The GRAPHENE mega thread - because it's technology you need to know about!

In 2017, Kim and his colleagues devised a method to produce “copies” of expensive semiconducting materials using graphene — an atomically thin sheet of carbon atoms arranged in a hexagonal, chicken-wire pattern. They found that when they stacked graphene on top of a pure, expensive wafer of semiconducting material such as gallium arsenide, then flowed atoms of gallium and arsenide over the stack, the atoms appeared to interact in some way with the underlying atomic layer, as if the intermediate graphene were invisible or transparent. As a result, the atoms assembled into the precise, single-crystalline pattern of the underlying semiconducting wafer, forming an exact copy that could then easily be peeled away from the graphene layer.

The technique, which they call “remote epitaxy,” provided an affordable way to fabricate multiple films of gallium arsenide, using just one expensive underlying wafer.

“We found that the interaction through graphene is determined by the polarity of the atoms. For the strongest ionically bonded materials, they interact even through three layers of graphene,” Kim says. “It’s similar to the way two magnets can attract, even through a thin sheet of paper.”

With this new understanding, he says, researchers can now simply look at the periodic table and pick two elements of opposite charge. Once they acquire or fabricate a main wafer made from the same elements, they can then apply the team’s remote epitaxy techniques to fabricate multiple, exact copies of the original wafer.

“People have mostly used silicon wafers because they’re cheap,” Kim says.

“Now our method opens up a way to use higher-performing, nonsilicon materials. You can just purchase one expensive wafer and copy it over and over again, and keep reusing the wafer. And now the material library for this technique is totally expanded.”

MIT.edu, News (news.mit.edu), Oct. 8, 2018 - Study opens route to flexible electronics made from exotic materials.

"Epitaxy" is the science term for crystalline growth (how atoms align). This is a study, so we are not going to have stamped out "faster than silicon" chips by Christmas! But it shows how to use graphene as a template (kind of like the mask for spray painting letters) to make copies of the material below.



Using a similar technique (they use electricity to control deposition from solution in a pre-cut pattern in graphene), an IBM team used different substrates at the same time! This will probably work for other things like carbon nanotubes.

Source: phys.org - Graphene puts nanomaterials in their place.



And the graphene gods have shined upon us! Three for Tuesday!

Working together with Eagle Industries and XG Sciences, has come up with a method for deploying the stuff in more than ten underhood components, including fuel rail covers, pump covers, and front engine covers. The graphene, which is remarkably thin and flexible, with very strong sound-barrier properties, will be mixed with foam constituents to produce parts that punch well above their weight with regard to strength and noise reduction.

“A small amount of graphene goes a long way,” says Eagle Industries President John Bull. “In this case, it has a significant effect on sound absorption qualities.”

Fordauthority.com, Oct. 9, 2018 - Ford F-150, Mustang To Feature First Under-Hood Uses Of Graphene.

It may be the "break through application" of graphene like storage tank paint or sound barriers in your truck. Which is a shame since there are other things I would rather see (*cough, cough* *battery*) come first.

According to the SNUR, the generic (non-confidential) use of the single-walled carbon nanotubes will be as an additive in composite materials for mechanical, thermal, and conductivity improvements. According to the SNUR, based on analysis of analogous carbon nanotubes, EPA identified concerns for pulmonary toxicity, as well as potential toxicity to aquatic organisms if the PMN substance is released to water.

The order requires:

1. Submitting to EPA certain toxicity testing before manufacture (including import) by the times specified in the order;

2. Providing personal protective equipment (PPE) to workers to prevent dermal exposure where there is a potential for dermal exposure;

3. Providing National Institute for Occupational Safety and Health (NIOSH) certified respirators with an Assigned Protection Factor (APF) of at least 50 to workers to prevent inhalation exposure;

4. No use of the PMN [premanufacture notices] substance in application methods that generate a dust, vapor, mist, or aerosol;

5. Use of the PMN substance only for industrial uses;

6. Use of the PMN substance only for the confidential uses specified in the order;

7. No release of the PMN substance to water; and

8. Disposal of the PMN substance only via landfill or incineration.

National Law Review, Oct. 10, 2018 - EPA Publishes SNUR for Single-Walled Carbon Nanotubes.

Not the most sexy graphene/carbon nanotube news, but a SNUR, significant new use rules, is a big step in manufacturing. It sets rules manufacturers must follow to ensure worker safety and environmental exposure. The use of CNTs as additives to other materials is a big step towards the Graphene Future!

Rules take effect 10 December, 2018. Will we see "CNT enhanced" materials in 2019??

To unlock the full potential of such metal structures, the IBS team led by Rodney Ruoff at Ulsan National Institute of Science and Technology (UNIST), along with JIN Sunghwan and SHIN Hyung-Joon, invented the "contact-free annealing" (CFA) technique. CFA involves heating the polycrystalline metal foils to a temperature slightly below the melting point of each metal. This new method does not need single crystal seeds or templates, which limit the maximum crystal size, and was tested with five different types of metal foils: copper, nickel, cobalt, platinum, and palladium. It resulted in a 'colossal grain growth', reaching up to 32 square centimeters for copper.

These large single crystal metal foils are useful in several applications. For example, they can serve to grow graphene on top of them: the group obtained very high quality single crystal monolayer graphene on single crystal copper foil, and multilayer graphene on a single crystal copper-nickel alloy foil.

sciencedaily.com, Oct. 18, 2018 - Producing defectless metal crystals of unprecedented size.

One method growing graphene is CVD upon copper foil then washing away the foil in an acidic bath. That method is OK but is also limited by how defect free the foil is. The method described above is another method but has been limited by how well the substrate itself is. Well, now they can take regular foil and create metal crystal substrates of atomic precision. It is only limited by how large your oven is! They place the foil in the oven, evacuate out the oxygen, add in hydrogen and argon, heat it up to just under the melting point, let the foil re-arrange its lattice structure, then cool it down.

That is a major accomplishment! No seed crystal needed. No crazy, robot assisted, computer controlled growing (like how Rolls Royce does their single seed carbon composite growth). Just a little contact-free annealing please!

Can we get to the graphene already?? It is 2018 after all. We are almost in the 4th quarter!

The system uses [...] graphene, which forms the outer structure of the tiny syncells. One layer of the material is laid down on a surface, then tiny dots of a polymer material, containing the electronics for the devices, are deposited by a sophisticated laboratory version of an inkjet printer. Then, a second layer of graphene is laid on top.

...

When the top layer of graphene is placed over the array of polymer dots, which form round pillar shapes, the places where the graphene drapes over the round edges of the pillars form lines of high strain in the material. As Albert Liu describes it, “imagine a tablecloth falling slowly down onto the surface of a circular table. One can very easily visualize the developing circular strain toward the table edges, and that’s very much analogous to what happens when a flat sheet of graphene folds around these printed polymer pillars.”

As a result, the fractures are concentrated right along those boundaries, Strano says. “And then something pretty amazing happens: The graphene will completely fracture, but the fracture will be guided around the periphery of the pillar.” The result is a neat, round piece of graphene that looks as if it had been cleanly cut out by a microscopic hole punch.

news.mit.edu, Oct. 23, 2018 - How to mass produce cell-sized robots.

The next sentence says "pita pocket" to give those who enjoy visual images yet another idea of what was done. Which is really cool as graphene is a crystal. They used the van der Waals force in bi-layer graphene to sandwich a polymer puck of electronics to envelop the electronics, then fracture the bi-layer graphene. The fractures go around the little islands creating the encased electronics! They are all uniform. The graphene shields the electronics too. And some Army Research Lab work they also did, since the robots are so small, they do not need to have an external energy source but can record electric conductivity from the surrounding which can be read later (or erased!).

I am not certain how to feel about this. Of course, "Way to go science"! but then the idea of mass produced nanobots sounds like a plot to a Proper Horror story!!

There have been numerous researches on the mass production of various 2D nanomaterial because they show outstanding physical and chemical characteristics when they are truly 2D.

With strong mechanical force or chemical reaction only, each existing exfoliation method has its limitation to make 2D material when the scale of manufacturing increases. They also face the issues of high cost and long process time.

After several years of research, Professor Do Hyun Kim in the Department of Chemical and Biomolecular Engineering and his team verified that optimized shearing in their reactor provided the highest efficiency for the exfoliation of nanomaterial. For the increased reactor capacity, they selected a flow and a dispersive agent to develop a high-speed, mass-production process to get 2D nanosheets by physical exfoliation with an aqueous solution.

The team proposed a flow reactor based on Taylor-Couette flow, which has the advantage of high shear rate and mixing efficiency even under large reactor capacity.

In this research, Professor Young-Kyu Han at Dongguk University-Seoul carried out the Ab initio calculation to select the dispersive agent. According to his calculation, an ionic liquid can stabilize and disperse 2D nanomaterial even in a small concentration. This calculation could maximize the exfoliating efficiency.

Additionally, they applied dispersive nanomaterials including graphene, molybdenum disulfide ( MoS2), and boron nitride (BN) to inkjet printer ink and realized micrometer-thick nanomaterial patterns on A4 paper. The graphene ink showed no loss of electrical property after printing without additional heat treatment.

nanowerk.com, Dec. 19, 2018 - Highly scalable process to obtain stable 2D nanosheet dispersion.

Thank you KAIST!

The two well-known methods of creating graphene are spraying a carbon source on a piece of flat metal in a vacuum chamber and burn it in a non-reactive gas while spraying more carbon source. Each carbon molecule is said to be "chemical vapor deposited" and the process is called "chemical vapor deposition" or CVD.

That gets you a sheet of 2D material... stuck on some piece of metal, there could "wrinkles" and overlaps (aka, defects), using this method. It is costly and time consuming, requires special equipment, etc., and you have to somehow remove it from the metal... a pain.

The other method is to take as pure a source of material. The 2D materials is layered via Van der Waal forces where like atoms "cling" together. Then either a physical or chemical process is applied to tear apart those bonds (nondestructively, of course). This is the method being discussed in the article: exfoliation.

Using a specialized exfoliation processor (Taylor-Couette flow is two rotating cylinders at a specific rate allowing material to pass through to be "exfoliated"). The researchers did the calculations for optimal processing, handed over their demands to another group, who made various samples of several materials (studied, write ups, comparisons, etc).

The list is impressive: graphene, boron nitride, and MoS2 (look! a TMD!). All of which fit into "semi conductor" realm and we all know how necessary those things are in the modern world (soon to be IoT?).

The result... could this be the "real" breakthrough to our 2D future?!!!!

Is this really the Christmas Miracle the world needs??


and

Currently, they typically grow the 2-D material by chemical vapor deposition (CVD) on pieces of copper heated to about 1000 °C. This results in graphene with large crystals, which means there are few crystal boundaries for electrons to bump into which, in turn, leads to good electrical qualities. After growing the film, researchers must somehow transfer the graphene to another surface, such as a silicon wafer or a plastic film.

The AIST researchers built an apparatus they call a plasma blower to gain finer control over the plasma’s composition and flow. The device blows methane, argon, and hydrogen gases through a microwave field that energizes the molecules to form a plasma before they hit the surface where the researchers want to grow graphene.

Blasting a copper substrate with this controlled plasma, the researchers produced high-quality graphene with large crystals at just 400 °C. The optical and electrical qualities of the graphene grown by this method are comparable to those of graphene grown at high temperatures by CVD. So far, the blower produces a plasma about 50 mm across, resulting in graphene strips of the same width. Kim believes it will be possible to grow sheets of graphene a meter wide.

C&EN (cen.acs.org), Jan 15, 2019 - Growing quality graphene at low temperatures.

Could this be the year that graphene (finally) steps out to dominate our world??

The ability to grow the crystal sheet in situ will change everything! A meter wide sheet would be awesome!

Nanotech Energy www.nanotechenergy.com..., the world’s top supplier of graphene, graphene oxide and graphene super batteries, announced today that it has cleared a monumental hurdle in the production of high-quality graphene-based materials. The first patent for Graphene, now exclusively licensed to Nanotech Energy, was filed in 2002 by Dr. Richard Kaner, Nanotech co-founder and UCLA professor of Chemistry and of Materials Science and Engineering.

AP (apnews.com), Jan. 16, 2019 - Nanotech Energy, the UCLA Energy Incubator and Holder of First Patent for Graphene Announces Profound Achievement in Production of High Quality Graphene Based Materials.

I went to their website and there is not much information their either. It is a hype driven site about what graphene can do but short on actual products (oh, they list them and what the wonder material can do but then, at the end, they ask that you email them, or call them).

But hey, I want our future now! And if this hype announcement is any indication, we may be in for the year of GRAPHENE (finally!!).

To grow graphene over large areas, the 2-D material is typically grown on a commercial copper substrate. Then, it’s protected by a “sacrificial” polymer layer, typically polymethyl methacrylate (PMMA). The PMMA-coated graphene is placed in a vat of acidic solution until the copper is completely gone. The remaining PMMA-graphene is rinsed with water, then dried, and the PMMA layer is ultimately removed.

Wrinkles occur when water gets trapped between the graphene and the destination substrate, which PMMA doesn’t prevent. Moreover, PMMA comprises complex chains of oxygen, carbon, and hydrogen atoms that form strong bonds with graphene atoms. This leaves behind particles on the surface when it’s removed.

After combing through materials science literature, the researchers landed on paraffin, the common whitish, translucent wax used for candles, polishes, and waterproof coatings, among other applications.

In simulations before testing, Buehler’s group, which studies the properties of materials, found no known reactions between paraffin and graphene. That’s due to paraffin’s very simple chemical structure. “Wax was so perfect for this sacrificial layer. It’s just simple carbon and hydrogen chains with low reactivity, compared to PMMA’s complex chemical structure that bonds to graphene,” Leong says.

The researchers transferred the paraffin-coated graphene into a solution that removes the copper foil. The coated graphene was then relocated to a traditional water vat, which was heated to about 40 degrees Celsius. They used a silicon destination substrate to scoop up the graphene from underneath and baked in an oven set to the same temperature.

Because paraffin has a high thermal expansion coefficient, it expands quite a lot when heated. Under this heat increase, the paraffin expands and stretches the attached graphene underneath, effectively reducing wrinkles. Finally, the researchers used a different solution to wash away the paraffin, leaving a monolayer of graphene on the destination substrate.

new.MIT.edu, March 6, 2019 - Smoothing out the wrinkles in graphene.

To make graphene they use CVD (chemical vapor deposition), where a pre-cursor, typically methane, is sprayed upon a substrate, this copper foil. Great. Now you have to get the graphene off of the foil. They were using a polyacrylate to hold the graphene while the copper was dissolved as described above (the CVD part is at the original article). That is where the problem lies. Making graphene on copper, no sweat. MIT even figured out a roll out process. It was the transfer process that introduces impurities and wrinkles which all affect the pristine 2D functionality.

Enter moustache wax!

Since, as the article points out, paraffin is used in current manufacturing techniques like waterproofing your tent, they used a known "spin coating" method to make a thin coating for the graphene. Then, as described above, they ended up with a stretched, wrinkle free, graphene with little, to no, impurities on the surface. The article actually shows the PPMA substrate vs. wax and one looks like one of my vinyl records that I salvaged from the Great Flood of '03 while the other looks flat and smooth.

Of course they say they are going to try and improve there method, yadda, yadda, yadda, but I say, "We have been waiting for a long time. Let's try your roll-to-roll graphene fabrication method transferred via paraffin substrate process while you tinker with you was formula!"

OMG!! I have lived to see the day!!

A recent University of Cambridge spin-out company, Paragraf, has started producing graphene—a sheet of carbon just one atomic layer thick—at up to eight inches in diameter, large enough for commercial electronic devices.

Paragraf is producing graphene 'wafers' and graphene-based electronic devices, which could be used in transistors, where graphene-based chips could deliver speeds more than ten times faster than silicon chips; and in chemical and electrical sensors, where graphene could increase sensitivity by a factor of more than 30. The company's first device will be available in the next few months.

phys.org, March 12, 2019 - Cambridge spin-out starts producing graphene at commercial scale.

The thread started at the end of 2011. There have stories about this breakthrough and that breakthrough. There have been "wonder material graphene" stories galore. But no graphene products except some bike tires (that end up wearing faster than normal), golf balls, a jacket made with aerogel, and maybe a canoe or two. But no electronic device or real battery. Nothing that we could turn and point to and say, "Hey! It is that wonder material, graphene! And it makes that device way better than before!"

Well good! My arms are tired of beating this dead horse!!

An 8" circle of graphene... might make for a cool phone screen! Let's play ball!!

Graphene updates! It must be something about this time of year because there seems to be news stories coming out daily about the "wonder material" (even though there is no "duck and cover" graphene mega app yet).

phys.org, April 29, 2019 - Purifying water with graphene.

They did not even make a membrane! They just suspended GO in saline and bacteria growth medium (many E. coli we were killed in the study!), showing that "2.5 g/l" was enough to significantly clear the water of bacteria (same source). The GO and bacteria would settle out ("flocculate") and they would rinse in an ultrasound bath to re-use the GO!

phys.org, April 29, 2019 - Decoupled graphene thanks to potassium bromide.

Here, they used a layer of potassium bromide that prevented the feedstock from forming bonds with the copper substrate when making graphene using chemical vapor deposition (same source). Since it is already used an industrial solvent, potassium bromide could be key to unlocking mass production of defect free graphene.

"We took a chemically modified form of graphene, [...] and attached functional groups that provide convenient chemical links for robustly bonding metal atoms [in a catalyst]. In this way, we chemically anchored individual copper atoms to the surface of graphene and found they had unprecedented efficiency for catalyzing the chemical reactions used for production of important pharmaceutical substances," said Radek Zbořil, the director of RCPTM and originator of the whole concept.

Strong anchoring individual atoms for catalytic purposes has been an attractive, but unfeasible 'pipe dream', until recently. "Most of the approaches previously developed do not provide sufficiently strong anchoring, eventually resulting in the catalytic atoms' release during the reactions or recycling. The technology developed in Olomouc has unique ability to firmly anchor a wide range of individual atoms in sufficient quantities and even control their oxidation state. Thus, the new catalysts offer a wide spectrum of applications," said Paolo Fornasiero from the University of Trieste, who has a wealth of experience in developing and applying new types of catalysts.

PRNewswire.com, April 29, 2019 - Scientists From Palacký University in Olomouc Accelerate Chemical Reactions With a Single Atom.

The quote says "copper" but they invented a simple chemical process to attach other atomic metals including gold, platinum, cobalt, and nickel (same source). Since the metal is attached to the graphene sheet, it is like a forest of single metallic atoms ready to react. They are thinking this can be used in many different processes.

While not here just yet, the Graphene Future is coming!

Hey!

What is up ATS?!??

Sick of politics and the Covid economy we are embraced with while rolling over the lemming sea cliff??

I am.

So I put my money where my mouth is and see how well one of these Oros graphene aerogel jackets for us folk flowing out of NASA tech stand up to the Great White North’s winter!

I have the second version of the Oros Orion jacket in my possession!!

Woot!

It went on sale and I pulled the trigger knowing full well that I could go hungry on Thanksgiving and have to delay my gratification until my meal the next day (I was afeared that we have the city shutdown the week of T-day, as I thought, they pushed until the following Tuesday... until New Years Day... ).

But that means walking to the grocery store and work (and anywhere else cabin fever sends me out into the cold!)

Full report coming on the wonder material, graphene and how well it works as a 2nm thick insulation on a ski jacket!





ETA: My original post on this company was 2016!

www.abovetopsecret.com...

Congratulations !! I hope the jacket excedes your
expectations. I am anxious to hear about it

a reply to: TEOTWAWKIAIFF

a reply to: HarryJoy

All last week we around 32°F (0°C) with threats of snow. We finally got some on Thursday and then them dropped.

Today, 3° F (-16.1 ° C), slight breeze, and clear as could be.

So I go to the store because they have a coffee shop there. It is some 15 blocks due west (have to walk around a school), about 30 minutes out in the cold. Just a long sleeve cotton tee shirt, light long Johns, and too light of socks (just to see how warm I will stay).

No adjustments. Jacket on. Out the door.

If this is a ski jacket, a powder skirt would be nice. Or, a draw string/belt at the waist to keep the snow (or cold) out. There is a useless chest strap thing that I can not see a need for. The sleeves have an inside liner with elastic wrist bands that are very functional!

There is a hood that is nondetachable. My color is called “Marachite” which is an olive green (too dark in the AK to walk around in a black jacket in winter time!). The pocket zippers seem flimsy compared to the main zipper down the front. They are not glove friendly. The main zipper has Velcro flaps that are easy enough to close.

I was warm enough while moving around. A couple of times while waiting for traffic I got a blast of Arctic chill up my back but if I layer up two shirts that would take care of that.

Compared to my fleece/Filson jackets, this is stylish and lightweight while keeping me just as warm. Below zero I would add my fleece back in to be sure but down to zero this passes the test!

When the next snow storm hits I will try out the hood (could be a better experience as it too can Velcro across your face).

Keep it zipped up to your neck and maybe have a backpack with a waist cinch and you are good to rock and roll!!

The pocket zippers are way too cheap for how much this costs (my only real concern).

(It is like a light fleece but kind of like a Filson vest with the tin cloth which feels dense but is rather light and keeps you warm).

This is v2 of the jacket and you can get v1 for 169US$ (if they have any in your size).

All in all, would not even have known about the graphene aerogel in there if I had not purchased it for that very reason!!

I am happy with my purchase and will figure out how to close the waist area!

It has been a long time since I have provided any graphene updates! (Two years! Wasn’t there some Covid thingy going on?…)

The news hasn’t stopped but neither has fabrication methods improved! The best news is from MIT that “punched out” repeating square holes in silicon wafers where they CVD atomic carbon which then grew perfectly flat graphene crystals in the spaces then they grew together to form a sheet of graphene! Of course, more studies, can it scale?, etc needs to be answered but that is the coolest thing going on that I have seen (news.mit.edu). I hope that it scales!

And here is some current news:

Nature.com, 8 Feb 2023 - Direct formation of carbon nanotube wiring with controlled electrical resistance on plastic films.

Basically, they etched wire paths in polypropylene (plastic) and then used a laser to create CNT in the pathways. They were able to control how much resistance the CNT wires had by how fast they allowed the laser to move!

Fast forward a bit and those “beer tent” wrist bands may be your next smartwatch!!

C’mon sheets of graphene!!!

Although I would settle for a graphene battery…

a reply to: TEOTWAWKIAIFF

Thanks TEOTWAWKIAIFF,

Much appreciated- I always keep an eye on this thread and enjoy your work in updating.

Again, much appreciated

a reply to: Paddyofurniture

My inner nerd thanks you!!

I find the brink of a breakthrough to be interesting in and of itself. But we are in a holding pattern (seems to be on several technological fronts) and all I can do is keep an eye open to the developments!



ETA, link, news.mit.edu, Jan 18, 2023 - MIT engineers grow “perfect” atom-thin materials on industrial silicon wafers.

a reply to: TEOTWAWKIAIFF

Whenever they say "grow" - it always makes me think back to those rumors about quasi-crystals being grown in a low/microgravity environment for use in classified aerospace applications.

At some point in the 90's/0's- and I cant find a link/the papers- LM paid a load of PhD's to skydive out of planes to study low G crystalline growth.

It's also notable that Icosahedrite (a naturally occurring quasi-crystal found on Earth) is believed to come from meteorites/asteroids where it "grew" in the micro gravity of space

If there was a zero G/micro gravity manufacturing pre requisite on your revolutionary grown material....it would be quite the barrier to entry.
Must have regular space access (or the money to emulate a microgravity manufacturing environment on earth) would exclude most.

I have an old bottle of graphite powder labeled of cause Graphene, the name has been used for probably 70 years at a guess reply to: Thermo Klein