Andre Geim is commonly asked why he never patented graphene. The Nobel laureate’s famous answer is that a representative of a large high tech company told him that in some years, the high tech company will hold so many graphene patents that Professor Geim will spend a fortune and his entire life suing them. But few people know that graphene was indeed patented, two years before the first research papers came out of the Geim lab in Manchester and the de Heer lab at Georgia Tech, by a company called Nanotek Instruments.

The world’s first graphene patent includes a sketch of carbon nanotubes unrolling to form graphene sheets.

US patent number 7071258, entitled “Nano-scaled graphene plates”, was filed in October 2002. The patent contains a drawing of single- and multi-walled carbon nanotubes, which unroll into monolayer and multilayer graphene sheets. The invention protects not only graphene itself, but also graphene composites that include other materials, such as polymers, metals, glasses, carbons, etc. The patent owners, Bor Jang and Wen Huang, also use the patent to coin the term “nano-scale graphene plates” (NGP), advertised by many companies today. So how come this visionary patent skims below the radar of most graphene researchers today?

“Unfortunately, Dr. Geim and most of the scientists in the field of nano materials failed to search for patent literature where many significant discoveries and technology developments are reported. Based on our open literature and patent document search results, there does not appear to be any report before 2002 that documented the actual production and use of single-layer graphene sheets for any application”, explains Ron Beech, Director of Marketing and Sales for Angstron Materials, the descendant company of Nanotek.

Ron Beech points out a rift that goes deeper than the graphene patent issue – most scientific researchers from the academic world never bother to look into the patent literature, where they could find solutions to many obstacles that they face in the daily lab grind. Whereas efforts have been made, especially in recent years, to promote the collaboration between industry and academia, the sharing of knowledge has in fact gone only one way. Industry leaders tend to follow the scientific literature very closely, but scientists fail to scout the patents.

“I couldn’t agree more with Ron”, says Elena Polyakova, CEO of Graphene Laboratories, best known for its daughter company Graphene Supermarket. “Scientists do not read patents, and often don’t know what the industry is doing”. Dr. Polyakova knows both sides of the coin, having followed up a successful scientific career with her post as a founder and CEO of one of the largest graphene suppliers.

“Dr. Bor Jang (co-owner of Angstron Materials and owner of the first graphene patent) is a rare scientific talent, and he did loads of work on graphene well before the academia caught up”, adds Dr. Polyakova. “He was one of the pioneers in the development of graphene and has over 40 patents related to graphene production and applications, including the first patent for single layer graphene in 2002 and the first patent on graphene reinforced metal, glass, carbon and ceramic-matrix composites and single layer graphene-reinforced polymer composites. But Dr. Jang almost never published scientific papers, for which reason he is almost unknown in academia.”

Working with emerging nano-technologies like graphene, one needs to overcome a series of obstacles and technological challenges to extract the full potential of the technology. While scientists tend to skim on the bottom-level details for the sake of displaying the magnificent properties of the material in scientific publications, patents are a platform through which the industry tends to present the solutions to exactly those challenges and obstacles. Perhaps a stronger cohesion and collaboration can be formed if academic scientists start looking the other way.

Marko is a scientific researcher (PhD in Physics, University of Twente, NL), with experience in graphene and other nanomaterials. He is the owner of Graphene Tracker, Assistant Professor at the Institute of Physics in Belgrade, blogger and online content manager for Graphenea, and a member of the Advisory Board of the Graphene Stakeholders Association.

Twitter: @graphenetracker

RLittle

Dear Mr. Marko Spasenovic,

Thanks for the very interesting article that you publish. US patent number 7071258, entitled “Nano-scaled graphene plates”, was filed in October 2002 but I would like to note for the factual record that this patent 70712158 was not the first patent filed on graphene and single walled carbon nanotubes. The first patent 6,761,871, entitled “Magnetic Production of Carbon Nanotubes and Filaments” was filed in Dec 2000 and May 22, 2001 by Reginald B. Little. This patent 6,761,871 was issued in July 2004. This patent by Reginald B. Little also clearly and transparently contained images and detailed descriptions of single wall carbon nanotubes and single layer graphene as well as multiwalled carbon nanotubes and multilayer graphene and carbon filament and how carbon nanotubes form from graphene and multilayer graphene intermediates. Furthermore the patent expresses how graphene can be formed rather than the nanotubes. Later in Aug 2002, Reginald B. Little extended this mechanism into a comprehensive mechanism for plasma/gas uncondense formation of graphene and carbon nanotube in laser plumes and electric arcs of graphite as presented (entitled : “Mechanistic Aspects of Carbon Nanotube Nucleation and Growth”) at ASC regional meeting 54th SERMAC in South Carolina by Reginald B. Little and published in March 2003 in Journal of Cluster Science. This is very exciting science, I thought I would note the facts by dates of documented patents and publications.

MarkoSpasenovic

Professor Little,

Thank you for the comment and for participating on the website. Indeed your patent predates the one by Bor Jang. What I wanted to show here is the oldest patent that protects a method of making graphene itself. Your patent seems to be focused more on carbon nanotubes. I think the issue is debatable and I welcome your contributions.

RLittle

Dear Spasenovic,

First let me clearly state that my comments in no way are meant to insult you nor anyone else. I do not know you but I respect you in your opinion. I also just focus on the facts. I hope facts are not offensive to those of excellence.

I thank you for your friendly response. Based on the published facts, My patent (6,761,871) focuses on both carbon nanotube and graphene, based on the content and semantics within the said patent. Even within the title ‘filamentous carbon’ is synonymous with layered nano to micro graphene as I clearly further illustrated and described in great details in many figures and in many large sections of this patent (6,671,871). So graphene is identified within the title of patent 6,761,871. Being original, I interchanged the terminology of filamentous carbon and graphene as this was written back in September – December 2000. But the illustrations clearly present the intent and expressed equivalence of graphene and filamentous carbon as described in this patent
6,761,871. Such interchanging terminology is not unusual within original inventions. Many major subheadings within my patent 6,761,871 (Dec 2000) clearly and repeatedly with many great details state, define and describe ‘graphene’ and there are many illustrations of graphene in US Patent 6,761,871. Graphene in my 2000 patent (6,671,871) is just as important as carbon nanotube. In fact, I identified graphene in patent 6,761,871 as the basis for how the carbon nanotube forms. The extremely honorable thing about my invention of graphene in this patent 6,761,871 in 2000 is that I do not stop in describing how graphene is the egg and seed for carbon nanotube formation. The honorable and excellent thing about this patent 6,761,871 is that I correctly and thoroughly gave details for how to stabilize the graphene (single layer) and thereby patent 6,761,871 invented (first) the correct method for forming graphene and for the stability of graphene. That is an excellent invention. Mr. Spasenovic with all due respect and kindness to you ‘that is extremely EXCELLENT”. It is excellent not because I did it. It just is excellent, regardless of who did it! That (6,761,871) is simply beautiful and excellence. That excellence in my invention of graphene in 6,761,871 was back in 2000. Please Sir, do not ignore that. That is an excellent invention worthy of honor. Moreover, I clearly back in Fall of 2000 in 6,761,871 invented the conditions and described the type of metal for which graphene would better grow. I called them B2 metals , in particular I identified Cu (copper) as best for forming single layer graphene; such invention, prediction and discovery in 6,761,871 were back in 2000. Now in 2013, scientists all around the world are growing the best CVD graphene on Cu. No one prior to 2000 (and prior to 6,761,871) had given a viable method for producing isolable high quality single layer pure crystalline graphene. I have the great admiration of Ruoff who in 1999 had an aim and objective of forming single layer graphene as presented in his 1999 method of rubbing of micron graphite pillars, but as to this date this 1999 method of Ruoff has not formed single layer graphene. The documented fact by ‘truth’ and many many subsequent observations is that the first correct method of forming single layer pure crystalline graphene was given by Reginald B. Little in this US patent (6,761,871). Excellence must acknowledge excellence else it is not excellent.

MarkoSpasenovic

Professor Little,

Thank you for your input. I include here links to the two patents for interested readers of this website:

Dear Marko,
I respect your wish not to discuss the priority any more and I do not write more expecting a response from you. But I thank you for the article and your friendly response. I also do not mean to upset you and I am sorry if I have.
It is not my intent to anger anyone. I only wish to tell the truth! If in telling the truth then I bring attention to my work then so be it!
As you have listed the two patents for readers to compare, I would like to note to the readers that in considering my patent 6,761,871 (and patents in general not just mine) that the fewer restrictions on the claims of the patent then the greater reach for that patent. On such basis, the claims for my patent note carbon nanotubes and such claims are very broad as NO restriction is placed on the diameter of the claimed carbon nanotube. Therefore these claims of 6,761,871 also embrace carbon nanotube of large radius (in principle radius going to infinity) which include graphene! So the claims embrace graphene as well as carbon nanotubes. Moreover graphene is included in the title of the patent 6,761,871 as it is expressed by carbon filaments and Figure 16 illustrates graphene layers constituting carbon filaments. Furthermore within the description of my patent 6,761,871 distorted graphene and carbon nanotubes are used interchangeably and the magnetism that contributes thereof. But clearly within the description the invention gives a basis for carbon nanotube of great radius as in the limit of larger radius the disclosure demonstrates the C atom production rate and diffusion distance limiting the growth and distortion of larger distorted graphene and favoring the nucleation of a new graphene sheet. The large size also restricting the bending of the graphene sheet.
The claims of 6,761,871 are not restricting in diameter of the nanotubes, so diameter of exceeding size is graphene as demonstrated by the processes within the description in details and clarity.
With Kind Sincerity,
Reginald B. Little

Jesse Jenkins

I’m a newbie to IP. Does owning a patent like graphene mean that anyone who manufactures graphene, or finds a use for it in a new product must pay the owner of the patent? And if the user has to pay by patent law, who decides how much?

MarkoSpasenovic

Hi Jesse,

If one would own a patent for graphene itself, then anyone who uses graphene in their product would have to arrange in advance to pay a certain percentage of the profits to the original patent owner, or face a lawsuit. The court which holds the lawsuit would then determine if an infringement has been made and how much the infringer would have to pay to the patent owner.

That said, there are some conditions that apply to patents that limit what can be patented. If something was already reported in the scientific literature, for example, it cannot be patented. That’s one of the reasons why graphene itself cannot be patented – the prediction that graphene exists has been in literature for decades. What can be patented is a method of producing graphene, as is the case with the original patent here.

There are now many patents that protect different methods of making graphene. This particular patent by Bor Jang seems to be the oldest, and was filed two years before any scientific literature describing the synthesis of graphene came out.

Thanks for this info Kenny. You asked me on Facebook what I think of this video and the patents; I thought I’d reply here.

I think the invention is interesting (the graphene-related invention), because many people are looking for ways of producing graphene and few-layer graphite by chemical or mechanical means directly from graphite. However, the patent in question explicitly claims that the chemical used is hydrochloric acid, heated between 100 and 200 degrees. Hydrochloric acid is very toxic, and especially heated to such temperatures can present a threat to human health and the environment. The fact that Mr. Petrik in his video explicitly claims that “there is no acid here” makes me very suspicious of the other claims of the video.

The patent itself took 6 years to get approved, which is very unusual. It seems that the reviewers had issues with prior art, which included some scientific papers in the Russian literature on getting carbon nanotubes with this method. The prior art papers also include Novoselov’s original 2004 Science paper, although I wouldn’t really count that as prior art, since the patent of Mr. Petrik was filed in the same year and anyways describes a totally different method of producing graphene.

China has no regards for patent laws so the entire patenting conversation is Moot. I can go online buy a product patented by a company in Ohio with a branch in S. Korea and sell it on EBay all day long and make huge money. Would I be held liable? That is a question I am researching the answer for, Perhaps Mr. Spasenovic can answer it. I have gone as far as contacting the patent owner today. I have done this by email which I saved, phone call and next registered mail. If I do not hear anything from them in 10 business days I will market the product full scale. I know this much. You would buy it!