Polymeric Materials: Science and Engineering Division

2017 ACS TEAM INNOVATON AWARD IN HONOR OF ROBERT DEVRIES, PHILIP GARROU, CAROL MOHLER, ERIC MOYER AND THEODORE (TED) STOKICH JR

Robert A. DeVries, Philip Garrou, Carol E. Mohler, Eric S. Moyer and Theodore (Ted) M. Stokich, Jr, winners of the 2017 American Chemical Society Team Innovation Award, are recognized for successful development and commercialization of novel, high performance photodefinable bisbenzocyclobutene interlayer dielectric materials.  As a result of the efforts of this Dow Chemical team in the 1990’s, polymeric dielectric materials were commercialized which enabled the microelectronics industry to miniaturize integrated circuit packaging.

“These individuals brought together an ensemble of complementary skills from a variety of scientific disciplines including organic chemistry, polymer science, photochemistry, analytical science and materials science.  As a team, their innovations led to the development and commercialization of a photodefinable bisbenzocyclobutene (BCB) interlayer dielectric material, which became an enabling material for the electronics industry for many years, and a foundational product of Dow Electronic Materials’ CYCLOTENE™ Advanced Electronics Resins product line. The numerous innovative technical breakthroughs and highly interdependent collaborative work by the Dow team resulted in a large number of refereed publications, issued patents, and ultimately the successful commercialization of BCB-based CYCLOTENE photodielectric products.” – David S. Bem, former R&D vice president of Advanced Materials at Dow.

The original development of BCB and the CYCLOTENE dielectric products dates back to the late 1980s, with the first commercial (non-photodefinable) product being launched in the early 1990s.  This product revolutionized the packaging and interconnect industry by delivering a low dielectric constant, low moisture uptake material with no volatile side products. These features allowed CYCLOTENE to penetrate further into adjacent market segments in the microelectronics industry like gallium arsenide integrated circuits, and bumping and redistributing silicon chips—to name a few.  However by the mid-1990s, the industry demanded a photodefinable material with sufficient photospeed, lithographic resolution, and stability to meet the increasingly broad range of new device schemes and fabrication processes.

The Dow team met this challenge by leveraging its diverse scientific expertise, market-focus, innovative and collaborative spirit by developing and commercializing the first photodefinable BCB-based CYCLOTENE product. Because of this successful combination of team innovation and collaboration a large percentage of all portable hand-held devices contain Dow’s photodefinable BCB technology in many of their components. 

Dr. Philip Garrou currently consults in the areas of thin film technology, IC packaging and interconnect, microelectronic materials and 3D IC integration for startups and Fortune 500 companies, through Microelectronics Consultants of North Carolina.  As program director at Dow Chemical for the development of photodefinable benzocyclobutene, Dr. Garrou provided the team with the overall vision, guidance, and definition of the industry-leading performance requirements for a photodefinable BCB-based resin.  He played a critical role in providing the necessary market insights to define requirements for key properties such as adhesion, stability, photolithography, solvent compatibility and reworkability.  He also served as liaison with end-use customers to convey timely performance feedback essential to accelerate the product development cycle.  Dr. Garrou received a B.S. in chemistry from North Carolina State University and a Ph.D. in chemistry from Indiana University, Bloomington, and has authored or co-authored more than 100 technical publications.  He is Fellow of both IEEE and IMAPS, and has served as President of the IEEE Components, Packaging and Manufacturing Technology Society (CPMT) and IMAPS.  Dr. Garrou has been an Associate Editor of IEEE Transactions on Components and Packaging, and is currently Contributing Editor/blogger for Solid State Technology. He has received numerous awards for leadership in advanced packaging for microelectronics, including the 2012 IEEE CPMT David Feldman Outstanding Contribution Award, 2011 IMAPS Presidents Award, the 2007 IEEE CPMT Sustained Technical Contributions Award “for 25 years of technical contributions and leadership in thin film dielectric materials and microelectronic applications including multichip modules, bumping and wafer level packaging, integrated passives and 3D integration”, the 2002 Fraunhoffer IZM International Advanced Packaging Award for “pioneering achievement in the introduction of new thin film polymeric packaging materials”, 2001 IMAPS WD Ashman Achievement Award and the 1994 Milton Kiver Award for Excellence in Electronic Packaging and Production for the commercial introduction of CYCLOTENE Advanced Electronics Resin.

Dr. Eric S. Moyer is a Senior Technology Manager at LORD Corporation.  As a Research Leader at Dow Chemical, Dr. Moyer applied his expertise in photoresist chemistry and lithographic characterization to identify a novel, sensitive photocrosslinker chemistry specific to the photodefinable BCB resin.  One of the key insights he provided involved the relationship between resin molecular weight and photolithographic properties, and how judiciously adjusting these properties resulted in excellent film retention, photospeed, and lithographic resolution.  Dr. Moyer received a B.S. degree in chemistry from Houghton College and a Ph.D. in polymer chemistry from Virginia Tech University; he also received a MIT Sloan Executive Certificate in Management and Leadership. Dr. Moyer holds over 37 issued patents and has authored or co-authored over 40 publications.  In addition to his experience at Dow Chemical, Dr. Moyer spent 18 years as a Global Product Platform Leader and Global Thin Films Product Platform Manager for the Electronic Solutions Business of the Dow Corning Corporation. 

Dr. Robert A. DeVries is currently a consultant at R. DeVries Consulting, Westlake, OH.    Dr. DeVries’ innovative contributions while a Scientist at Dow Chemical on the photodefinable BCB project involved developing new methods for synthesizing both BCB monomer and polymer resins for high volume manufacturing.  His inventions included new scalable processes for producing high purity, consistent materials absent impurities that could result in premature curing and poor process control.  In partnership with Eric, Robert devised a new way to control the base resin molecular weight characteristics in a production-scale process, critical for providing photodefinability. He also co-invented a novel self-primed adhesion promoter system with Ted to ensure device performance reliability.  Dr. DeVries received a B.S. degree in chemistry from Michigan State University and a Ph.D. in organic chemistry from Michigan State University under the supervision of Prof. Robert H. Grubbs.  He holds over 30 patents and 35 publications.  He has served on the Board of Directors of the Organic Reactions Catalyst Society (ORCS), and received the Dow Inventor of the Year Award for his work on dielectric resins, as well as the Dow Scientist Award for his leadership and research on benzocyclobutenes.  In addition to his experience at Dow Chemical, Dr. DeVries has held the position of Lead Scientist for reactive processing of nanomaterials at PolyOne Corporation, as well as Technical Director at Michigan Biotechnology Institute (developing novel biobased polymers) and at OMG Americas (new metal carboxylate additives). 

Dr. Theodore (Ted) M. Stokich, Jr is a retired Research Scientist, Dow Chemical, Midland, MI.  He led the effort to develop a deep fundamental understanding of the physics of the BCB polymer matrix. He used a combination of spectroscopic, rheological, and thermal techniques to work out the curing and oxidative mechanistic pathways of these new polymeric materials. By building a unique, custom-designed thermal fixture he was able to probe the vibrational spectroscopy of thin films to advance cure and oxidation kinetic understanding. His development of new time-temperature superposition predictions of cure profiles was critical to the measurement and control of photodefinable BCB in manufacturing processes.  Dr. Stokich also spent several years in Dow Core R&D – Analytical Sciences working on the development and application of comprehensive two dimensional chromatography of polyolefins, as well as paste rheology for advanced ceramics and rheology of adhesives for automotive applications.  Dr. Stokich received a B.S. degree in chemistry from the University of Minnesota-Duluth, and an M.S. and Ph.D. in analytical chemistry from the University of Wisconsin-Madison.  He has authored or co-authored more than 50 technical publications and presentations.  Dr. Stokich is also a 29-year veteran of the US Navy and Naval Reserve, with a retirement grade of Captain, USN.

Dr. Carol E. Mohler is a Principal Research Scientist in Core R&D with Dow Chemical, Midland, MI.  Her innovative contributions on the photodefinable BCB project included developing novel “fab-friendly” in-situ cure and oxidation metrology, which enabled cure and oxidation analyses to be performed on BCB films regardless of substrate or device integration scheme.  She also discovered a unique spectroscopic method to correlate photocrosslinker activity in photodefinable CYCLOTENE formulations with end-use lithographic performance, providing an unparalleled ability to control the accuracy and reproducibility of photocrosslinker addition during plant production runs.  These methods are still in use today by customers and in material production.  In addition to her work on photodefinable BCB, Dr. Mohler also drove the development of novel in-situ metrology for nanoporosity in low dielectric constant materials, by identifying, recruiting and leading collaborations with tool vendors, academia and consortia.  She has also pioneered research at Dow on high-throughput approaches to accelerate development of new high-value products in diverse market segments (architectural and pharmaceutical coatings, bio-based food additives, building and construction, and oil and gas applications). Dr. Mohler received a B.S. in chemistry from the University of Michigan, a Ph.D. in physical chemistry from the University of Wisconsin-Madison, and completed postdoctoral work at the University of Delaware.  She has authored or co-authored more than 65 technical publications and presentations.

 

CYCLOTENE™ Advanced Electronic Resin is a Trademark of The Dow Chemical Company. 

2014 ACS TEAM INNOVATON AWARD IN HONOR OF RAMIN AMIN-SANAYEI, ROICE WILLIE, JOHN STULIGROSS, KURT WOOD AND KEVIN HANRAHAN

 

 

Ramin Amin-Sanayei, Roice Wille, John Stuligross, Kurt Wood, and Kevin Hanrahan (pictured from left to right), winners of the 2014 American Chemical Society Team Innovation Award, are recognized for their work leading to the introduction of Kynar Aquatec® emulsion resins, a new polymer platform for highly weatherable waterborne coatings.

Industrial coatings based on Kynar 500® polyvinylidene fluoride (PVDF) resins were first commercialized in 1965 and offer outstanding exterior durability, color retention, and resistance to dirt-pickup, with a demonstrated 30+ year service life.  However, these traditional PVDF-based coatings are solvent-based and require high-temperature baking, necessitating factory application to control emissions and metal substrates to withstand the high bake temperatures. To bring the excellent PVDF coating performance to other substrates (composites, glass, polymers, wood, etc.), and to improve sustainability, the Arkema Inc. team invented, developed, and commercialized novel water-based fluoropolymer technology. Low VOC coatings formulated with this technology can now be used over multiple substrate types in both air-dry field applications and lower-bake temperature factory applications, ultimately delivering the same durability and performance as traditional solvent-based PVDF coatings.

This multidisciplinary team overcame several technical challenges to make Kynar Aquatec® emulsion resins a success. In conventional solvent-based PVDF coatings, the liquid paint formulation contains both PVDF and acrylic resins that must “alloy” at high temperature. This team was tasked with delivering the PVDF/acrylic morphology on a molecular level through in-situ emulsion polymerization, and with maintaining this morphology throughout the coating application process and the lifetime of the product.

Three key inventions were made: generation of a stable “fluoropolymer seed” dispersion (latex), identification of acrylic monomers that would be thermodynamically miscible with the seed, and an elegant acrylic staging process. The chemistry to make the fluoropolymer seed was especially innovative because it is very difficult to synthesize and stabilize a fluorosurfactant-free fluoropolymer aqueous dispersion with small particle size, high solids, and low crystallinity. This challenge was overcome by using a combination of theories (surface energies, partitioning coefficients, and compatibility parameters) to predict surfactant properties, ultimately ensuring the surfactant did not interfere with the polymerization kinetics. The choice of initiator type and structure also played a major role in successfully synthesizing the fluoropolymer seed. These discoveries enabled the team to produce stable fluoropolymer/acrylic hybrid dispersions that deliver the required lower-temperature film formation, substrate adhesion, and weathering resistance.

Subsequently, the team successfully tackled new technical issues relating to inadequate mixing and coagulation as the process was taken to pilot scale and commercial manufacturing. Throughout the entire development process, the applications team developed and optimized coating formulations incorporating Kynar Aquatec® emulsions, to ensure compliance with end-use customer application requirements.

The Kynar Aquatec® team, through the development of this innovative technology, has enabled access to markets and applications that was considered impossible just a few years ago. With several customers already in each major geographic region, Arkema predicts double-digit growth for the next 10 years. In fact, the technology has already been highlighted in many flagship projects throughout the world. This technology is currently used for, but is not limited to, the following applications:

     -- Field-applied reflective white roof coatings: “Cool roof” technology has received increasing national attention as a key component of energy conservation initiatives, and is being mandated through new regulations (e.g., California Title 24). To qualify for an Energy Star® rating, low-slope roofs must have an initial total solar reflectance (TSR) of >65%, with a three-year aged TSR of >50%. This aged TSR value has been a weak point for other roof coating systems due to poor dirt, microbial, and weathering resistance. A typical white paint based on Kynar Aquatec® emulsion resin has an initial TSR of about 81%, dropping to only ~78% after five years of exterior exposure. With so little reflectance loss, this paint technology exceeds current mandates for reflectivity retention and extends energy savings by many years. When the longer lifetime of the Kynar Aquatec® coating system and the energy savings are factored in, its life cycle cost is lower than traditional roof coatings.

    -- Factory-applied low-bake durable coatings: Component manufacturers can now provide building components (e.g., trim, moldings, siding, shutters, window and door profiles, fencing, railing, decking) with long-lasting Kynar Aquatec® emulsion resin-based topcoats, regardless of which substrate is used to manufacture the article.  Some examples include cellular PVC siding for homes, pultruded composite window profiles that combine the strength of aluminum profiles with the excellent insulative properties of non-metallic construction materials, and aluminum doors with thermal breaks, which are coated after assembly. 

The development and commercialization of this patented and innovative technology has been a major project at Arkema, and has been possible only through the efforts and contributions of the entire Kynar Aquatec® emulsion resin team. Furthermore, this technology continues to enable new fluoropolymer chemistries for use in numerous next-generation, high-durability, water-based coatings applications.

Dr. Ramin Amin-Sanayei is a Principal Research Scientist at Arkema Inc. in the Fluoropolymers R&D synthesis group.   He was the lead scientist developing the process for the small particle  size, fluorosurfactant-free seed latex used at the base of the first KYNAR Aquatec® products.  Beyond this, he has designed, synthesized, and commercialized many other new fluoropolymer products including low crystallinity fluoropolymers, co-continuous alloys of fluoropolymers, “ultra-High-MW” PVDF, binders for membranes and lithium ion batteries, and open-cell foams based on waterborne fluoropolymers.  Most of these products are made using more environmentally friendly “fluorosurfactant-free” processes, based on several new classes of surfactants discovered by Dr Amin-Sanayei.  He received a BASc. In Chemical Engineering from Sharif University, Tehran, Iran, and an MASc and Ph.D. in Polymer Synthesis & Characterization/ Chemical Engineering, from the University of Waterloo, Waterloo, Canada.  He joined Arkema Inc. in 1994.

Kevin Hanrahan is currently General Manager for Arkema’s Specialty Polyamides- North America business. Prior to becoming Global Business Director, Coatings Market for the KYNAR® PVDF business, he was a Business Development Manager playing a key leadership role in commercializing several new technology platforms including the Kynar Aquatec® platform.  The commercial success of the KYNAR Aquatec® platform depended on Mr. Hanrahan’s design and implementation of a development strategy across diverse markets, focusing on end-use education and pull-through marketing.  The strategy was launched through a strong “cold call” methodology to identify and cultivate new partner customers.  .In previous positions with the predecessor sister companies of Arkema, Mr. Hanrahan was an Internal Auditor for Total, N.A., and Technical Service Manager & R+D Manager for Cook Composites and Polymers, where his team won Atofina’s “Prix de l’Innovation” award in 2000. Prior to that, he worked in ink formulation for JM Huber Corporation and BASF Corporation. He received a B.Sc. in Industrial Chemistry from the University of Limerick.

John Stuligross is a Principal Process Technology Engineer in the KYNAR® PVDF Kynar Process Technology group at Arkema Inc.  He was the principal engineer working on the commercial scale up both of the small particle size, fluorosurfactant-free seed latex used as the base of the first KYNAR Aquatec® products, as well as the processes for several of the products themselves.   He also coordinates pilot plant activities, and provides process support and optimization for Arkema PVDF plants worldwide.  Before joining Arkema, he worked as a process engineer at hte (equipment design and operation for high throughput experimentation), PPG Industries (new product development, and process development and support for several businesses), and OxyChem (process development ans support for chlorination and fluorination processes).  Mr. Stuligross received a B. A. in Chemistry from Lawrence University, and an M.S. in Chemical Engineering from the University of Wisconsin-Madison. 

Dr. Roice Wille is a Principal Scientist at Arkema Inc. in the Fluoropolymers R&D synthesis group.   He was involved in some of the earliest studies to develop the KYNAR Aquatec® resin platform, and is the main scientist developing processes for new Kynar Aquatec® products and improving the manufacturing processes for existing products to improve environmental stewardship and process reliability.  Beyond this, he has also overseen the development, from laboratory through commercial scale up, of several other new PVDF product lines in the Arkema fluoropolymers business including Kynar Flex® 3120 for extrusion and molding applications, Kynar Powerflex® LBG for lithium batteries, and Kynar Superflex® for extrusion and molding applications.   He has made significant contributions in the area of promoting environmentally sound materials and practices, both in Arkema’s processes, and also in the larger fluoropolymers industry through work with the Fluoropolymers Manufacturing Group.    Dr Wille received a B.B.A. in Business Administration from the University of Michigan, a B.S. in Chemistry from Michigan State University, and an M.S. and PhD. in Chemistry from Rensselaer Polytechnic Institute.  He joined Arkema Inc. in 1990.

Dr. Kurt Wood is a Principal Scientist at Arkema Inc. in the Fluoropolymers R&D Coatings Applications group, where he is a new product development specialist.  For many of the KYNAR Aquatec® developments, including the first commercial product launch, he has served as the main technical interface with potential customers—working both with Synthesis colleagues on product design, and with customers’ formulation scientists to develop coating formulations with the developmental products which will fully meet end-use performance requirements. One important contribution was to develop new methodology for the rapid prediction of weatherability for 30-year PVDF coatings, leading to the identification of composition and morphology requirements that would permit optimum weatherability in KYNAR Aquatec® latex-based coatings.  This work has lead to a more general interest in service life prediction and he has been an active contributor to international consortia and conferences on this topic.   Dr. Wood received a B. S. in Chemistry from the University of California at Davis, and a PhD. in Physical Chemistry from the University of California at Berkeley.   He worked for a number of years in Industrial Coatings R&D at the Rohm and Haas Company and then joined Arkema Inc. in 1996.

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Kynar Aquatec® and KYNAR 500® are trademarks of Arkema, Inc.

 

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