Nano Technology & Nano Materials
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Nano Technology & Nano Materials

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Nano Technology & Nano Materials
by Ray Fernando, PHD

California Polytechnic State University
Polymers and Coatings Program
Department of Chemistry and Biochemistry
San Luis Obispo, CA
www.polymerscoatings.calpoly.edu

Delivered 22 June 2009 @ SLINTEC

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  • 1. Ray Fernando, PhD Fernando 22 June 2009 California Polytechnic State University Polymers and Coatings Program Department of Chemistry and Biochemistry San Luis Obispo, CA p , www.polymerscoatings.calpoly.edu
  • 2. Nanotechnology Overview Nanomaterials Properties Potential Benefits Commercial Applications Challenges
  • 3. Nanotechnology is the understanding and control of matter at dimensions of roughly 1 to 100 nanometers, where unique phenomena enable novel applications…. ……………encompassing nano-scale science, engineering and t h l i i d technology; nanotechnology t h l involves imaging, measuring, modeling, and manipulating matter at this length scale scale. (www.nano.gov)
  • 4. U.S. National Nanotechnology Initiative (NNI) Initial phase funded by Federal Government in late 1990’s Formal NNI proposal on March 11, 1999 Funded in 2001 with a$489 million “…….a ‘new industrial revolution’ powered by systematic control of matter at the nanoscale….” y NNI is largest nanotechnology investor over last 7 years ($7 billion) Now NNI involves 26 independent agencies $1.5 l d d $ billion (2008) “Top ten advances in materials Science”, J. Wood, Materials Today, 1(12), 40
  • 5. Global Initiatives Over 65 countries have national research focus projects on nanotechnology 2007 global nanotechnology related R&D budget was g gy g in excess of $12 billion Industry investment surpassed governments’ in recent years. years “Top ten advances in materials Science”, J. Wood, Materials Today, 1(12), 40
  • 6. http://www.nano.gov/html/facts/The_scale_of_things.html
  • 7. C-C bond – 1.5 angstroms g C-H bond – 1.1 angstroms Ethanol: CH3-CH2OH 10-4 10-2 100 102 104 106 108 1010 Nanometer
  • 8. Size and refractive index of particles are important Nanoparticles are smaller than the wavelength of visible light; reduces chance of light scattering
  • 9. Polymer latex particle size 50 - 500 nm Hiding Hidi grade TiO2 particle d ti l 200 - 250 nm size Polyurethane Dispersion 50 - 100 nm particle size Polymer molecular size in 2 - 100 nm solution
  • 10. A = 4Πr2
  • 11. Volume = 4/3*π*r3 Surface area = 4*π*r2 1 gram of TiO2 Volume = 0.25 cm3 Particle P ti l Particles P ti l Surface S f Surface S f diameter per gram area per Area / (nm) gram (m2) Volume 200 6 x 1013 7.5 1.8 x 1012 20 6 x 1016 75 1 8 x 1016 1.8 2 6 x 1019 750 1.8 x 1020
  • 12. Bulk properties are not scalable to nanoscale
  • 13. A particle of 10nm diameter has 20% surface atoms A particle of 2nm diameter has 80% surface atoms A particle of 1nm diameter has ti l f 1 di t h 100% surface atoms Single wall Carbon nanotube A capped single-wall carbon nanotube with a slight bend. http://www.thomas-swan.co.uk/pages/nano_images.html
  • 14. Particle Diameter (nm) ( ) 300 250 200 150 100 50 Interfacial 0.03 0.04 0.05 0.06 0.10 0.22 Volume Fraction 10 nm Interfacial Layer Dispersed particle volume fraction is 0.3 in all cases
  • 15. Extensive interfacial area 103 to 104 m2/ml Large number density of particles 106 to 108 particles/μm3 Low percollation threshold ~0.1 – 2 volume% Short d Sh distance between particles b l ~0.1 – 2 volume% Bulk B lk material properties not scalable t i l ti t l bl Optical clarity
  • 16. Polymer molecules at i t f P l l l t interface Surfactants t S f t t at water/air i t f t / i interface
  • 17. “Thermo-mechanical properties of LLDPE/SiO2 nanocomposites”, E. Kontou and M. Niaounsikis, Polymer, 47, 1267, 2006 - Tg K t d M Ni iki P l 47 1267 T increases of 25 to 30oC observed with up to 10% nano silica “Glass-Transition Temperature Behavior of Alumina/PMMA Glass Transition Nanocomposites”, B. J. Ash, R. W. Siegel, and L. S. Schadler, J. Polym. Sci.: Part B: Polym. Phys., 42, 4371, 2004. – Nano alumina / PMMA composites. 25oC drop in Tg with less p p g than 1% 38nm and 0.5% 17 nm. Up to 10% further addition did not lead to additional Tg reductions
  • 18. “Glass Transition of the Polymer Microphase”, Bares, J., Macromolecules, 8, 244, 1975 - Tg of finely dispersed phases (~12 nm) was 20oC lower than the analogous bulk phase; proposed the first equation (modified Fox-Flory) relating the Fox Flory) Tg to the enhanced surface to volume ratio “Nanofiller effect on the glass transition of a polyurethane”, J. G.-I. Rodriguez, al., J. Rodriguez et al J Thermal Anal Calorimetry, 87(1), 45, 2007 - Anal. Calorimetry 87(1) 45 DSC study on polyester PU with “nano” silica. Silica particle sizes are 175, 395, 730 nm, and levels are up to 10 wt.%; PU Tg ( oC) did not change with the nanoparticles ; g (-10 ) g p
  • 19. y “Dynamic and viscoelastic behavior of natural rubber/layered silicate nanocomposites obtained by melt blending”, Ramorino, et al., Polym. Eng Sci Polym Eng. Sci., 2007 “Natural rubber nanocomposite reinforced with nano silica”, Chen, et al., Polym. Eng. Sci., silica , 2008 “Sol-gel process of alkyltriethoxysilane in latex for alkylated silica formation in natural rubber”, Siramanont, et al., Polym. Eng. Sci., 2009
  • 20. Dispersion of layered inorganics in polymer In-situ generation of nano-phases Incorporation of nano-particles
  • 21. Nylon/Clay Nanocomposites (Toyota/Ube, 1980’s) 1980’ ) 70% higher tensile modulus 125% higher flexural modulus Heat distortion H t di t ti temperature increased from 65 oC Epoxy / Layered Silicate (Vaia – to t 152 oC Materials Today, 2004)
  • 22. X-ray diffraction pattern Dispersed Intercalated Exfoliated •Pinnavaia, T.J., and Beall and G.W. (Ed.), “Polymer-Clay Nanocomposites”, Wiley (2000) •Gao F Materials Today November 2004 F., Today, •Vaia, R.A. and Wagner, H.D., Materials Today, November 2004
  • 23. Barrier Gas, Water etc Gas Water, etc. Anti-Corrosion Fire Retardancy Mechanical Properties Microcomposite Aspect Ratio 25:1 Nanocomposite Aspect Ratio 250:1
  • 24. Nano-Clay Suppliers Elementis Nanocor Southern Clay Others Product Manufacturers P d M f Inmat, Inc. 2001 Wilson double core tennis balls Recent efforts on PET, PP film barrier coatings Others
  • 25. TEOS Hydrolysis/condensation
  • 26. Sol- Sol-Gel Hybrid Nano-Composite Nano- Coatings OCH3 TEOS H3CO Si OCH2CH2CHCH2 Cyclo-aliphatic Epoxy OCH3 O OC2H5 + + O H2 GPTMOS C C Si O C2H5O OC2H5 O O OC2H5 Inorganic / Organic Nanocomposite g g p
  • 27. Aluminum Oxide Copper Oxide Antimony Tin Oxide Indium Tin Oxide Barium Sulfate Iron Oxide Bismuth Oxide Nano-Clays Boehmite POSS Calcium Cabonate Silicon Dioxide Carbon Nanotubes Titanium Dioxide Cerium Oxide Zinc Oxide Cobalt Aluminate ...……
  • 28. Anti-microbial Optical Properties Antistatic Photocatalysis Gas/Stain Barrier Surface Energy Corrosion Modification Fire Retardant UV Stability IR-Absorption X-Ray Shield Magnetic ……….. Mechanical
  • 29. 100 90 Gloss Retention (20 ) o 80 70 Alumina C 60 Alumina D %G 50 Silica A 40 0 0.5 05 1 1.5 15 2 2.5 25 3 3.5 35 Nanoparticle Content (Wt.%)
  • 30. Transformation of a Simple Plastic into a Superhydrophobic Surface Erbil, Demirel, Avci, and Mert, Science, Vol 299, Issue 5611, 1377-1380 , 28 February 2 Figure 1. (A) The profile of a water drop on a smooth i-PP surface that has a contact angle of 104° ± 2° Th i PP film was prepared by melting at 200°C t t l f 2°. The i-PP fil db lti t between two glass slides and crystallizing at 100°C. (B) The profile of a water drop on a superhydrophobic i-PP coating on a glass slide that has a contact angle of 160°. The i-PP was dissolved in a 60% p-xylene/40% MEK mixture by volume at an initial concentration of 20 mg/ml at 100°C. The solvent mixture was evaporated at 70°C in a vacuum oven The morphology of the i-PP coating 70 C oven. is shown in Fig. 4. Fig. 4. SEM picture of an i- PP coating obtained using the nonsolvent MEK as described in Fig. 1B
  • 31. θ θ - Contact Angle Zero Contact Angle Spontaneous Wetting & Spreading
  • 32. Rainwater cleans lotus leaves because of their bumpy surface. Abramzon, et al., Chemistry & Life (1982) y ( ) Barthlott et al., Annals of Botany (1997)
  • 33. Nano-Structuring Methods Nun, Oles, & Schleich, Macromol. Symp., 187, 677-682 (2002) “Nanostructured superhydrophobic surfaces”, H. M. Shang, Y. Wang, K. Takahashi, G. Z. Cao, D. Li, and Y. N. Xia, J. Mater. Sci., 40, 3587, 2005
  • 34. 1.0 Wt. % Alumina D ~25nm Avg. 0.67 Wt. % Alumina C ~25 nm Avg. particle size, 10 micron scan area particle size, 10 micron scan area
  • 35. g Self-cleaning surface Antibacterial Activity Super hydrophilicity Anti fogging Anti-fogging activity
  • 36. 1.2 1 UV Visible Region IR ce 0.8 08 Reflectanc 0.6 R 0.4 Rutile Anatase 0.2 0 360 400 440 480 520 560 600 640 680 720 Wavelength (nm) W l th ( )
  • 37. TiO2 + UV light ⎯→ e- + hole+ e- + hole+ ⎯→ TiO2 + heat hole+ + OH- ⎯→ OH• e- + O ⎯→ O • 2 - 2 • O2- + OH• + (-CH2-) ⎯→ intermediates • O2- + OH• + intermediates ⎯→ CO2 + H2O UV light + O2 + (-CH2-) ⎯→ intermediates → UV light + intermediates ⎯→ CO2 + H2O Self-Cleaning Surfaces
  • 38. Chalking: loose pigment particles form on the surface from the erosion of the binder as a result of photodegradation. photodegradation Type I Type II Type III Type IV Anatase Rutile Rutile Rutile Product Name LW R-900 R-900, R-901 R-960 TiO2 min % min.% 94 92 80 80 Chalking free medium medium medium resistant resistant resistant Surface treatment none Al2O3 SiO2 +Al2O3 SiO2 +Al2O3 Complete encapsulation to protect TiO2 from UV free radical reaction
  • 39. www.nanotechproject.org www.nanoshop.com
  • 40. Umicore – transparent Cerium Oxide and Zinc Oxide in Waterborne and solvent-based PU coatings for wood. Nanovations - Lignol® Wood Coating with nanoscale UV absorber; Nano- Silver, antimicrobial and energy saving façade paint from Bioni Paints “Bioni Paints are the only chemical free coatings in the world that can prevent Bioni the growth of moss, algae and mildew permanently” Teak Guard® Marine with Nanotechnology UV protection Nanotec Ultra® Coating UV protection Nanolinx™ “First wood floors finishing system to use a network of crosslinked g y nanoparticles” Nanoseal® Wood by Nanotec “…is not a sealer; nano particles adhere directly to substrate molecules……hydrophobic surface”; Nanoprotect® AntiG is a molecules hydrophobic surface ; water based nanotechnology treatment that provides a layer against Graffiti on concrete and natural stone surfaces
  • 41. •Nichiha Fiber Cement - “Nichiha uses Nanotechnology to create self- Nichiha self cleaning fiber cement panels” •Markilux – Awning fabric SNC (Swela Nano Clean); dirt and water repellant •STO Lotusan® Self Cleaning Paint – water repellant surface •AVM Industries – E-85 Nano 2000™ Self cleaning and deodorizing Titanium Dioxide coatings – water based based. •Akzo Nobel – Herbol® brand for professional architectural paints and coatings has introduced Symbiotec based on BASF’s COL.9 technology for façade coatings. Water based, water-thinnable, easy to handle, less thermoplastic, low dirt pick-up •Behr – Nanoguard Behr
  • 42. •Nanoclean - supplier of ultrathin glass treatments •NanoSafeguard - supplies photocatalytic self-cleaning hydrophilic NanoSafeguard self cleaning coatings for outdoor. •Saint-Gobain Glass supplies BIOCLEAN for window glasses (UV activated) ti t d) •Pilkington Activ™ Self Cleaning glass – nano thin layer •Nanoprotect® Glass Coating by Nanotec – easy to clean; self-cleaning; hydrophobic •nanoCotz™ Eco Refresh and nanoCotz™ Eco-Refresh, •Eco-Clean by Inspiraz, “The best self-cleaning clay roof in the world” by Erlus, Germany •n-tec, Germany – Photocatalytic Self-Cleaning Coatings – titania
  • 43. •Centrosolar supplies glasses with or without nano-coated anti-reflective properties •Bioni Roof by Bioni – Heat reflecting roof coating with unique nano effects Bioni,– •Delphi Labs– “Asgard™ is comprised of a strong, ultra-thin, transparent silica binder that holds tin-oxide and other functional ingredients in place •NaturalNano – supply cell phone blocking paint based on nanotechnology •Halloysite nanotubes 100nm X 500nm; claim that the tubes are inserted Halloysite with copper particles to reflect radio signel; other applications claimed as well.
  • 44. Nanoparticle Suppliers Altair Nano BYK-Chemie Clariant Degussa g Fuso Chemical Co. Hybrid Plastics Ishihara Nanophase Nanoscale Corp. Sachtleben Chemie Solvey Sukgyung A.-T. Sumitomo Osaka Cement Co Co. …..& many more
  • 45. Carbon Nanotubes (CNTs) Multiwalled Sumio Iigima Nature 354 56 1991 Iigima, 354, 56, Radushkevich and Lukyanovich, Zurn. Fisic. Chim., 26, 88, 1952 First direct observation reported p Oberlin et al.. J. Cryst. Growth, 32, 335, 1976 First image published Single-walled Iigima and Ichihashi, N t Ii i d I hih hi Nature 363 603 1993 363, 603, Bethune et al., Nature 363, 605, 1993 Nano-buds; Bucky-ball Graphene Calling all Chemists, Nanure Nanotechnology, 3, 10 January 2008 by Rod Ruoff UTexas Recent report b P d’h R t t by Prud’homme – F Functionalized G h ti li d Graphene N Nano- Sheets. Tg of PMMA increased to 118C from 95C at 0.25 wt.% level
  • 46. Mechanical Properties Light Weight Conductivity Metallic to Semiconductor
  • 47. p More than 50 companies worldwide Aerospace Corp. Applied Carbon Nanotechnologies Arkema Bayer Materials Nanoledge Canatu Nanocyl N l ZYVEX Performance Materials Hyperion Ilgin Nanotech Shenzhen Nanotech Mitsui-Hodogaya
  • 48. Dispersion and Dispersant Demand Surface Functionalization • Application Specific Rheology Aggregation & Flocculation Characterization Cost/Performance Balance Health Safety Health-Safety Concerns
  • 49. BASF COL.9 Nano binder (Example) Nano-binder Herbol (Germany) Façade coating Major US Paint Manufacturer j Low dirt pick-up and better durability claimed Composition: Nano-silica embedded in polymer latex particle d i synthesis l i l during h i Avoids dispersion by formulator Minimum interference with polymer particle coalescence
  • 50. Characterization Techniques For Bulk/Surface Morphology, Microstructure and Dispersion Micro- (Meso-) Macro- Nano Nano- nm μm mm AFM TEM - SEM Optical Microscopy Laser Scanning Confocal Microscopy Light Scattering Neutron Scattering SANS USANS Scattering metrology X-ray Scattering SAXS/WAXS USAXS Courtesy of LiPiin Sung - NIS
  • 51. •Nanoscale Materials Stewardship Program – launched by EPA January 28, 2008. TSCA Inventory Status of Nanoscale Substances – Jeneral Approach 2008 pdf available at website website, •Epa.gov/oppt/nano/stewardship.stm •“The potential risks of nanomaterials: a review carried out for p ECETOC”, P. J. A. Borm and 10 other authors, Particle and Fibre Toxicology, 3(11), 2006. Open Access at Journal website. ECETOC – European Centre for Ecotoxicology and Toxicology of Chemicals - 35 page review with 172 references •Nanosafe2.org
  • 52. Volume / Mass: y Gravity Volume Vol me d3 Surface: Friction F i ti Surface Energy Van der Waals Charge capacity Surface S f d2 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 101 meters
  • 53. Dispersion and Dispersant Demand d d Rheology Characterization Material Safety/Health Effects Cost/Performance Balance *FSCT Virtual Learning Conference -- 2004
  • 54. Theory DLVO Th (Two Particles) S Inter Particle Inter-Particle Forces a - Van der Waals, Long-range (Attractive) b - Electrostatic, Long-range (Attractive or Repulsive) R l i ) c - Steric, Short-range (Repulsive) g ( d - Solvation, Short-range (Attractive or Repulsive) e - Born, Atomic-range (Repulsive) 64
  • 55. Repulsive Potentia Energy c b e S al d a Attractive Att ti Repulsive ergy otential Ene S Flocculation/ Po Aggregation Agglomeration Attractive 65