ON PAGE 4New graphene batteries

ON PAGE 7Hazard assessment for nanomaterials

ON PAGE 17Graphene in China

IN THIS MONTH’S ISSUELatest news on commercial activity in graphene and 2D materials

Graphene in the oil & gas industryENVIRONMENTALLY FRIENDLY PRODUCTS AND ENHANCED MATERIALS FOR DRILLING AND EXTRACTION.

Graphene in AsiaDRIVE TO COMMERCIALIZATION OF GRAPHENE IN ASIA.

Graphene Quantum DotsAPPLICATIONS IN PHOTODETECTION, PHOTOVOLTAICS, (LEDS) AND PLASMONICS.

Business newsALL THE LATEST BUSINESS AND PRODUCT NEWS.

Materials Magazine | Issue 4 – April 2016 A Future Markets Publication

GRAPHENE & 2D

03 EDITORIAL

04 2D MATERIALS NEWSLatest industry, product, research and policy developments in graphene and other 2D materials.

08 GRAPHENE QUANTUM DOTSPromising the exceptional properties of quantum dots but without the toxicity, graphene quantum dots could be the next big thing.

11 GRAPHENE IN THE OIL & GAS INDUSTRYAs fossil fuels deplete and oil & gas companies have to dig deeper and in more extreme environments, the need for advanced materials with new capa-

16

bilities is required. Graphene is a prime candidate to meet this need.....

16 GRAPHENE IN ASIAAsia continues to lead the way in terms of product development, patenting and government funding in graphene, with new funding initiatives in China and Asia.

Cover StoryGraphene-based products are already under develop-ment in the oil, gas and petrochemical industries in sensors, absorbents, drilling fluids, coatings and waste-water treatment.

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contentsGRAPHENE & 2D MATERIALS MAGAZINE

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Welcome to Graphene and 2D Materials Maga-zine, brought to you by Future Markets, publisher of Nanotech Magazine (www.nanotechmag.com, and the world’s leading provider of nano-technology and nanoma-terials market informa-tion.

Asia leads the way in gra-phene The market for graphene contin-ues to expand, with new product launches, multi-million dollar fund-ing for companies and start-ups and new government initiatives worldwide. This process is most ap-parent in Asia, with government’s strongly backing graphene to meet future technology challenges. China especially is strongly com-mitted to the commercialization of graphene with increased funding for product development centres a core part of the 13th five year plan (2016-2020). Malaysia has also recently announced plans to fund graphene commercialization initia-tives with the hope of generating billions of dollars in product rev-enue by 2020. These time frames

are very optimistic but funding to meet these objectives is significant with China planning to fund over 100 new centres. In November the government issued an official document “Guidance on Graphene Industrial Innovation and Develop-ment” that outlined a strategy for accelerating graphene commercial-ization in China. Numerous gra-phene enhanced products (mainly conductive additive based) have hit the market in China over the past twelve months and this trend is continuing into 2016.

2DMATERIALSMAG

Issue 4 Editorial

by LINDA ERIKSSONChief Editor

ABOUT 2D MATERIALS MAGAZINE2D Materials Magazine (www.2dmaterialsmag.com) is published by Future Mar-kets (www.futuremarketsinc.com), the world’s leading provider of nanotechnology and nanomaterials market information. Future Mar-kets provides leading-edge market research reports on advanced materials.

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© Future Markets, Inc. 2016

EDITORIAL

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Versarien has signed a memo-randum of understand-ing (MOU) with Warwick

Manufacturing Group to collaborate on the production of graphene-enhanced lithium batteries and supercapacitors, using graphene nano platelets. Working with the SME team and battery specialists, Versarien will have access to WMG’s expertise and world leading facili-ties in the Energy Innovation Centre.Read more at www.versarien.com

Anson announces graphene productionAustralia-based minerals explora-tion company Anson Resources

Limited has announced production of Single Layer Graphene from the company’s Ajana Graphite Ajana Graphite Project, located inWestern Australia. The research work was carried out by Flinders University of South Australia under the direction of Professor Amanda Ellis. The graphene was produced by exfoliating the Ajana graphite sample with a high energysurfactant system. Read more at ww.ansonresources.com

Skeleton Technologies signs €3.5 million distribution agreement Skeleton Technologies has signed a new agreement to supply its patented graphene ultracapacitors to French transport tech developer Adgero. Under the deal, the Stras-bourg-based Adgero will source SkelMod 50F 160V ultracapacitor modules for its Kinetic Energy Re-covery Systems (KERS) pioneered to increase efficiency for the trucking industry. Read more at http://www.skeletontech.com

Flinders Resources Limited has successfully produced graphene for the first time us-

ing graphite concentrate from the Company’s Woxna mine in Sweden. The concentrate has been pro-cessed into graphene by Swedish start-up 2D Fab AB, a spin-off from Mittuniversitetet (Mid Sweden University). Sven Forsberg, of 2D Fab AB, stated, “The large size of natural graphite flakes in Woxna concen-trate, combined with a gentle ener-gy efficient exfoliation process, are the keys to producing customer

tailored, molecular thick graphene, with superior electrical conductiv-ity and barrier properties. Addi-tionally, the potential competitive advantage for these graphene products is that the graphitic raw material comes from a sustainable EU source.”Graphene was produced using 2D Fab’s proprietary low environmen-tal footprint manufacturing tech-nology which utilises a low energy, hydro-mechanical exfoliation pro-cess to produce high conductivity graphene . This process is more en-ergy efficient and less destructive

Flinders successfully produces graphene

Versarien signs battery agreement

2D MATERIALS

to the final graphene product, compared to other hydro-me-chanical exfoliation processes, such as rotary dispersers and ultrasonic treatments. Read more at http://2dfab.se/en/part-ners-2/

Garmor develops com-posites for energy and electronics applicationsGarmor has developed a new range of graphene-based composites for high-volume electronic and energy storage applications. The company has produced compression-mold-able GO-composites that can be shaped and stamped into almost any form factor. Read more at http://garmortech.com/

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Graphene 3D Lab Inc. is increasing production capacity of graphene oxide 5-fold due to increased demand from industrial customers. Elena Polyakova, Co-CEO stated, “We are delighted to see increasing demand for graphene materials and composites. We are committed to stay on track to satisfy this demand.” The company is also continuing to develop its research, develop-ment and royalty agreement with a Fortune 500 listed manufacturer.

Graphene 3D has successfully con-cluded the initial task of the Agree-ment. Elena Polyakova, Co-Chief Execu-tive Officer said, “We are fortunate to have a world leading R&D team in the graphene and nanomate-rial field. Meeting or exceeding all of a client’s performance criteria is another example of how we are ideally suited to work with existing manufacturers to assist them with incorporating graphene into their

products’”.Upon successful completion of the research phase, and subject to approval by the U.S. Food & Drug Administration, the developed materials will become a part of a consumer retail product. The Agreement calls for all re-search and development costs and royalty obligations to be paid by the partner. Read more at www.graphene3dlab.com

I taly based graphene produc-er Directa Plus has received international certification

from Farcoderm Srl. for all of its graphene-based products, confirming them to be safe for human contact. Farcoderm is a specialist testing agency that as-sesses safety, tolerability and sen-sory aspects of all products which may come in contact with human skin. Giulio Cesareo, Chief Execu-tive Officer of Directa Plus, stated: “We believe we are the first gra-phene producer to be awarded such certification. The results confirm that our graphene-based products are created through a process that uses only physical forces and no chemical additives.” Read more at http://www.directa-plus.com/

Imagine Intelligent Mate-rials announce large scale production for applica-tions in geotextilesImagine IM, an Australian devel-oper of graphene applications has entered into a licensing agree-

ment with Australia’s largest geo-textiles manufacturer, Geofabrics Australasia Pty Limited. The agreement will see Geofab-rics become the exclusive Aus-tralian licensee of Imagine IM’s graphene coating technology for applications in geotextiles. Geo-fabrics will use the technology to offer Australian civil engineering companies significantly improved capacity to locate and remedy leaks with applications in landfill and mining construction. Read more at http://imgne.com/

Talga Resources announc-es ramping up of graphene production Talga Resources Ltd has an-nounced that wet commissioning of its Phase 2 pilot scale test facil-ity in Germany has commenced. Phase 2 is an expansion of and improvement on Talga’s Phase 1 equipment and involves process-ing shaped raw graphite ore from Talga’s Swedish deposits in slabs up to 50 kg in weight each (up from 10 kg previously). Additional

Directa Plus graphene products certified safe

Graphene 3D increases capacity

2D MATERIALS

modified cells have been installed to increase total capacity of the facility to 365 kg ore feed at a time. The pro-duction process begins by ‘unzipping’ layers of graphite at an atomic level from Talga’s raw ore slabs in custom designed electrochemical exfolia-tion cells, followed by proprietary recovery and concentration stages. At full commercial scale, the process aims to deliver industrial volumes of high quality product, at competitive prices. Read more at http://www.talgaresources.com

Graphene-based patch devel-oper receives fundingThe University City Science Center, a research park in Philadelphia, has announced the six startups that will be part of the second class for its health tech accelerator, called Digital Health Accelerator (DHA). Graphwear Technologies has received $50,000 from the DHA, as well as $50,000 from Dreamit Health, in exchange for 8% equity to develop a graphene patch which measures dehydration, glucose, and lactic acid levels, from sweat. Read more http://www.graph-

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wear.co

Versarien collaborates for Graphene 3D Printing tri-alsVersarien is teaming up with E3D Online Ltd, a 3D printing special-ist, to carry out initial trials using graphene. By incorporating gra-phene into the 3D printing pro-cess, Versarien want to find out if 3D printed parts can benefit from the material’s properties. The gra-phene material is provided by the company’s subsidiary 2D-Tech.

Researchers develop new graphene based inks for high-speed manufactur-ing of printed electronics Researchers at the University of Cambridge in collaboration with Cambridge-based tech-nology company Novalia, have developed a method that allows graphene and other electrically conducting materials to be added to conventional water-based inks and printed using typical com-mercial equipment, the first time that graphene has been used for printing on a large-scale commer-cial printing press at high speed. “We are pleased to be the first to bring graphene inks close to real-world manufacturing. There are lots of companies that have pro-duced graphene inks, but none of them has done it on a scale close to this,” said Dr Tawfique Hasan of the Cambridge Graphene Centre (CGC), who developed the method. Read more at http://www.graphene.cam.ac.uk/

Vittoria launches new range of graphene wheelsVittoria Industries North America has launched the latest additions to its graphene-enhanced wheel

range. The Qurano 30C, 46C and 60C are tubeless-compatible car-bon clincher wheels. The compa-ny said the addition of graphene to the rims helps them deliver up to 50 percent improvements in spoke-hole strength, material strength and impact strength. Read more at: http://www.vit-toria.com/

Hazer Group signs two agreements to accelerate development of graphene production technologyHazer Group, an early stage development company, has announced a new agreement with the University of Western Australia (UWA) to develop Hazer technology for production of graphene. The project will focus on further tailoring of the Hazer Process reaction (a hydrogen and graphite production process) to improve the yield and quality of graphene produced.Under the agreement, Hazer will fund the development work which will see the University pro-vide a full time researcher to work with the company. Read more at http://www.hazergroup.com.au

U.S. start-up to launch range of graphene glovesU.S.-based company Oros Ap-parel is developing gloves made from graphene-coated aerogels that keep body warmth inside the gloves and insulate from low outer temperatures. The products will be on the market by end-2016. Read more at http://www.orosapparel.com

Thomas swan launches 2D Boron Nitride productsUK materials manufacturer Thomas Swan has launched a new

2D MATERIALS

range of 2D boron nitride products. The products are manufactured by a proprietary Direct Liquid Exfoliation process which exfoliates hexagonal boron nitride to produce 2 dimen-sional nano-platelets of boron nitride or 2D boron nitride.Read more at http://www.thomas-swan.co.uk/advanced-materials/our-products

All the latest 2D Materials business news is available at www.2dmaterialsmag.com

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A new publication by ECHA, RIVM and the JRC illustrates how to use data for different

nanoforms within the same sub-stance registration. The approach will form a cornerstone in the future guidance development on hazard assessment for nanoforms. The pa-per ‘Usage of (eco)toxicological data for bridging data gaps between and grouping of nanoforms of the same substance - Elements to consider’ is a scientific reference paper. At EU level, it offers regulators, research-ers, industry and NGOs an approach of how to scientifically justify that studies on one nanoform of a sub-stance can be used to predict the

hazard properties of other forms of the same substance. Read more at http://echa.europa.eu/publications/technical-scientific-reports

Nouveau Monde Receives Grant for Graphene produc-tionNouveau Monde Mining Enterprises Inc. has received a grant from the Natural Science and Engineering Re-search Council of Canada (NSERC), to help fund one of its ongoing research and development projects. The $25,000 grant, approved under NSERC’s ENGAGE program, was awarded last week to Dr. Mohamed

Siaj, Professor at the Department of Chemistry at the Université du Qué-bec à Montréal (UQAM) and Director of the NanoQAM Research Centre. Dr. Siaj, in partnership with Nouveau Monde, is spearheading the project titled: Development of a Chemical Process for Low-Value Graphite Ore Transformation to Value-Added Graphene-Based Electroactive Materials.

UK-based graphene producer Haydale has developed roll-to-roll gravure printing

of biosensors based upon electri-cally conductive graphene struc-tures and adherence proteins. The work was carried out as a result of a project undertaken by a con-sortium of organisations lead by the Frauhofer Institut fur Biomed-izinische Technik (IBMT) and involv-ing Haydale in the development of biocompatible and electrically conductive graphene ink suited for gravure printing. Using their proprietary HDPlas™

plasma technology, Haydale were able to develop the required surface functionalised graphene ink that was gravure printed and implemented as a base biosensor on cell culture microplates. Read more at http://www.haydale.com/biocompatible-graphene-ink-for-gravure-printing-of-biosensors

Grafoid signs MOU with Chinese tungsten companyGrafoid Inc. has signed a Memoran-dum of Understanding (MOU) with Chinese tungsten producer Xia-men Tungsten CO. Ltd., of Xiamen,

Haydale develops graphene ink for biosensors

Hazard assessment for nanoforms

2D MATERIALS

China, for the establishment of a strategic joint venture partner-ship.The companies will establish their joint venture in China for the production of Grafoid’s marketed suite of Mesograf™ and Amphioxide™ for commer-cial applications in composites, coatings, solar, batteries, fuel cells and catalyst materials for the China market. In February 2015, Grafoid received an $8.1 million investment from the SD Tech Fund™ of Sustainable De-velopment Technology Canada (SDTC) to develop a technology that will automate Mesograf™ graphene production and end-product development. Read more at http://www.grafoid.com

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Graphene Quantum DotsPromising the exceptional properties of quan-tum dots but without the toxicity, graphene quantum dots could be the next big thing.

C arbon and graphene quantum dots (CDs, GQDs) represent relatively new members of the carbon nanomaterials family. Graphene

is a ground-breaking two-dimensional (2D) material that possesses extraordinary electrical and mechanical properties that promise a new generation of innova-tive devices in flexible displays, transistors, photosen-sors, RFID tags, solar cells, secondary batteries, fuel cells, supercapacitors, conductive inks, EMI shielding heat insulation, anti-oxidation and LEDs. Studies have demonstrated that quantum confinement could appear

in graphene with finite size and edge effects-graphene quantum dots (GQDs).1

PropertiesGQDs are promising materials as substitutes for Cd, Ir, Ga, S, Se and P quantum dots (QDs) and possess unique structural and photophysical properties. Theoretical and demonstrated properties include high quantum yield, high electrical conductivity, high thermal conduc-tivity excellent photostability, biocompatibility, highly tunable photoluminescence (PL) property, exceptional

GRAPHENE QUANTUM DOTS

Types Optical properties Stability Toxicity Cost

Quantum yield Emission Half-height

Graphene QDs 90+ % (potentially) 380-570nm (no red)

>40nm (ca. 70nm)

Yes No Low

Semiconductor QDs

• CdSe 10-25%• ZnSe/CdSe 30-50%

480-640nm

40nm> No Yes High

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multi-photon excitation (up-conversion) property and non-toxicity.

SynthesisThere are two main strategies for synthesizing GQDs:

• Top-down method: Graphene oxide is manufactured then the graphene sheet is cut through controlled oxidation or the reduction process to the desired size to fabricate GQDs. • Bottom-up method: Low molecular weight com-pounds are polymerized to nm-size to obtain GQDs.

Specific approaches for preparation include:• molecular assembly of carbon ring structures• chemical exfoliation of graphite nanofibers2

• chemical synthesis• modification of graphite nanoparticles• electron beam lithography3

• pulsed laser synthesis• microwave pyrolysis 4 5

• hydrothermal graphene oxide reduction, resulting in the fracture of GO sheets into ultra-small pieces. 6 7 8 9

The bottom-up approach only produces a small quan-tity of GQDs, limiting it’s use. The top-down method potentially offers low-cost and high yield and is the main focus of commercial production. There are a number of technical hurdles that need to be overcome for successful production with low synthe-sis yields at present due to aggregation 10 11 that limit industrial scale-up. Also the synthesized GQDs currently display low quantum yield, poor control of the emis-sion wavelength and optical instability. 12 Researchers have recently turned their attentions to developing new methods for synthesis.

ApplicationsApplications of graphene QDs include catalysis, 13 14 bioimaging (e.g. membrane markers), 15 16 optoelectron-ics (LEDs), 17 18 19 printing, 20 photodetectors, 21 quantum computing and energy conversion devices. 22 These are also the main market for quantum dots. The advan-tage of GQDs is that demonstrate similar properties to cadmium-based QDs but without the potentially haz-ardous health and environmental effects, and at lower

Figure 1: Schematic of (a) CQDs and (c) GQDs. HRTEM images of (b) C-dots and (d) GQDs showing combination of zigzag and armchair edges (positions marked as 1–4). Image credit: Wiley. The Royal Society of Chemistry.

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cost. In the coming years they could be utilized as inexpensive and eco-friendly alternatives to QDs for opto-electronic devices such as displays and lighting devices.

ProducersACS Materials, LLC, USAwww.acsmaterial.comThe company is a graphene producer. They also pro-duce a range of graphene QDs.

KRI, Inc., Japanhttp://www.kri-inc.jpThe company produces graphene quantum dots and has developed proprietary synthesis methods.

Shanghai Simbatt Energy Technology Co., Ltd., Chinahttp://www.simbatt.com.cnThe company produces GQD powder and in solution.

References

1. L Li, X Yan, The Journal of Physical Chemistry Let-ters, 1(17), 2572 (2010).2. S Schnez, F Molitar, C Stampfer, et al., Applied Phys-ics Letters, 94(1), (2009)3. H Zhu, X Wang, Y LI, Z Wang, F Yang, X Yang, Chem. Commun, no. 34, 5118 (2009).4. X Wang, K Qu, B Xu, J Ren, X Qu, Journal of Materi-als Chemistry, 21(8), 2445 (2011).5. Libin Tang, Rongbin Ji, et al., ACS Nano, 6(6), 5102 (2012).6. D Pan, J Zhang, Z Li, M Wu, Advanced Materials, 22(6), 734 (2010).7. D Pan, L Guo, J Zhang, C Xi, Q Xue, H Huang, et al., Journal of Materials Chemistry8. J Lu, P S E Yeo, C K Gan, et al., Nature nanotechnol-ogy, 6(4), 247 (2011)9. http://pubs.rsc.org/en/content/articleland-ing/2015/nr/c5nr00814j#!divAbstract10. Zhu, S. J. et al. Strongly Green-Photoluminescent Graphene Quantum Dots for Bioimaging Applica-tions. Chem. Commun. 47, 6858–6860 (2011).11. Pan, D. Y., Zhang, J. C., Li, Z. & Wu, M. H. Hydro-thermal Route for Cutting Graphene Sheets into Blue-Luminescent Graphene Quantum Dots. Adv. Mater. 22, 734–738 (2010).

12. Lin, L. X. & Zhang, S. W. Creating High Yield Water Soluble Luminescent Graphene Quantum Dots Via Exfoliating and Disintegrating Carbon Nanotubes and Graphite Flakes. Chem. Commun. 48, 10177–10179 (2012).13. Zhuo S, Shao M and Lee S T 2012 ACS Nano 6 105914. Li Y, Zhao Y, Cheng H, Hu Y, Shi G, Dai L and Qu L 2012 J. Am. Chem. Soc. 134 1515. Zhu S, Zhang J, Tang S, Qiao C, Wang L, Wang H, Liu X, Li B, Li Y and Yu W 2012 Adv. Funct. Mater. 22 473216. S. Nandi, R. Malishev, K. Parambath Kootery, Y. Mirsky, S. Kolusheva, R. Jelinek, Chem. Commun. 2014, 50, 10299 – 10302.17. Luk C, Tang L, Zhang W, Yu S, Teng K and Lau S 2012 J. Mater. Chem. 22 2237818. http://www.nature.com/articles/srep1103219. Kwon, W. et al. Electroluminescence from gra-phene quantum dots prepared by amidative cutting of tatterd graphite. Nano Lett.14, 1306–1311 (2014).20. J. Wang, C.-F. Wang, S. Chen, Angew. Chem. Int. Ed. 2012, 51, 9297 – 9301; Angew. Chem. 2012, 124, 9431 – 9435.21. http://www.nature.com/articles/srep0560322. http://www.sciencedaily.com/releas-es/2015/06/150614225649.htm

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The last decade has witnessed significant advances in technology utilized for finding, estimating, and produc-ing oil and gas. Advances in fracking and horizontal drilling have had a huge impact on the industry. The decline in the price of oil has led to demand for tech-nologies that can reduce operating costs, improve operational efficiency and reduce costly non-productive time issues.The days of finding “easy oil” are more or less at an end and therefore enhanced reservoir extraction techniques are required. Exploration for oil increasingly needs to focus on hydrocarbon prone sedimentary basins that are much deeper, and more difficult to access. There-fore, new technologies are required that can cope with there environments. Nanomaterials are leading candidates for providing solutions for the extreme conditions of the harsh down hole environment (including high pressure, high heat

properties up to 300OC, 20,000 psi), and can protect equipment and prevent corrosion or fire. Reservoir recovery rates are typically 35% or less and the average size of new discoveries is only 25% of mid-1960s levels. It has been estimated that another trillion barrels will be available if existing reservoirs can be fully tapped. Current technology is very expensive and relatively inefficient for accessing these reserves. At present, about 60 percent of oil remains underground after primary, secondary and in some cases even third level recovery methods.As a result of these market needs, nanomaterials-based solutions are now beginning to find application in a range of areas in the oil and gas industry, such as coat-ings for pipelines, exploration and remediation as com-panies seek new ways to locate and extract oil and gas.

MARKET

Graphene in the oil & gas sectorAs fossil fuels deplete and oil & gas companies have to dig deeper and in more extreme environments, the need for advanced materials with new capabili-ties is required. Graphene is a candidate to meet this need.....

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0 Sensing and reservoir management

Reservoirs are complex subsurface permeable rock formations containing oil, gas or both. They have diverse internal properties and can be can be skinny, flat, or fragmented, as shallow as 1000 feet or as deep as 30,000 feet. Nanoscale materials can permeate oil-bearing rock, (low-micron range in sandstones, mid-nanometer range in carbonates). Due to their small sizes, nanoparticles are able to pen-etrate deeper into the formation and therefore, mitigate problems at early stages or provide a better resolution of the reservoir formation. Also, nanoparticles could potentially aggregate at the surface and prevent fluid loss where it is not desired.Down hole and process sensors are one of the impor-tant technology areas for the oil-field as to extract more oil it is of fundamental importance to characterize and monitor the reservoir. Nanosensors are being investi-gated for monitoring and exploring reservoir fluids and rocks beyond the wellbore. The exceptional electri-cal and magnetic properties of nanomaterials means they are suited for use as injected sensors and contrast agents. There have been a number of trials for nanotech solutions in this area; however there are still issues in terms of the mobility of the nanosensors, dispersion stability and up scaling. Schlumberger Ltd is working with Nantero to develop applications of their carbon nanotube memory devices in high temperature envi-ronments.

Figure 1: Schematic of boron doped graphene for ap-plication in gas sensors.

There are extensive research efforts on graphene-based ultrasensitive gas sensors that can detect noxious gas molecules in extremely low concentrations for applica-tion in the oil, gas and petrochemical industry.1 2

Gas sensors incorporating graphene display exceptional promise due to their high selectivity and sensitivity.Graphene-based pressure sensors have also been in investigated for applications in oil field bore-hole ex-ploration and characterization.

0 Coatings

As oil and reserves deplete it has become necessary to dig deeper and deeper. The International Energy Agency estimates that more than 70% of remaining oil and gas reserves across the globe are highly corrosive. Most new reserves are in environments that are deeper, hotter, higher pressure and farther offshore. As a result, there is high demand in the oil & gas industry for high performance coating materials to protect metal assets. With capital expenditure in the oil industry exceeding $1 trillion annually, a significant percentage of which is spent on Deepwater pipelines, there is a significant op-portunity for new protective coatings. Therefore the use of high temperature and abrasion and erosion resistant nanomaterials is desirable. Drilling equipment in the oil and gas industry tends to wear down very quickly. Oil and gas well pipes, nor-mally consist of relatively low cost, low carbon steel susceptible to hydrogen embrittlement, hydrogen sulfide induced corrosion, and chloride stress corrosion and cracking. While efforts have been made in the past to overcome such problems, they have not met with wide acceptance. For example; while the entire pipe, or pipe liners may be formed from stainless steel, this is a far too costly solution. Stainless steel liners have been proposed but it has been found that hydrogen diffus-ing into the clearances between the liner and pipe bore causes problems such as hydrogen embrittlement, and deformation of the liner when the hydrogen expands.The use of nanomaterials can improve the way com-panies drill and complete their wells through increas-ing strength, durability (e.g. surface coating to avoid erosion or scale attachment) and potentially provide completion design options not possible with existing technologies. Nanocoatings have already been applied as anti-wear coatings for drilling parts, thermal coatings to lower deformation and anti-corrosion for pipelines and other long-term structures.

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The oil and gas industry has adopted nanostructured coatings for anti-corrosion applications. A major prob-lem in the Oil Country Tubular Goods market (OCTG) is the degradation of down hole pipes and tubes, sur-face piping, pressure vessels, storage tanks and other equipment due to corrosion, abrasion and other factors. Long-lasting coatings are needed to protect under sea pipes from seawater. Coatings currently used on rigs and other platforms to prevent rust and corrosion can cause safety issues and environmental issues. The an-nual cost of corrosion consists of both direct costs and indirect costs. The direct costs are related to the costs of design, manufacturing, and construction in order to provide corrosion protection, and the indirect costs are concerned with corrosion-related inspection, mainte-nance and repairs.Nanomaterials providing thermal barrier, wear-resis-tance and corrosion-resistance are of great interest for refurbishing and lengthening the working life of equip-ment and pipelines. Incorporated into coatings, they protect structures like drilling platforms, bridges and metal construction from corrosion; they safeguard shut-off valves and pumping and compressor fixtures; they protect equipment for drilling, oil and gas extraction, and processing and refining from wear and tear.Manchester University has teamed up with Amsterdam-based paints and coatings company Akzo Nobel, to investigate graphene oxide-based paints that provide protection against rust and corrosion for large metal structures, such as oil rigs, tankers and bridges.This collaboration between Akzo Nobel and Manchester University is part of a €1m partnership in corrosion re-search. Akzo Nobel says graphene oxide could provide an ultra-strong, non-corrosive coating for a wide range of industrial applications. Corrosion in its various forms is estimated to cost the global economy $3 trillion a year. Products to protect against corrosion represent an $18 billion world market.

Figure 2: An uncoated copper condenser tube (top left) is shown next to a similar tube coated with graphene

(top right). Image credit: MIT.Oil and gas companies are also seeking to exploit graphene-based icephobic coatings for exploration in cold regions. With the decreasing availability of easy oil, the industry is turning to areas in extreme conditions, such as the Arctic (where 20% of the world’s resources lie). Due to the low temperature, exploration can be compromised due to the exposed structures and equip-ment being affected by ice accretion and adhesion, resulting in damage, degraded reliability and occasional loss of lifetime. Active de-icing involving chemical, thermal and me-chanical methods are traditionally used to remove the ice that has already accumulated. These techniques however require periodic applications and high-energy consumption, and have major detrimental effects on the structures and the environment. Functional nano-coatings that offer enhancements in hydrophobic, anti-icing, and anti-drag properties can enhance efficiency and reduce operating and maintenance costs.SAAB has filed a patent for the development of de-icing coatings. The graphene additive could strengthen the acrylics and shield against EMI interference. GE are also one of a number of companies developing anti-icing nanocoatings that reduce ice adhesion and have also been shown to delay the onset of ice formation.

0 Drilling fluids

Nanoparticles have been used in drilling fluids for de-cades; however more recently developed nanomaterials will greatly enhance this area. Drilling fluids, commonly referred to as drilling muds, are an integral part of drilling oil and natural gas wells. This action not only cools and lubricates the drill bit; it also helps to convey rock debris and drill cuttings from the drilling area to the surface. The drilling fluids can also help prevent blowouts and wellbore cavings by creating hydrostatic pressure that stops formation fluids from entering the well prematurely. Suspension of nanoparticles in fluids (nanofluids) can offer enhanced thermal properties such as heat transfer and insulation of wells. The addition of nanoparticles improves the rheological, mechanical, and thermal properties of drilling fluids. Graphene is a promising candidate as an additive to base drilling fluids with the ability to enhanced include the flow assurance properties of the fluid, the fluid loss control properties of the fluid, the electrical and thermal conductivity, emulsion stabilizers, wellbore

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strengthening components, drag reducers, wettability changers, as corrosion coatings, etc. These fluids can be used in conventional operations and challenging opera-tions that require stable fluids for high temperature and pressure conditions (HTHP).Graphene NanoChem has developed PlatDrill, a graphene-based drilling fluid that they claim Is en-vironmentally friendly, biodegradable and less toxic that competitor products. Competitors include Baker Hughes, Newpark Resources, Haliburton Corporation, Tetra Tech, Canadian Energy Service and Schlumberger, who account for over 80% of the drilling and comple-tion fluids market. The company produces oil and water based graphene-drilling additives. They also produce oil recovery products, water treatment additives and coat-ings for pipes and equipment based on graphene.Baker Hughesd has a patent for Graphene-Containing Fluids for Oil and Gas Exploration and Production.

0 Sorbent materials

As sorbent materials, a variety of carbon-based aero-gels, such as carbon nanotube (CNT) sponge, graphene, graphene/CNT hybrid foams and NFC, exhibit very high sorption capacities, good recyclability and environmen-tal friendliness. Directa Plus are developing a graphene based “Graphene Plus “ eco-innovative adsorbent for oil spills clean-up.

Figure 3: Directa Plus Grafysorber.

0 Catalysts

Nanomaterials are playing an increasingly important role in liquid fuel production and clean combustion. Nanostructured catalysts show potential for replacing Platinum, Rhodium, PGM and other metals tailored spe-cifically for oil and gas refining. For the production of liquid fuels from fossil energy sources, nanostructured catalysts are applied in oil refinement.

0 Separation

Nanomateirals-based filtration methods are under de-velopment for Gas Separations, Heavy Metal Separation, and Oil-water Separation. Nanoscale zeolites are used as membranes for gas separation as well as nanoscale metal oxides of Al, Si, Ti and Zr. Graphene and graphene oxide are promising gas sepa-ration membrane. As they are only one carbon atom thick, they could potentially form the thinnest separa-tion membranes to maximize flux. There are a number of technical hurdles to overcome before this is a viable opportunity, as graphene is impermeable to small gas molecules.Water is a by-product of virtually all oil and gas explora-tion (18 billion gallons of wastewater each annually). When oil and gas is brought to the surface, it is ac-companied by varying quantities of so-called produced water, which tends to increase with the age of the well. Energy reserves of oil and natural gas have seen signifi-cant increases in exploitation over the past 20 years, especially those from unconventional origins such as heavy crudes, tar sands, gas shale, coal seams and tight sands. Vast quantities of water are used and co-pro-duced during the extraction of these resources.Environmentally and in terms of economy and ex-traction it is desirable to filter this water. The largest growing source of produced water originates from the development of unconventional gas resources, particu-larly those from coal bed methane (CBM) and gas shale. Nanomaterial membranes have an order of magni-tude increase in permeability over traditional polymer membranes current used for filtration in oil and gas. This leads to reduced pressure requirements leading to lower capital costs for pumps and lower energy costs.

Figure 4: Nanometer-scale pores in single-layer free-standing graphene membrane can effectively filter NaCl salt from water. Image credit: MIT.

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Graphene and derivatives thereof are impermeable, have well-defined nanometer pores and exhibit low fric-tional water flow. It is impermeable to all gases due to the electron density of its Aromatic rings. Membranes containing functionalized or pristine graphene display excellent potential for selective uptake and transport of molecular or ionic species. Ionic and molecular sieving membranes that enable fast solute separations from aqueous solutions are essential for processes such as water purification and desalination, sensing, and energy production. Desirable properties of graphene that are important for membrane technology include:• Over 20,000 x thinner than other membranes.• Ideal pore size for separation (Improvement of 500x compared to other membranes).• Large surface area (Up to areas of 1 mm ^2).• Resistant to oxidation (for temperatures less than 450 Celsius).• Very mechanically stable.

Locheed Martin Corp is developing graphene-based filters for wastewater treatment in the oil and gas in-dustry. The company’s Perforene membrane is currently being tested by oil and gas companies. Read more at http://www.lockheedmartin.com/content/dam/lock-heed/data/ms2/documents/Perforene-datasheet.pdf.

Figure 5: The Perforene graphene filter allows saltwa-ter to pass through an extremely thin membrane at relatively high speeds with very little energy. Image: Locheed Martin.

References:1. Ultrasensitive gas detection of large-area boron-doped graphene, http://www.pnas.org/content/ear-ly/2015/10/29/15059931122. Innovative Application of the New Generation of Gas Sensors Based on Graphene Hybrids in Oil, Gas

and Petroleum Industries: A Systematic Review, http://petrotexlibrary.com/wp-content/uploads/2016/04/V4.I2.69-74-1.pdf

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Graphene in AsiaThe main market for carbon nanomaterials such as graphene and carbon nanotubes is Asia, due its prominence as a hub for advanced electronics and energy technologies.

I n nanoelectronics, the application of graphene and carbon nanotubes to displays, touch panels, flexible electronics and nanoelectronc devices is a

main research thrust both at an academic and com-mercial level. As a result, the main regional demand for CNTs and graphene is in Asia-Pacific. Japan is the largest nanotech market globally with product development ongoing in a number of large multi-national companies. Asia-Pacific is the largest market for lithium-ion batter-ies and transparent conductive films by a considerable margin, markets that CNTs and graphene are impact-ing greatly. A major percentage of the battery market is occupied by China, South Korea and Japan. China and South Korea are investing heavily in graphene and Japan already has a large manufacturing base in CNTs.

JAPANJapan is home to a number of the leading carbon nano-tubes producers. Companies with production facilities include:

• Carbon Nanotech Res. Inst. Inc. • Hanwha Nanotech Corporation• Showa Denko• Taiyo Nippon Sanso• Toray (MWNTs and SWNTs)• Mitsubishi Rayon Co., Ltd. (SWNTs)• Zeon Corporation.

Hitachi Zosen Corporation has developed a mass pro-duction system for producing vertically aligned carbon nanotubes (VA- CNT) on metal foil and metal sheet substrate, resulting in a continuous sheet substrate that can be wound onto a roll. Companies producing CNT products include:• KJ Specialty Paper (CNT Sheets for composites)• Teijin’s (CNT Fibers for electronics and batteries)• Toray (Double-walled CNTs for printable electronics)• Nippon Chemicon’s (SWNT capacitor)• Nitto Denko ( “Gecko Tape” Biomimetic Adhesive).

ANALYSIS

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The CNT industry in Japan currently takes precedence over graphene. However, there are a number of produc-ers.

COMMERCIAL ACTIVITY IN The CNT industry in China is far behind Japan; however they have ramped up activity in graphene considerably in a short space of time. China and South Korea holding 43% of global graphene patents (the U.S. has 23%). Six of the ten top patent holders are located in Asia, with four of those being research universities. The National Natural Science Foundation (NSFC) has spent more than $65 million on graphene R&D projects to date, mainly as part of the country’s 12th Five-Year Plan. In July 13 2013, China Innovation Alliance of the Graphene Industry (CGIA) was established by a group of laboratories and companies, under the guidance of China Industry University Research Institute Collabora- tion Association. It also receives a variety of supports from the Ministry of Science and Technology, Ministry of Industry and Information Technology National Develop- ment and Reform Commission, and NSFC.China has established several graphene development bases in Chongqing, Wuxi, Nanjing and Qingdao. The Ningbo regional government has plans to provide $14.7 million over three years (2014-2017) to develop the graphene industry, and plans a $1.62 billion industrial scale-up investment over ten years.

Main CNT producers in China are • Shenzhen Nanotech Port Co., Ltd. • Sun Nanotech Co., Ltd. (SUNNANO)• Beijing CNano Technology Limited (CNano)• Sun Shun Zhong Ke New Material Co., Ltd.• Timesnano.

Product developers include Tianjin FUNA Innovation Technology Co., Ltd. and Suzhou Creative-Carbon

Nanotechnology Co., Ltd. Wuxi Suntech Power Co., Ltd. (www.suntech-power.com), in partnership with Taiwan Carbon Nanotube Technology Corporation (TCNT), it has successfully developed what they claim to be the world’s first low-cost and highly reliable carbon nano-tube photovoltaic module frame. Huawei Technologies (www.huawei.com) is utilizing carbon nanotubes in smart- phone screens.

A number of Chinese start-ups have built multi-ton graphene facilities with government funding in a very short period. Total annual production capacity of small graphene sheets and graphene films in China is in ex-cess 400 tons and 110,000 m2.

Graphene Powder producers• Ningbo Morsh Technology Co., Ltd.• Xiamen Knano Graphene Technology Co., Ltd.. • Jiangsu Yueda Mote New Mstar Technology Co., Ltd.• The Sixth Element (Changzhou), Ltd.• Fangda Carbon New Material• Beijing Kangde Xin Composite Material• Tianjin PuLan Nano Technologies Ltd.• Nanjing JCNANO Technology Co., Ltd.• SuperC Technology Ltd.• DT Nantech Ltd.

Graphene Film Manufacturers • Sichuan Jinlu Group Co., Ltd.• 2D Carbon Graphene Material Co., Ltd.• Chongqing Morsh Technology Col, Ltd. • Institute of Aeronautical Materials (IAM) of Aviation Industry of China (AVIC)• Nanjing XFNANO Materials Tech.

In 2015, the government sought to accelerate the com-mercialization of graphene. In March 2015, the Ministry of Science and Technology established the National

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Industry Base of Graphene New Materials in Changzhouand the National Torch Industry Base of Graphene and Carbon Materials in Qingdao in August.

The National “13-5” Project was also established. From 2016 – 2020, 100 graphene industry parks will be built with the intention of generating revenues up to 100 billion RMB of graphene products and revenues up to 1000 billion RMB of graphene related products. Ap-plication focus areas are new energy and electrical cars, composite materials, coatings, energy saving and environment protection technologies, desalination, soft and foldable touch display screen, intelligent wearing materials

13th Five-Year PlanIn November 2015, the Ministry of Industry and Infor-mation Technology, the NationalDevelopment and Reform Commission, and the Ministry of Science and Technology issued an officialdocument “Guidance on Graphene Industrial Innovation and Development” that outlined a strategy for acceler-ating graphene commercialization in China

The key points of this guidance were:1. Seize the opportunity of the rising period of gra-phene industrialization: The guidance indicatesthat it is the critical time for graphene technology mov-ing up from R&D to industrialization.2. Build graphene technology as the forerunner indus-try: a. To 2018, the production chain of graphene manufac-ture, downstream R&D, and commercialproducts shall be built up.b. To 2020, well established graphene manufacture and marketing system shall be completed.This includes about 10 strong competitive companies that can manufacture standardizedgraphene products with competitive prices, and 3 – 5 world leading innovation platforms.3. Drive key technology innovation:a. Solve problems in processing, ensure controllable product quality and processing stability.b. Secure IP system.c. Establish public service system including analytical laboratories and quality control platforms.4. Promote exemplary of downstream applications:a. Focus on energy storage devices, functional coatings, re-enforced rubber and tires, thermalmanagement products, sensors, touching components,

and electronic components etc.b. From 2016 to 2018, build up 12 exemplary produc-tion lines for commercialization of graphene applica-tions, i.e., 4 lines per year.5. Develop green and recyclable processing, and ensure sustainable development.6. Serve for the national key engineering projects and for continuous improvement of life quality.7. Supporting systems include privilege policy made by the governments, oriented investment, standardization system, and other necessary supportive services.Overall, it emphasizes the importance of international cooperation in graphene commercialization.

As part of the 13th Five-Year Plan (2016-2020) places heavy focus on new materials. By 2020, advances should be made in core technology in telecommuni-cations, new energy, new material and aviation, and support the development of new industries, including energy conservation, biotechnology and information technology sectors. Many of these advances will be enabled by graphene.

SOUTH KOREA

In 2012, the South Korean government approved a roadmap for graphene commercialization with $200 million budget for the next 6 years. They are also look-ing at a research institute that they would fund with $200-300 million per year.

The commercialization plan includes:1) graphene-based touch panels2) organic light-emitting diodes (OLEDs)3) electrochromic smart windows4) secondary batteries for electronic vehicles5) high-voltage high-power supercapacitors6) ultra-light and strong composites7) high-performance gas barrier films,8) electromagnetic interference shielding, and9) environmentally friendly anti-oxidation steel plates.In 2013, the Korean Graphene Project was initiated with funding of $44 million over 5 years.

According to the Korean Intellectual Property Office, a total of 2,921 graphene-related patents were applied for in Korea between 2005 and June 2013. Companies developing graphene products include Hanwha Chemical and Samsung SDI. These companies also have activities in carbon nanotubes. Graphene

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Square (www.graphenesq.com) produces CVD grown graphene films for application in electronics.KH Chemicals, Co. Ltd. (www.khchem.com) has a propri-etary continuous process that enables the mass produc-tion of SWNT with uniform and high quality, which can be applied for various applications including Transpar-ent conductive films. There are numerous other Korean producers and product developers in carbon nanoma-terials including Carbon Nano Material Technology Co., Ltd (www.carbonnano.co.kr), Korea Kumho Petrochemi-cal Co., Ltd. (www.kkpc.com/eng/index.asp) and Nano Tec Co.,Ltd. (http://enanotec.co.kr). Kumho Petrochemi-cal Co., Ltd. has a production capacity of over 300 tons per annum of carbon nanotubes.

TAIWAN

Carbon nanomaterials activity in Taiwan is mainly focused on carbon nanotubes. Producers and prod-uct developers include Advanced Nanopower, Taiwan Carbon Nanotube Technology Corp. (www.tcnt.tw) and XinNano Materials, Inc. (www.xinnanomaterials.com). Hon Hai Precision Industry/Foxconn (www.foxconn.com) and Tsinghua University have jointly developed and commercialized a smartphone touch panel using CNTs. Taiwan Carbon Nanotube Technology Corp. also produces graphene and is involved in product develop-ment in energy and consumer electronics. The government is funding graphene projects mainly through the Industrial Technology Research Institute (ITRI) under three application areas:- Smart Living: involves efforts to integrate technologies in information and communication technologies (ICT), cloud services, big data, etc., to develop smart services, logistics, and next-generation handheld devices. - Quality Health: focuses on the development of innova-

tive therapeutic biologics, composite medical materi-als and instruments along with healthcare assistance technologies. - Sustainable Environment: focuses on green energy, smart transportation, biomass, advanced green manu-facturing, and disaster relief technologies.

MALAYSIA

NanoMalaysia (www.nanomalaysia.com.my), a company set up under the Malaysian Ministry of Science, Technol-ogy and Innovation (MOSTI) to promote nanotechnolo-gy commercialization activities, announced n early 2016 that Malaysia’s National Graphene Action Plan (NGAP) 2020 will lead to 360 new products.NGAP2020 aims to generate about 9,000 jobs and RM20 billion ($4.86 Billion) GNI impact by the year 2020.MOSTI announced during a recent ceremony that companies have signed memorandums of agree-ment (MoUs), which will help to build a local graphene ecosystem and speed up graphene-based application development for specialty and consumer products such as tyres, automotive components, water pipes and ultra-capacitors.

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