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A Pioneer in Specialty Chemicals Turns Its Attention to Graphene

Posted By Dexter Johnson, IEEE Spectrum, Thursday, September 5, 2019
Updated: Friday, August 23, 2019

 

One of the groundbreaking companies in specialty chemicals, Kenrich Petrochemicals Inc. has been a vanguard in developing products for the polymer industry.

The company has turned its expertise and long history of developing industry-leading compounds to the area of graphene and making the “wonder material” even better.

Kenrich recently joined The Graphene Council as a Corporate Member and we took that opportunity to interview Salvatore J. Monte, the president of Kenrich, to learn how Kenrich became involved in graphene and where the company expects graphene development to go in the future.

Q: Can you describe the genesis of how Kenrich started to look at graphene for its specialty chemicals portfolio?

A: The name Kenrich comes from three graduates from the University of Kentucky who planned to get rich by selling a unique aromatic resin/polymeric plasticizer called 'Kenflex® A', produced at Socony Mobil’s R&D laboratories in Paulsboro, NJ via a formalite condensation polymerization of certain gasoline bottoms consisting of polycyclic aromatic hydrocarbons. 

In 1959, DuPont approved Kenflex® A for use in Neoprene® and Hypalon® rubber high voltage wire and cable insulation compounds. The aromaticity worked well in dispersing carbon black and metal oxides.  As a result, Kenrich also got into the business of making paste masterbatches of the metal oxides and other raw materials used to accelerate and cure the rubber insulation compounds.

Kenrich’s current President Sal Monte had married Erika Spiegelhalder, the daughter of the owners of Kenrich Petrochemicals, Inc. and was made VP when he joined the company in April of 1966.  At the time, Monte was a licensed P.E.  He went back to school and in 1969 obtained a M.S. degree in Polymeric Materials at NYU Tandon School of Engineering. 

In 1973, the first titanate coupling agent was invented in an effort to make a good dispersion of 85% of a fine particle ZnO in a naphthenic oil base. Monte tested most of the then known surfactants and could not obtain a satisfactory dispersion.  Frustrated, he had the Kenrich Bayonne, NJ laboratory synthesize a titanate coupling agent by transesterifying 3-moles of isostearic acid with 1-mole of Tetraisopropyl titanate. The resultant titanate dubbed “Ken-React® KR® TTS” worked “best ever” on the ZnO and all the other inorganics and organics such as carbon black in the various masterbatches the company was producing. 

KR® TTS is 2019 EU REACH registered in 680-cosmetic and sunblock formulations based on ZnO and TiO2.  As an example, a 55% masterbatch of the ZnO was made smooth and creamy with just 0.5% additive.

The titanate coupling agents evolved into a distinct product line with 64-commercial titanate and zirconate products under the Ken-React® tradename.  They proved to work where silane coupling agents didn’t in compositions like CaCO3 filled Polypropylene.  The first published technical article on the material appeared in the December 1974 issue of Modern Plastics Magazine with the title: “A New Coupling Agent for Polyethylene”. 

Keep in mind that this article positioned Kenrich’s titanate and zirconates as an alternate coupling agent technology to silane coupling agents that were used in the 1950’s to develop the Corvette glass reinforced polyester composites and that initiated the generation of “plastic” automobiles.  Silanes worked well on silica/fiberglass but did not couple to carbon black and carbon fiber since carbon does not have hydroxyl groups for silane hydrolysis coupling mechanisms.  The producers of silanes state their non-functionality with carbon interfaces in their literature.

Monte went on to write a 340-page book, filed 31-patents worldwide, and wrote over 450-ACS CAS Abstracted “Works by S.J. Monte” and was voted a Fellow of the Society of Plastics Engineers in 2004 around the same time when Professor Sir Andre Geim and Professor Sir Kostya Novoselov of the University of Manchester discovered and isolated a single atomic layer of carbon for the first time known as graphene.

Efforts to make thin films of graphite by mechanical exfoliation started in 1990, but nothing thinner than 50 to 100 layers was produced before 2004. The term graphene was introduced in 1986 by chemists Hanns-Peter Boehm, Ralph Setton and Eberhard Stumpp. It is a combination of the word graphite and the suffix -ene, referring to polycyclic aromatic hydrocarbons.  Monte did his M.S. thesis on the synthesis of polycyclic hydrocarbons such as dimethylnaphthalene in the presence of formaldehyde and sulfuric acid clay catalysts to make a better Kenflex® A.

In the early 1960s, Dr. Akio Shindo at Agency of Industrial Science and Technology of Japan developed a process using polyacrylonitrile (PAN) as a raw material. This had produced a carbon fiber that contained about 55% carbon. In 1960 Richard Millington of H.I. Thompson Fiberglas Co. developed a process (US Patent No. 3,294,489) for producing a high carbon content (99%) fiber using rayon as a precursor. These carbon fibers had sufficient strength (modulus of elasticity and tensile strength) to be used as a reinforcement for composites having high strength to weight properties and for high temperature resistant applications. 

In 1988, Kenrich and General Dynamics wrote a SAMPE technical paper comparing the property improvements in glass, carbon, and Kevlar® fiber reinforced thermosets demonstrating significant improvement and maintenance of mechanical properties of various polymeric compositions.  The maintenance of tensile strength of long carbon fibers in anhydride cured epoxy subjected to 240-hour 10% salt water boil—and other thermosets tested—were quite revealing as they were 5 to 7 times stronger than the control with less than a 3% loss in original properties.  In other words, the carbon interface with a polymer was not deteriorated due to the presence of the zirconate and titanate coupling agents. 

Part of this resistance to deterioration of the carbon/polymer interface is a result of the neoalkoxy coupling mechanism of the patented Ken-React® zirconates and titanates as they couple via proton coordination with the hydrogens and hydroxyls on the carbon interface to form 1.5-nanometer atomic monomolecular layers in the absence of water with no leaving groups.  This is in contradistinction to silanes, which need water and leave water at the interface after coupling.

In simple layman terms, if graphite is the unsliced bologna then graphene are its one-molecule thin slices. The physics of fiber reinforcement materials such as graphite, fiberglass and aramids work on a simple reinforcement principle:  Any composition subjected to direct compression forces will act as a column with no bending stresses if the ratio of the length of the column to the diameter of the column is less than ~ 15:1.  Once the column becomes longer, bending forces come into play.  It’s why the Romans built fat columns and round arches.  For example, concrete has 3,000 psi compression strength and only 300 psi bending strength and that’s why steel rebars are inserted in concrete beams to carry the bending loads.  The reinforcement that carbon fibers bring is in proportion to their length over diameter ratio.  Graphene provides the greatest reinforcement because it is the ratio of its thinness over its cross sectional area.

Kenrich has worked with conductive carbon black for silicone rubber for decades. And in early rubber experiments before graphene was created, Kenrich could disperse carbon black with its titanate and zirconate additives as discussed in the 340-page Ken-React® Reference Manual. 

 Q: How are you currently incorporating graphene into some of your products?

A: We don’t make graphene or graphene-reinforced products – we make graphene work better. Researchers work with our products using graphene. The Chinese are copying a lot of my old literature and using a lot of the older titanates. 

I am much complemented in China and totally ripped off in Japan under a forced licensing of IP to Ajinomoto in an attempt to gain access to the Japanese microelectronics market in the late 1970’s-early 1980’s. For example, all the magnetic recording media and digital copier toner uses my pyrophosphato titanates to eliminate tape hiss and blurred reproduced images. 

We have been doing nanotechnology from the beginning – and graphene is an extension of that work in fulfillment of my mission statement: To make more efficient use of raw materials using titanium and zirconium chemistry.

 Q: How are you sourcing your graphene and what basic types of graphene are you using to create your compounds?

A: We have a full program established with Matthew McGinnis, PhD and Jeff Bullington and will be working with them at Garmor Inc.’s labs in Orlando by MCO airport, which is 20-minutes from my house in Oviedo, FL.

Q: You have worked extensively with carbon black in applications such as Neoprene. Could you explain some of the benefits and challenges that graphene offers over carbon black in those applications in which both can be used?

A: We can compatibilize the interfaces of almost any dissimilar materials – even Addition and Condensation polymers without fillers.

We have recently been awarded a patent compatibilizing oil (polycyclic aromatics - #4 fuel oil) soaked seawater sand with ordinary Portland cement. Graphene has great potential to make any composition stronger – even concrete – and the solutions are at the nanocarbon interface.

Q: What has proven to be the biggest challenge in incorporating graphene into your products?

A: We believe we will achieve complete deagglomeration of Garmor’s graphene oxide and keep it stable in suspension to take full advantage of its geometry.

 Q: Do you anticipate that Kenrich will be using graphene for other products in the future, or do you believe you have already explored all the possibilities for it in your product line?

A: Graphene needs an effective coupling agent in the 21st century such as the mentioned titanates and zirconates, just as silanes did in the 1950’s for fiberglass composites. The work has just begun.

 Q: What are your expectations for the commercialization fo graphene over the next 5 to 10 years?

Graphene will grow significantly once the interfacial coupling agent art becomes part of the fabric of the industry.

 

Tags:  masterbatches  specialty chemicals  titanates 

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Leading Supplier to Composites Companies Adds Graphene to Its Portfolio

Posted By Dexter Johnson, IEEE Spectrum, Friday, February 1, 2019

 

 

As an association trying to support and promote the use of graphene over the last half-decade, The Graphene Council has rightly focused on the interests and developments of the graphene research community as well as those companies marketing graphene materials. In addition, the Council has also sought to serve as an educational platform to help inform other vertical industries about the impact graphene can make on their businesses.

The Graphene Council recently got a boost to its knowledge base on how graphene is perceived by its largest commercial market: composites. Composites Onethe leading supplier in North America of materials and solutions to advanced composites manufacturers, recently joined The Graphene Council as a corporate member. Composites One positions itself as a team of composites experts that can provide insights on the latest advanced materials ranging from advanced fibers, to high-performance thermosets and thermoplastic systems, prepregs, and specialty core materials. The Graphene Council believes Composites One's expertise should reinforce its own knowledge that can then be distributed throughout our community.

To start this knowledge sharing, we took the opportunity to ask Jason Gibson, the Chief Applications Engineer at Composites One, a little bit about their business, how they came to graphene and what kind of outlook the company has for graphene in the composites market.

Q: Could you tell us a bit more about Composites One business, i.e. what kind of composites are you making and for what applications?

A: As North America’s leading provider of solutions for advanced composites manufacturers, Composites One stands ready to assist you, whatever your needs. We utilize the broadest portfolio of advanced raw materials to build comprehensive solutions, bringing you multiple options to meet your needs. Composites One supports our offering with strong technical expertise, along with local service and storage for reduced lead times. We are uniquely capable of handling complex requirements.

Our network of 41 stocking centers throughout the U.S. and Canada, including AS9120 and prepreg freezer locations, along with local delivery on our own fleet of trucks, ensures that your products are there when you need them. All of this is supported by a dedicated team of advanced composites specialists and our 80+ local technical sales representatives.

Q: What are some of the more advanced materials that Composites One has investigated for possibly integrating into your composite offerings?

A: From advanced fibers, to high-performance thermoset and thermoplastic systems, prepregs, specialty core materials, and ancillary products, we have the broadest product offering in the industry.   Our Advanced Composites product managers are specialists in epoxy resin, prepreg, carbon fiber, high performance core, and many other advanced composites solutions.

Q: What made you consider using graphene as a material for your composites, i.e. have you seen other composite manufacturers employing the material, or is it simple due diligence for all emerging materials?

A: We have seen graphene enhance many of the physical properties across the portfolio of resin systems we distribute.  Specifically, we've seen improved toughness, modulus and strength improvements allowing us to fill the needs of engineers and designers at many of our customers.  Composites One focuses on evaluating and distributing cutting edge products that allow us to help our customers meet their goals of improved products.

Q: Can you outline the process by which you would need to test to see if graphene, or any other new material, could be, or should be, integrated into your composites?

A: Composites One works in partnership with our suppliers, industry organizations and academic resources to vet and validate many nano-particles, including graphene.  We maintain a portfolio of diverse nano-particle products that enable us to provide objective solutions to our customers' needs.  This allows us to focus on an optimized solution based on the unique requirements of our customer.

Q: Based on your initial impressions of graphene, where are you expecting the material to fit into your product offerings?

A: We offer graphene in masterbatch form in multiple resin platforms, but focused mainly in our epoxy offerings.  Loadings can vary depending on the desired end results, and offering the masterbatch in the resin side of the epoxy allows for alternative hardening and additive solutions.  We have seen these products have success in multiple markets including sports and recreation, oil and gas, automotive and aerospace.

Q: At this point, what seems to be the issues that remain unclear about graphene, i.e. industry standards, how it will actually integrate into your composites, etc.?

A: Implementing these products into an industrial manufacturing process can be difficult.  Composites One has extensive experience in the process-ability of the nanoparticle enhancements we offer.  We do this in order to help our customers get over the usual hurdle of incorporating it into their manufacturing process.  It can be difficult to implement these solutions and our breadth and depth of experience in this product lines allows us to partner with our customers and help them move forward with minimal difficulties.

Tags:  composites  Composites One  masterbatches  prepregs  thermosets 

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Graphene and Industry: Where is the Disconnect?

Posted By Dexter Johnson, IEEE Spectrum, Monday, September 18, 2017

With buyers uncertain of how to integrate graphene into their products and suppliers often in a race against time to bring a product to market, can the gap be bridged?

The myriad industries that potentially can be impacted by graphene seems at times a bewildering blizzard of possibilities with no clear path on how to access any of them. If graphene does work for applications ranging from photovoltaics to advanced composites, how does it do it and how can those underlying industries extract the benefits from it for their products?

While the major chemical companies struggle with the learning curve of how they can best use graphene to enable their products effectively, graphene suppliers are struggling with the time it takes to walk those buyers through that learning curve.

“The biggest challenge is accelerating the testing of products with large companies to convince the rest of industry to make the change to incorporate a new material,” said Mark Thompson, Chief Executive Officer of Australia-based Tagla Resources, in a Q&A interview with The Graphene Council last month. Thompson added that in addition to the challenge of time, companies like his face the perennial problem of lack of investor and business knowledge of how graphene really works in an application.

Graphene suppliers face this lack of knowledge among their buyers almost universally. While some suppliers are better equipped to last out the long vetting process, the results are not just taxing to the financial stamina of small companies, but are impacting the overall business of graphene.

“We have encountered customers who are either using low-quality graphene, or graphene oxide in some cases, where they are not maximizing the potential of their products,” said Mr. Ho, Chairman of Perfect Right Limited, an Asia-based graphene producer and a subsidiary of Oovao Powers Holdings Limited, in a Q&A with The Graphene Council last June. “Until commercial applications of graphene-enhanced products become widespread and the application of graphene in products is better understood, we will continue to see a fragmented industry where end users are not able to maximize the potential of graphene in their products.”

While much work is done to improve manufacturing processes of graphene—both in terms of the quantity and quality of the product to improve industry uptake—these efforts both may be missing the larger point, which is to make a masterbatch material.

“I believe that in any industry you always start with the customer need. Quality is less important than functionality and price,” said Chris Gilbey, CEO of Australia-based Imagine IM, in a Q&A with The Graphene Council last March.  “What we focus on is developing fit-for-purpose graphene at the lowest possible price, and at a location that meets the supply chain objectives of customers.”

While this, of course, makes logical sense for any supplier, are the real-world experiences of graphene producers lining up their product with buyers’ expectations? UK-based Haydale Graphene Industries Plc has had an exclusive agreement with Huntsman Corporation to develop a graphene infused Araldite® epoxy resin, and according to Haydale’s CEO, Ray Gibbs, in an interview with The Graphene Council last month, it has been a journey. 

“There are no sales yet but it’s been good for us though because we've learnt an awful lot of know-how about how to mix, choosing appropriate dispersions methods, what cure protocol to adopt and how the surface activations of materials affect our materials,” said Gibbs in the interview. “One fundamental thing that it proved to us is that Huntsman did not want any change to the resin once we added in nanomaterials. Generally, adding nanomaterials at low levels will alter the viscosity and downstream processing methods. The minute you do that is when capital expenditure happens and that alerts the finance teams to cash outflows (often not in any budget). The key then is to avoid processing changes and the need for capital spend. The work has produced some fundamental know how on mixing, dispersion and processing.”

All the suppliers spoken to acknowledge that this learning curve needs to be shortened. Certification is cited by most as a way to shortcut through the quality assurance concerns for buyers. It would help the buyers to de-risk their business plans with graphene.

“We spend a lot of time going around the world doing a lot of presentations just trying to grow belief by providing verified data, which is crucial in getting the customer to say, “OK, it's not just been verified by the suppliers it’s been verified by an independent third party.” For me, that’s another area of credibility that needs to be driven by the industry,” said Gibbs.

Certification can be costly and the bodies that have established those certifications remain often in the planning stages. What remains is an educational process. And the responsibility of that education is increasingly being taken up by not just the graphene suppliers, but by industry groups, such as The Graphene Council.

Gibbs added: “I think the Graphene Council has got a role to play where it's important to inform and to get industry to think about the benefit derived from a consistent, quality supply of material.”

Tags:  buyers  certification  masterbatches  suppliers 

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NanoXplore Brings Unique Perspective to Graphene Production

Posted By Dexter Johnson, IEEE Spectrum, Thursday, January 26, 2017

 

After Montreal-based NanoXplore launched in 2011, its initial business was contract research in the field of carbon-based technologies. But its identity as a contract R&D company changed in 2014 when it filed a series of patents focused on graphene production.

As the company further developed its technology since then, the main focus of the company has become providing graphene-enhanced polymers for plastics that have enhanced electrical, thermal and mechanical properties.

The company website suggests that these graphene-based polymers have a variety of applications, ranging from photovoltaics to supercapacitors

We wanted to get to know how a relatively new company that started out as an R&D contractor evolved into a graphene-enhanced polymer manufacturer and how they now see the downstream market for their product. To do that, we took the opportunity of NanoXplore becoming a corporate member of The Graphene Council to talk to the company’s chief operating officer, Paul Higgins, and here is that interview.

Q: NanoXplore started out as an R&D contractor in carbon-based technologies. How is it that the company was able to file a patent in graphene production patent just two years after being formed? Were you always doing research in this area, or did you make a concerted effort to find a place in the graphene market?

Working with other carbon-based materials, especially CNTs, it became evident that many commercialization challenges were due to the production processes. The processes had been developed in research environments and were not designed from the ground up with an industrial mindset. We focused from the beginning on low cost, high-yield processes, using existing capital equipment, and with no pre- and post-processing. For example, our graphene production process functionalizes the graphene in-situ, avoiding costly functionalization post-processing for most applications. We were also very cognizant of the need for sustainable, “green” processes; our patented process is water-based, uses no strong acids, and no organic solvents.

A key insight underpinning our patents is that high energy and strong chemical processes create many downstream problems in graphene production. High-energy processes are inefficient and create defected planar structures, resulting in graphene with poor electrical and thermal benefits, in turn requiring high, non-economic loadings of graphene in nanocomposites.  Strong chemical processes require complicated post-processing and recycling processes to be cost effective and require very tightly controlled production environments, adding costs.

Once we had established the frame of potential solutions based upon the above, developing our new technology platform was relatively straightforward.

Q: Were you looking to enter a particular niche of the graphene supply chain or did the process you came up with dictate somewhat the point in the supply chain that you now occupy?

Our process is high yield, large volume, low cost, and produces graphene powder with very high quality. This allows us to target mass industrial material markets such as polymers, markets requiring large volumes of material. And due to the quality of our graphene, we can provide significant benefit to industrial materials at low loadings and viable price points.

Of course, the graphene must be effectively mixed into the polymer matrix. To do this we have developed production processes for the manufacture of graphene-enhanced plastic masterbatches. These masterbatches, which we have been manufacturing and selling since early 2016, are the perfect form factor for the plastic industry. Plastic formers, such as injection and blow molders, and compounders are very comfortable with masterbatches and easily incorporate them into their existing processes.

Q: Do you see the company evolving to develop products further up the supply chain? For instance, it appears you’re involved in energy storage technologies enabled by graphene. Is this where you see your business moving or do you see this is just diversification of your portfolio?

NanoXplore is focusing our current commercial efforts on graphene-enhanced polymers. We see this as a large market, hungry for innovative materials, where our graphene has a strong competitive advantage.

We also have a patent on a unique graphene-graphite composite material that is useful for energy storage applications. This material was the impetus for our original research in the energy field. This initial research showed great promise and leads us into development of a range of materials for Si-graphene anodes and S-graphene cathodes.

From our current polymer efforts and the emerging energy storage materials, we see a sustainable growth model for the company. Our core research efforts develop graphene-based technologies for a target market, and then transition to product development. During the transition, we will develop technologies for the next target industry. And repeat. Graphene is so broadly applicable that we foresee being able to continue in this vein for some time.

Q: How does your company envision the landscape for the graphene market evolving over the next five years, i.e. are there particular markets that will be winners and losers, what applications are not being sufficiently targeted, etc.?

The graphene market has changed significantly over the last three years. Three years ago the challenge for end users was to obtain decent material, in volume, at a reasonable price. Today there are several producers, including NanoXplore, producing large volumes of good quality graphene. Prices per kg for high quality graphene have fallen during this period from $30,000 kg to $100 Kg and are set to fall to $30 kg over the next five years.

[NB: Above and subsequent comments pertain to high quality - low defect, functionalized few layer graphene and graphene nanoplatelets. Graphene from CVD is excluded as is reduced Graphene Oxide (rGO)].

The current challenge for the graphene industry is to incorporate graphene into real-world products and industrial processes. One of the major hurdles is that graphene is sold into a supply chain, with many players between the graphene producer and the final product. And each of these players has their own calculus of risk versus benefit. To be successful the graphene producer must demonstrate benefits to each player at every step along the supply chain, while meeting standards, helping to modify processes, overcoming regulatory hurdles and minimising supply chain disruptions. The successful companies will expand to cover several steps in the supply chain – for example graphene material, polymer compounds, plastic forming – and develop partnerships with other key supply chain players.

Over the next 3-5 years, one can imagine the commercial introduction of novel graphene enabled subsystems and systems. This category of products will include strong, light weight and highly functional nanocomposites for electric transportation vehicles, greatly improved energy systems (e.g., next generation batteries), high barrier packaging, smart textiles, and others. Solutions for highly regulated industries (e.g., medical, aerospace), some being demonstrated today, will start to exit their testing regimes and enter the marketplace.

Ultimately graphene will be part of building a sustainable future, playing a significant role in the replacement of costly, single function, or scarce materials with abundant, cheaper, and higher-performing ones. It will replace multiple and occasionally toxic additives with a single multi-functional material. It will reduce weight while increasing strength for a wide range of structural polymers and composites often leading to significant fuel savings in vehicles. It will extend the useful lifetime of paints, coatings and lubricants. And it will improve thermal management and energy storage in a wide range of applications, again improving efficiency while husbanding scarce resources.

NanoXplore is very well positioned to help customers participate in this emerging new world. With the combination of high quality graphene material, expertise in mixing graphene with a wide array of industrial materials, and a team of seasoned business leaders and material scientists with broad industrial experience, NanoXplore enables customers to achieve significant and affordable product improvements with very little added graphene.

Tags:  masterbatches  photovoltaics  polymers  supercapacitors 

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