Practical Use Of Nanomaterials In Plastics


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Practical Use Of Nanomaterials In Plastics

  1. 1. Practical Use of Nanomaterials in Plastics Innovative Technologies Symposium for Plastics July 31, 2007 Joseph J. Schwab Hybrid Plastics ™
  2. 2. What is Nanotechnology? Nanotechnology is the understanding and control of matter at dimensions of roughly 1 to 100 nanometers. Nanotechnology involves imaging, measuring, modeling, and manipulating matter at this length scale. At the nano-scale, the physical, chemical, and biological properties of materials differ from the properties of individual atoms and molecules or bulk matter, creating improved materials, devices, and systems that exploit these new properties.
  3. 3. What is Nanotechnology? “A hundred years ago, or even fifty, nanotechnology would have just been called chemistry” Economist, 5 July 2001
  4. 4. What is Nanotechnology? Nanotechnology Nanostructured Materials Nanotools Nanodevices Fabrication Molecular Nanoparticles Techniques Electronics Nanocomposites Instrumentation Mems & Metrology & BioMems Analysis Supramolecular Lab on Chip Assemblies Software Computation Sensors & Simulation Detectors Device Miniaturization
  5. 5. Representative Types of Nanoparticles Nanoparticles Carbon Tubes POSS® -Single Walled -Molecular Silicas -Multi Walled -Monomers -Silanols -Polymers Fullerenes Dendrimers Graphenes Nanofibers Clays Metal & Metal Oxides -Montmorillonite -Halloysite Silica -Vermiculite
  6. 6. Why is Nano Important in Materials? Field Property Critical Length 1 mm Electronics Tunneling 1-100 nm • Sewing Needle • Razor Blade Thickness Optical Quantum Well 1-100 nm Wave Decay 10-1000 nm 100 µm Polymers Primary Structure 0.1-10 nm • Human Hair Secondary Structure 10-1000 nm • Most Cells & Fibers Mechanics Dislocation Interaction 1-1000 nm 10 µm Crack Tip Radius 1-100 nm 1 µm • Bacteria, Fillers & Entanglement Rad. 10-50 nm Polymer Morphology Therm-Mech. Chain Motion 0.5-50 nm 100 nm • Viruses & Nanofillers Nucleation Defect 0.1-10 nm 10 nm Critical Nucleus Size 1-10 nm • POSS® Building Blocks Surface Corrugation 1-10 nm 1.0 nm • Macromolecules Catalysis Surface Topology 1-10 nm 0.1 nm • Atoms / Small Molecules Biology Cell Walls 1-100 nm Membranes Porosity Control 0.1-5 nm
  7. 7. Nanomaterials Are Really Not New What has been, that will be; what has been done, that will be done. Nothing is new under the sun. Even the thing which we say, “See, this is new!” has already existed in the ages that proceeded us. Ecclesiastes 1, 9-10 Source: University of Dayton NEST Lab
  8. 8. Carbon Nanotubes Source:Peter Harris Source:Wikimedia Commons Source:Peter Harris
  9. 9. Multi-walled Nanotubes Source:Hyperion Catalysis Source:Hyperion Catalysis Source:Hyperion Catalysis
  10. 10. Carbon Nanotubes Carbon Nanotubes (CNTs) typically have diameters 1000 times smaller than traditional carbon fibers. Single-walled CNTs (SWCNTs) consist of a single tubular graphene sheet and have diameters of 1-2nm. Multi-walled CNTs (MWCNTs) typically consist of 5-15 tubular graphene layers and have diameters of 10-12nm. CNTs can be up to 50 times stronger than steel and have excellent thermal and electrical conductivity.
  11. 11. Fullerenes O O RO OR C60Fullerene Endohedral C60Fullerene Chemically Modified C60Fullerene
  12. 12. Timeline for Fullerenes (A Cautionary Tale) In 1985 C60 is discovered. By 1990 a process for making gram quantities is developed and accelerates research efforts. At the end of 2001 Mitsubishi Chemical Corporation and Mitsubishi Corporation establish a joint venture called the Frontier Carbon Corporation (FCC) with the goal of becoming the world leader in the commercial production of nano-scale carbon products. In 2002 FCC claims mass production of 400kg/yr of fullerenes. By 2003 FCC claims to be operating a 40 tons/year commercial-scale, low-cost plant to produce fullerenes. FCC claims delivery of fullerene samples at prices ten times lower than 2002 prices. FCC also claims first commercial product, a bowling ball. In 2004 FCC claims 400 Japanese companies have purchased samples. Claims that commercial products in Japan include fiber reinforced composites for badminton rackets, tennis rackets, golf club shafts, snow boards, ski and snow board wax, lubricants for car air conditioners, and coatings for glass. In December 2004 FCC establishes Frontier Carbon Corporation of America (FCCA) “To meet the growing commercial demand for nano-scale products in the United States and Europe”. FCCA is to begin production of fullerene materials in the U.S. In 2005 FCCA announces an agreement with TDA Research to offer a range of fullerene products under the Nanom product line. Although many claims about mass production, costs remain high.
  13. 13. Nanoclay Source:Southern Clay Source:Wikimedia Commons Source:Natural Nano
  14. 14. Nanoclay Almost all nanoclays used in the plastics industry are minerals which are mined from naturally occurring deposits. Montmorillonite is the most widely used clay. It has a plate-like anisotropic structure and is nano in only one dimension. Halloysite is a tube shaped clay having a typical diameter of 40-200nm and a length of 0.5-10um.
  15. 15. Metal & Metal Oxide Nanoparticles Source:Nanophase Technologies Source:Nanophase Technologies Metal oxide nanoparticles are actually isolated as agglomerates, typically over 1,000 nanometers in size, and behave similarly to conventional powders. Source:Nanophase Technologies
  16. 16. POSS® Nanostructures Unreactive organic (R) One or more reactive groups for solubilization groups for grafting or and compatibilization. R polymerization. O X Si Si O O R O Si Si O R O O R O Si Si O O R Nanoscopic size O Thermally and chemically Si Si Si-Si distance = 0.5 nm O robust hybrid R R-R distance = 1.5 nm. R (organic-inorganic) framework. Precise three-dimensional structure for molecular level reinforcement of polymer segments and coils. R R OH O Si M Si O O O O OH R O R Si Si Si Si O O O R R OH O R O O R O Si Si Si Si O O R O O R Si Si O Si Si O O O R R R R Metal Containing Stable Silanols
  17. 17. Why Should We Expect Improvements? A unique aspect of nanotechnology is the vastly increased ratio of surface area to volume present in many nano-scale materials. Nanoparticles in particular have a very high surface area to volume ratio. For example, montmorillonite nanoclay platelets have a surface area of 750 m2/g. This means that ~7g of platelets could cover an area the size of a football field. This enormous surface means that in a nanocomposite almost all of the matrix (polymer) will be in contact with the nanoparticle. Since the physical properties of the nanoparticles themselves are generally superior to the polymer matrix this suggests that the properties of the nanocomposite will trend toward those of the nanoparticle.
  18. 18. Keys to Nanocomposite Polymers Unfortunately nanoparticles are rarely compatible with polymer matrices and a tremendous amount of time, money, and effort has gone into trying to overcome this problem. If the nanoparticle is not acting act the nanometer level we really should not expect results any different from those obtained with ordinary macroscopic fillers. – Compatibility: Nanoparticle must have compatibility with matrix. – Dispersion: If good compatibility is achieved, complete dispersion at the molecular/nano level should occur. – Properties: If dispersion at the molecular/nano level is achieved, improved optical, physical and mechanical properties should result. Compatibility  Dispersion  Improved Properties
  19. 19. Dispersion of Nanotubes Poor compatibility between the CNT surface and the matrix lead to difficulty in exfoliating and debundling CNTs. Poor adhesion of the matrix causes poor dispersion, phase separation and aggregation of the CNTs making incorporation of untreated CNTs into polymers difficult. Several companies have now begun to address these issues by developing proprietary compatibilizers: CNT Surface compatible functionality Polymer compatible functionality
  20. 20. Dispersion of Nanoclay Clay Particle Clay Platelets Clay particles consist of groups of stacked platelets. The challenge is to process the clay nanocomposite so as to achieve complete dispersion of individual platelets.
  21. 21. Dispersion of Nanoclay Nanoclay must be organically modified in order to achieve compatibility with a polymer matrix. Long chain alkyl ammonium cations are typically used + OH N HO Source: Southern Clay Source: Southern Clay
  22. 22. Dispersion of Nanoclay Source: Southern Clay Poor Dispersion Source: Southern Clay Good Dispersion, Partial Dispersion, considered complete considered incomplete Source: Southern Clay
  23. 23. Dispersion with POSS® Blended into 2 million MW Polystyrene R R O R Si Si O O O Si Si R O O O Si Si R O O R O Si O Si R O O R O Si Si O R O O O R Si Si O O R Si Si O O Si Si O R R O R R R = cyclopentyl R = cyclopentyl domain formation partial compatibility R O R O Si Si Si Si O O O O R O R O Si O Si Si O Si R O R O O R O O R O Si Si Si Si O O R O O R Si Si O Si Si O O O R R R R R = styrenyl R = Phenethyl phase inversion 50 wt% loading and transparent!
  24. 24. Dispersion with POSS® Imaging studies on Nanoreinforced® PP fibers Molecular Silica™ dispersion confirmed at molecular level. * Each black dot represents a 1.5 nm POSS® cage. R O R Si Si O O R O Si Si O R O O R O Si Si O O R Si Si O R O R R R R R Si O O O Si Si O O Si R O Si O O O R Si R O O Si O Si Si R R O O O Si O Si R O Si R *scale = 50nm. R Source: Viers - US Air Force Research Laboratory
  25. 25. Representative Suppliers of Nanoparticles Company Material supplied How supplied Hybrid Plastics POSS Raw Material & Masterbatch Nanocor Nanoclay-Nanomer, Imperm Raw Material & Masterbatch Sothern Clay Nanoclay-Closite Raw Material Foster Corp. Nanoclay-Nanomed Compounded nylon Basell Nanoclay-Hyfax Compounded polyolefin RTP Company Nanoclay, Nanotube Compounded products Polyone Nanoclay-Nanoblend Compounded, Concentrates Nycoa Nanoclay-nanoSEAL Compounded products Hyperion MWCNTs-Fibril Masterbatch Bayer MaterialScience MWCNTs-Baytubes Raw Material Arkema MWCNTs-Graphistrength Raw Material, Masterbatch Carbon Nanotechnologies, Inc SWCNTs-HiPco and CNI X Grades Raw materials Nanocyl CNTs Raw Material, Masterbatch Nanoledge CNT-Nanoin Concentrates Zyvex CNTs-Kentera Concentrates Nanophase Metal oxides-NanoArc, NanoDur, NanoGard Raw Material
  26. 26. Representative Applications of Nanotubes For the most part, the plastics industry has focused on the use of MWCNTs, primarily because they are lower cost and the difference in property enhancements relative to SWCNTs is slight. Largest use of CNTs is for electrostatic dissipation. Also targeted are improved mechanical and thermal properties. In the area of electrostatic dissipation the two largest applications are in automotive and electronics handling equipment. In automotive applications CNTs are used in body parts to provide a Class A surface for electrostatic painting. Another automotive application is fuel line components such as pumps, lines and housings. In electronics applications CNTs are used in trays for wafer manufacturing and in housings for disk drives. Many applications are in sporting goods to improve mechanical properties of composites. Competes with carbon black and carbon fiber.
  27. 27. Representative Applications of Nanoclay Applications in plastics principally revolve around improving barrier properties, flame resistance, thermal and structural properties. Early commercial targets were in automotive and packaging applications. For automotive applications the target has mainly been weight savings, as lower loadings of nanoclay can be used to reinforce polymers vs. other mineral fillers. Clay nanocomposites also provide better surfaces, reduced CTE and are potentially amenable to recycling. In packaging the target has been barrier properties. Mainly in the area of beverages. Other barrier applications have focused on tires and sporting goods (balls). Applications for improving fire resistance of plastics also vigorously pursued. Competes with traditional inorganic fillers.
  28. 28. Representative Applications of Metal & Metal Oxides Primary applications in plastics include antimicrobial, fungal and mold resistant materials. Other applications include protection from visible and UV light and abrasion resistant coatings.
  29. 29. Representative Applications of POSS Major focus on aerospace and defense applications. Radiation hardening and shielding. Food Packaging. Electronic materials. Space Resistant materials.
  30. 30. POSS® Barrier in Food Packaging POSS® incorporation provides longer product shelf life. Improves color printing.
  31. 31. POSS® Oxidation Resistance MISSE 1 POSS Polyimide Samples: Erosion Depth (µm)
  32. 32. POSS® Oxidation Resistance Etch Capabilities in Bilayer Resist Design SLR Resist Si-based Resist LER 5.0 nm LER 6.6 nm After Strip Before Strip LER 12.9 nm LER 6.0 nm Much Improved LER after Pattern Transfer due to Excellent Etch Characteristics of Silicon-based Resist
  33. 33. POSS® Oxidation Resistance No Pattern Collapse after Etch Transfer (75 nm line/150nm Pitch) 75nm L/S after dry development of UL Silicon based resist can support high aspect ratio due to excellent etch selectivity
  34. 34. POSS® Tooth Restoration Products
  35. 35. Examples of Commercial Nanocomposites Source: Southern Clay Source: GM While reports on the use of nanocomposites in automotive applications were quite frequent as recently as 2005, there has been a significant reduction since. Some sources reported that Nanocomposites would be used in 2006 models, but it is unclear how much is currently being used.
  36. 36. Examples of Successful Nanocomposites Nanotube-containing surfboard Source: Oceanit is tested near San Francisco. Source: Nanoledge Source: Montreal Hockey Additional examples include golf clubs, tennis rackets, sail boat masts, and skis.
  37. 37. Commercial Success can be Short Lived Triton Systems, Inc. - Converse All Star He:01 using ORMLAS polymer nanocomposite discontinued after initial launch. InMat, Inc. - Wilson discontinues development of Double Core tennis ball after initial launch. Honeywell Aegis NC - no longer manufactured. Aegis OX no longer contains nanocompoite. Eastman Chemical’s Nanocomposites - after significant effort in the area, intellectual property portfolio for polymer nanocomposites was donated to the University of South Carolina.
  38. 38. Truths about Nanotechnology For a successful technology, reality must take precedence over public relations, for Nature cannot be fooled. Richard Feynman US educator & physicist (1918 - 1988)
  39. 39. Truths about Nanomaterials “Nano” is not as important as the solution it provides. Nano has no intrinsic merit other than what it does! The entry and market capture for “nanosolutions” requires vastly more time, capital, and support than anyone is willing to admit. Each nanosolution must earn a right to survive via the application of hard science and economics rather than reliance on slick marketing.
  40. 40. Trouble Brewing? Earlier this year DuPont and Environmental Defense combined to launch a Nano Risk Framework. The framework is designed to provide a systematic and disciplined process to evaluate and address the potential risks of nano-scale materials. In 2005 the EPA announced that it was reclassifying nanosilver as a pesticide. In 2005 the Berkeley, CA City Council approved an amendment to their hazardous materials law to include nano-sized particles which requires researchers and manufacturers to report what materials they are working with and how they are handling them. Earlier this year the Cambridge, MA City Council announced that it is considering a similar law. Several studies have indicated that carbon nanoparticles might act as cytotoxins while others have shown that CNTs can have an asbestos like effect on lung cells. Other studies have found no links between carbon nanoparticles and cytotoxic effects.
  41. 41. Thank You R O R Si Si O O R O Si Si O RO O O R Si Si O O R Si Si O O R R