

       As a welder and armchair metallurgist, I'm familiar with innumerable practical properties of carbon (in graphite form and others) but my scientific understanding, as is well-known on this forum, is limited, so this may be a dumb question. Feel free to give me a smart answer, as long as it doesn't involve too many greek characters.   

       I know that carbon is 'sticky'*; it likes to grab onto other elements that have open valence electrons, like iron. That's essentially what makes it so useful to people like me (an experienced fabricator has 101 uses for a #2 pencil that don't involve writing). So wouldn't your proposed liquid metal substrate have to be treated in such a way as to eliminate every single vacancy (difficult) and also kept 100% pure (nigh impossible on a mass-production scale, even in a clean-room) throughout the process? Every time you bring a metal, any metal as far as I know, to a molten state and then cool it again, a tiny amount of molecular breakdown is inevitable as the crystalline structure passes through multiple configurations.   

       *[Alterother] terminology
Alterother, Jan 31 2012
  

       I am definitely not a metallurgist of armchairs or anything else but fools rush in and all that. I was actually very tempted to say "Carbon?, why mention that when I'm using graphite? Sheesh guys, you're embarrassing yourselves here."   

       The contamination issue you mention is basically the same as the one [MB] raised and may well be a fatal flaw. I do know, however, that if I use pure elemental tantalum or rhodium or gold or whatever and pure carbon there won't be any 'molecular breakdown' as long as the elements can indeed be kept from combining.   

       As to what form the carbon takes when it cools, who knows. "Damn! Another sheet of pure diamond when I wanted graphene." In reality, and based upon my personal history, I would probably just end up with a very awkwardly shaped pencil lead and some nasty burns. (BTW, the only relevant Greek character I know of is Hephaestus who was the crippled god of fire and metalworking.)
AusCan531, Jan 31 2012
  

       I don't know how to melt graphite, but it practically vaporizes under a welding arc. When I need to weld cast iron and don't have any Nirod, I scribble a pencil up and down my weldment until the root is loaded with graphite, then use 7018 (an electrode made for welding mild steel) and peen the hell out of the weld while it cools. The graphite burns white on the leading edge of the puddle, brighter than magnesium. Somehow I can't picture it just calmly melting.
Alterother, Jan 31 2012
  

       [8th] hit the nail on the head by pointing out the need to conduct the process in an inert atmosphere. No oxygen = no burning.
AusCan531, Jan 31 2012
  

       There's no oxygen in a weld puddle either; the solid flux burning off of the electrode (or the flux gas introduced by a wire-feed gun) creates an artificial atmosphere around the arc and puddle. If any oxygen gets in there, it means I screwed up and will spend the next few minutes grinding it out and starting over. Much profanity is typically involved, as well.   

       I guess that must mean that the graphite isn't actually combusting, but having seen it dozens of times, I'm hard pressed to come up with a better description of what it looks like. It definitely doesn't melt in the same way common metals melt.
Alterother, Feb 01 2012
  

       Anything at temperatures over 3000K will be glowing brightly whether it's oxidising or not.
mitxela, Feb 01 2012
  

       My idea for creating large sheets of graphene would be using the Czochralski process.   

       I'd start with a long diamond blade that is single atom thickness at the blade's edge. The blade would initially rest on a carbon substrate. A laser would be fired in a line directly below the blade's edge, heating the carbon to 5000ºK and thus melting it. The blade would slowly be lifted, and a graphene sheet would (hopefully) form on and hang from the blade.
xaviergisz, Feb 01 2012
  

       At atmospheric pressure I believe carbon vaporizes, not melts. In order to get liquid, you need to keep it up around a hundred atmospheres, plus or minus.   

       Ignoring that, I suspect even if you could find a liquid substrate that won't preferentially absorb the carbon, at best you're going to end up with unordered graphite, including some small graphene sheets.
MechE, Feb 01 2012
  

       Yeah OK, you'd need to do the whole thing in 100 atmospheres of inert gas. That shouldn't be impossible since that it's less than the pressure inside a scuba tank.
xaviergisz, Feb 01 2012
  

       (c) There's no such thing as "melted graphite".   

       (d) Carbon cannot exist as a liquid below 10800 kPa (about 100 atmospheres).
spidermother, Feb 01 2012
  

       //Is tantalum expensive? //   

       Not really. The best I could find on the net after a short search is $100+/lb or $300/lb for capacitor-grade tantalum powder. You'd only need a few millimetres thickness just as long as you provide enough thermal mass to keep it from cooling. It would last indefinitely as it isn't consumed in the process. Even gold would be financially viable over the short-to-medium term due to the value of the end product.   

       As the more learned HB'ers chime in, I think it is becoming obvious that the technical difficulties outweigh the financial ones. We need to ensure that the graphene doesn't combine with the substrate after we somehow 'melt' the carbon in over 100 atmospheres pressure of an inert gas in a crucible that retains integrity at over 4000K whilst spinning rapidly in a centrifuge. If guys like [MaxwellBuchanan] and [spidermother] solve those little issues, I'll be happy to pony up $3k for 10 pounds of tantalum.   

       The engineering obstacles can all be overcome, but it is the solubility/contamination issues which worry me. I'm not saying it can't be done but p'raps it needs to be a 'shared' Nobel Prize.
AusCan531, Feb 01 2012
  

       //It would last indefinitely as it isn't consumed in the process.// Heated liquid metal evaporates just like anything else. The rate of consumption may be low, but it's non-zero.
MechE, Feb 01 2012
  

       Just guessing, but I'd think the simple Brownian motion of an extremely hot substrate would interfere with getting a 1-atom thick deposition layer on top of it.   

       And my guess for [Alterother] - I think that bright emission you mentioned would be like the light from a carbon arc lamp, maybe?
lurch, Feb 01 2012
  

       Maybe one could use glass instead of tantalum. Avoid oxidation, miscibility problems.   

       If one could use two different substances (maybe glass and tantalum) chosen such that the density of the apparently semilegendary liquid graphite was right between them, and if liquid graphite did not love itself in such a way as to form blobs in the manner of hydrophobic liquids in water (which I think it would as Max noted above), then one could have a self-assembling sandwich in which you lift the cool top layer of glass (which is several meters thick, heavy and made of salvaged cathode ray tubes, and so serves to keep the graphene below under adequate pressure) and see the vast expanse of pristine graphine lying atop the bed of tantalum, all in one enormous sentence.
bungston, Feb 01 2012
  

       What are the limitations of the current method using adhesive tape?
MaxwellBuchanan, Feb 01 2012
  

       I asked because the stickytape method seems inherently good and amenable to improvement. If it can, indeed, only produce small patches of graphene then the problem must be:   

       1) The graphite itself is uneven, with single- molecule "steps" on its surface, leading to a patchwork on the adhesive film.   

       2) The monolayer is broken during or after the peeling and dissolving of the adhesive film or   

       3) The adhesive is not good enough, such that only patches of graphene are pulled off the graphite.   

       All of these ought to be soluble problems, shirley?   

       Another option would be to find a way to reassemble large graphene sheets from small ones, perhaps by cutting them into tiny uniform triangles and floating them on a liquid so that they form a continuous raft (the right surface energies would encourage them to sit next to eachother), then doing some chemical magic to form new carbon-carbon bonds at the joins.
MaxwellBuchanan, Feb 01 2012
  

       That'd be it.
MaxwellBuchanan, Feb 01 2012
  

       // like the light from a carbon arc lamp, maybe? //   

       Very much so, I think. It's not uncomfortable to view through a shade 11 or 12 faceplate, but it's definitely brighter than the arc itself.   

       One thing I do know is that the graphite won't 'float' on molten steel or iron; that's why my little tricks work. By introducing graphite to a white-iron weldment when using a mild steel rod, it's absorbed directly into the matrix and raises the carbon content to the requisite ratio.   

       Interestingly enough, graphite can also be used to _prevent_ weld adhesion in other processes. For example, if I need to extract a bolt that has sheared off deep inside a threaded well, coating the threads with graphite will keep spatter and slag from sticking to them when I carefully fuse the end of an electrode to the broken bolt, allowing me to remove it by twisting the rod with pliers. I have no idea why this trick works, but it's never failed me.
Alterother, Feb 01 2012
  

       Another idea for forming graphene would be to float a thin film of coronene on a substrate and then heat in the absense of oxygen.
xaviergisz, Feb 01 2012
  

       All the great annotations showing up on this posting make me happy. Not Nobel Prize happy, but happy nonetheless. Thanks guys.
AusCan531, Feb 01 2012
  

       /an experienced fabricator has 101 uses for a #2 pencil that don't involve writing/   

       I was ruminating on this. I wonder how many uses are left after excluding those that involve poking/prodding other less experienced fabricators, and those that involve personal hygiene.   

       /coating the threads with graphite will keep spatter and slag from sticking to them/ Pretty much anything coated with graphite will have less stuff stick to it, I would guess.
bungston, Feb 02 2012
  

       // I wonder how many uses are left after excluding those that involve poking/prodding other less experienced fabricators, and those that involve personal hygiene. //   

       Forty-seven.
Alterother, Feb 02 2012
  

       [Alterother] must have bought that new translation of the _Kama Sutra_
mouseposture, Feb 02 2012
  

       //Pretty much anything coated with graphite will have less stuff stick to it, I would guess.// Unless "anything" is a piece of cast iron, and "stuff" is white-hot molten low-carbon steel surrounded by plasma, is the point [Alterother] was making.   

       (Even further off topic, it's annoying that in terms of carbon content, it goes iron < steel < cast iron.)
spidermother, Feb 02 2012
  

       //those uses (for graphite) that involve personal hygiene//   

       Do they put lead in your pencil?
AusCan531, Feb 02 2012
  

       [spidermother], also there is 'liquid iron' from blast furnaces which is cast into 'pig iron'. At 4.5% carbon, this is to the right of your list.
Ling, Feb 03 2012
  

       Irony.
spidermother, Feb 03 2012
  

       Then of course there are the virtually innumerable stainless steels, which in terms of carbon content typically fall between Iron (no carbon) and mild (or low-carbon) steel (.05%-.3% carbon), but can contain up to .5% carbon. It's all really quite simple and straightforward once you accept that almost every grade and/or permutation of iron and/or steel has at least three or four different names dependant on origin, end-purpose, specific industry, etc. Sometimes I wonder why, with so many different types of this incredibly useful material, we even bother with trying to come up with something newer and better.*   

       *rhetorical musing
Alterother, Feb 03 2012
  


 

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