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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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Long-Established Chemical Company Continues to See Graphene Demand Increase

Posted By Dexter Johnson, IEEE Spectrum, Wednesday, July 11, 2018

When we first spoke to William Blythe back in 2016,  we were trying to get a handle on how a 170-year-old specialty chemical company found itself involved as a major graphene producer. Now nearly two years later we got to visit with the company again to see what’s changed from since we last spoke.

For those of you who would like more regular updates on what William Blythe is doing and thinking about when it comes graphene, you can visit their blog. And while there you can order some material on the same site

 Q: When we spoke to you 18 months ago, William Blythe expected to boost graphene oxide production to the tonnage scale within the next 6-12 months from a lab production level of around 20Kg. Has that production capacity increase happened?

A: William Blythe has definitely seen an increase in demand for graphene oxide since we last spoke. We have been working on scale up of all three of our graphene oxide products, with significant investments made and planned to ensure we always stay ahead of our customers’ needs. As application development has been slower than originally predicted by our customers, we have been able to scale to an interim production capacity of about 200 kg pa.

Q: At the time we spoke last, William Blythe was investing heavily in R&D, focusing on innovation and product development. How has that program developed over the last 18 months?

A: William Blythe has continued building its R&D program and has added several projects since we last spoke. One significant area of investment is in the energy storage sector, with a commitment to spend £1m over the next 3 years in energy storage research. One of these projects is in collaboration with the National Graphene Institute at the University of Manchester and aims to develop novel anode materials. As a company, we are very committed to developing the materials needed to enable the exciting technologies needed for the future.

Q: Can you also address along these lines how your supply line has developed, i.e. what are the expectations of your customers in terms of batch-to-batch consistency?

A: William Blythe’s customers, across our whole product range, always require the highest level of batch-to-batch consistency. Our products are generally used in demanding applications, where the performance of the product could be hugely affected by small variations in either the chemical or physical properties of the materials we supply. We pride ourselves on offering consistently high-quality products. Both the quality and batch-to-batch consistency of our graphene oxide has been commended by several customers.

Q: Are you still supplying strictly graphene oxide or have you branched out to other graphene products, such as single-crystal monolayer graphene? Why have you chosen one product approach, or the other?

A: As we discussed previously, William Blythe is an inorganic specialty chemicals manufacturer. The chemical exfoliation route we use to synthesize our graphene oxide is very well aligned with our core capabilities, which means we are very well positioned to scale the process effectively and successfully.

Q: We discussed ad hoc industry standards for graphene last time we spoke. Have those become more formalized? And what is the state of graphene standardization across producers?

A: A lot of work is taking place on standardization of graphene materials, however the early standards are more focused on graphene as opposed to graphene oxide. While standards are now being written and the first standards are now published, there is still a need to get the wider market on board as terminology is not always being fully understood and adopted by those in the graphene community.

Q: A year-and-half ago, William Blythe expressed confidence that graphene "will be well established in the supply chain of several industries within the next 5 – 10 years”. Has anything occurred since that then enforces that belief, or perhaps you have become more cautious?

A: Based on the work we know of in this market, the forecast of graphene oxide being well established in some industries by 2026 is very realistic. William Blythe is, as you know, working on increasing production capacity of their graphene oxide to meet customer demands over the coming years. While some applications are commercializing right now, William Blythe is also working on several longer-term projects, we expect these applications to take several years to commercialize, but would still anticipate commercial volume demand in these areas before 2026.

Tags:  graphene oxide  graphene production  specialty chemicals 

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Quality Is Timeless: How a 170-Year-Old Speciality Chemical Company Found Itself at the Forefront of Graphene

Posted By Dexter Johnson, IEEE Spectrum, Wednesday, September 28, 2016
Updated: Wednesday, September 21, 2016

 

When we think of graphene, we conjure up cutting-edge and emerging technologies that have a place in a sci-fi movie, and rightly so. But to make those dreams into reality it is coming down to a nearly two-century-old specialty chemical company to produce the building blocks. William Blythe, a 170-year-old inorganic specialty chemical and advanced materials company based in the UK, has established itself as one of the premier graphene oxide producers, enabling other companies to fabricate next-generation devices.

In May of this year, William Blythe added graphene oxide to its portfolio of products and ramped up production of the material to large lab-scale manufacturing, reaching kilogram capacity production. At this point, the company can manufacture up to 20 kg of powdered graphene oxide per annum with the aim of increasing to tonnage scale in the next 6 – 12 months.

To accompany the launch of this new product line, William Blythe has created its GOgraphene website at which you can order the company’s graphene oxide product, as well as find a blog that discusses the experience of launching a graphene-based business.

The Graphene Council took the opportunity of this recent business launch to talk to William Blythe’s Global Marketing & Sales Director, Marc C.G. de Pater, and in the interview below you can read how this company evolved and found itself at the forefront of  one of the most cutting-edge materials, graphene.

Q: Can you explain how a 170-year-old specialty chemical company like William Blythe found itself transitioning into the production of graphene oxide?

A: William Blythe was originally founded to support the textile industry, however over the last 170 years, William Blythe has transformed into an inorganic chemicals manufacturer, who is now on its way to becoming an advanced materials supplier. The expertise William Blythe has developed over the years, as well as its focus on innovation and product development, means the chemistry of graphene oxide fits very well with William Blythe core capabilities.

Q: Can you explain a little bit about the graphene oxide dispersions you produce and how these dispersions fit into the value chain that ultimately lead to products that may find their way into our store shelves?

A: William Blythe currently manufactures a high concentration graphene oxide dispersion at 10 mg/mL, or 1%. The manufacture of a high concentration is designed to maximize the options for graphene oxide users – the optimal concentration of graphene oxide is still being researched but is likely to be highly dependent on the application in question. Higher graphene oxide concentrations can lead to difficulty when diluting the dispersion, however William Blythe has developed a dispersion which can be very easily diluted, as demonstrated in this video: https://www.youtube.com/watch?v=xLixtvZRq0w.

In terms of the value chain, the nature of graphene oxide means William Blythe is positioned at the start. The graphene oxide dispersions offered allow William Blythe’s customers an opportunity to revolutionize the products they sell. Any graphene oxide, or graphene oxide derivative, that ends up on the store shelves is likely to be present in small concentrations, with consumers only aware of its presence through the enhanced properties they observe in the products they purchase.

Q: Why has your company struck upon graphene oxide production rather than single-crystal monolayer graphene? Was that because of what your customers were looking for or did it fit your business plans better in terms of both current production and how you see the market developing?

A: A combination of both – while the chemistry of graphene oxide synthesis fits very well with William Blythe expertise, there is also a strong argument for graphene oxide use over graphene in many situations. Graphene is a hydrophobic material, which means it can be very difficult to obtain good dispersions in various media. Graphene oxide, however, is highly hydrophilic and is reported to disperse very well in many polar solvents. By obtaining the required dispersion with graphene oxide and then reducing to graphene, graphene oxide may also allow users to gain the desired properties of graphene while achieving the dispersion characteristics needed.  William Blythe therefore believes graphene oxide has the ability to exist in the graphene market, employed in systems and applications where graphene would not be suitable.

Q: There seems to be an issue of wide disparity in the quality of graphene products. Is this something that will just be sorted out in the marketplace, or do you think standards will need to be instituted before this problem is fully addressed?

A: Graphene products are so new to the market it is understandable that there is so much variation in product quality. As more users investigate and adopt graphene or graphene oxide products into their applications, a consensus is likely to evolve naturally over what constitutes appropriate material for use. Formal standards may come into place at some point, however if graphene derivatives are already well established by this time it would be reasonable to expect these to take the approximate form of the informal standards already adopted. William Blythe will of course support the establishment of both informal and formal standards for graphene oxide where possible.

Q: What is the range of applications that your customers are using for the graphene oxide that you produce? And what is it about your product that makes them choose yours rather than others, i.e. price, quality, etc.?

A: William Blythe’s graphene oxide is of interest to a wide variety of applications. While it is not possible to disclose specific applications or customers, we can indicate that the range is broad enough to cover applications from membrane technology to advanced coating technology. The biggest attractions to William Blythe’s graphene oxide are its quality (dispersibility and number of layers) and the scale at which the material can be supplied. As a long established chemical manufacturer William Blythe is already planning to scale up manufacture to tonnage quantities. This, combined with a long history of manufacturing and supplying high quality chemicals gives customers confidence in William Blythe’s ability to support the launch of their technologies.

To support those still in research phases of graphene oxide application development, William Blythe recently launched a webshop, www.go-graphene.com , which sells research quantities of graphene oxide powder and aqueous dispersions. The feedback from this indicates the biggest draws are the competitive pricing and excellent dispersion characteristics.

Q: You are located near the University of Manchester where graphene was first discovered and a major research facility has been created. Has this proximity had an impact on your business? If so, in what way?

A: To an extent, the proximity of William Blythe’s headquarters to the University of Manchester has been of benefit. Members of both the commercial and technical teams at William Blythe have been able to attend meetings and conferences which may have been more difficult if the locations had been less convenient. These events have helped William Blythe to establish some of the understanding and network which are invaluable to the business today. Having said that, William Blythe is sufficiently committed to the development, manufacture and commercialization of graphene oxide that the same activities would have been pursued irrelevant of geography.

Q: Do you foresee William Blythe moving further up stream in the value chain by manufacturing products that employ your graphene oxide? Or will you remain producing dispersions of graphene oxides?

A: William Blythe intends to continue selling both graphene oxide dispersions and powders as well as any other relevant graphene derivatives which make sense in the future. Alongside these it is possible that William Blythe will offer products which fit in further down the supply chain. The volume and caliber of global graphene oxide research is so high at the moment it seems very likely there are other opportunities for William Blythe in the graphene derivative marketplace.

Q: Can you paint a picture of both William Blythe’s graphene business in the next 5 to 10 years and how the market will look more generally in those time periods?

A: Based on William Blythe’s market intelligence, it is anticipated that graphene products will be well established in the supply chain of several industries within the next 5 – 10 years. Naturally this means graphene oxide volume requirements will have risen and potentially the market price will be lowered. William Blythe expects to still be offering highly competitive pricing for high quality graphene oxide, with manufacture moving to a new dedicated graphene oxide plant. Early estimations predict William Blythe’s graphene oxide plant will have an annual production capacity of 10 tonnes.

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Tags:  graphene  graphene oxide  graphene producer  graphene production  specialty chemicals  University of Manchester  William Blythe 

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