Nanotechnology and the paperforest product industry

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Nanotechnology andthe paper/forest product
industry

• Dan Coughlin
• Paul Gilbert
• Steven Masia
• Tety Roper

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Growing Trend in Nanotechnology
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Nanotechnology Based on the Application in
Various Market Segment
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Mechanical Tailoring and control (Lightweight
paper with high strength Aerogel)
Electronic Functionality and Sensing (Printed
electronics displays, solar cells, fuel cells,
medical sensors)
Surface Functionality and Tailoring (
Hydrophobic /Hydrophilic Biosensors)
Optical properties (Specialized optics by
photonic nanostructure)
Lignocellulose Control and conformation tailoring
( Improved construction materials)
Modeling Smart Cellulose structures
(Piezoelectric- Electro-rheostatic and
Magneto-rheostatic )
Application Areas Nano-lignocellulosics
Thermal Properties and functionality (
Controlled heat conductivity and capacity)
Polymer Interaction and control of water
interaction (Improve dimensional stability)
Particle interaction and Grafting (Self assembly
and reinforcement for tensile strength, and
elasticity)
Nano scale Polysaccharide Processing ( New
biopolymers Ethanol biorefinery)
Nanoscale composites (Formation of nanofibers for
composite processing)
Porosity and Control ( Improved filtration and
membranes Improved printability)
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Nanotechnology

• Current Products, Approaches and New Processes
• Current challenges
• Forest Nanomaterials
• Strength improvements
• Water-Lignocellulose interaction
• Cellulose nanocomposites
• Viscose and Rayon containing Nanoparticles
• Applications of Nanopigments and Nanocoatings
• Photonics and Electronic/Piezo properties
• What is possible?

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Current Products, Approaches and New Processes
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Current products

• Method of making paper products using calcium
  carbonate nanoparticles.
• US patent 20050247421
• Retention systems
• http//www.tappi.org/s_tappi/doc_bookstore.asp?CID
  5071DID526601
• http//www.tappi.org/s_tappi/doc_bookstore.asp?CID
  5071DID526602
• http//www.papermaking-chemistry.com/spring05.htm

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Cellulose Synthesis and Material Production
Nature Working Across a Length Scale
gt1010!
Cellulose nanofiber bundles
6 Assembly proteins (rosette) which produces
cellulose nanofibers
28nm
www.ita.doc.gov/td/forestprod/
jupiter.phys.ttu.edu/corner/1999/dec99.pdf
Candace Haigler and Larry Blanton, Cellulose
You're surrounded by it, but did you know it was
there?
Source Jeffery Catchmark , Penn State University
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http//www.forestprod.org/woodfiber05sain2.pdf
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Nanotechnology in Paper Application

• Nano-Engineering Particle Surfaces
• Controlled particle dispersion in polymer matrix
• Improved effectiveness of light scattering
• Protection of filler or pigment from external
  influences
• Improved compatibility by promoting interaction
  between filler with binder or co-binder
• Increased surface area leading to improved ink
  receptibility
• Stimuli responsive triggered by pH, temperature,
  moisture, or magnetic response
• Nanofiber

Key Utilized key learning in other areas. For
example nanotechnology based on sol-gel reaction
has been known in semiconductor for a long time
re-inventing this (architectural coating,
abrasive resistant topcoat in automotive)
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Controlled Modification of Clay platelets

• Physical Approach driven by electrostatic
  interactions between oppositely charged species
  that generates a stable end product
• Chemical Approach functionalization of clay
  surface using covalent bonded molecules allowing
  the tuning of hydrophobicity and functionality

D.J. Voorn, W. Ming, A.M. van Herk,
Macromolecular Symposia 2006, 245-246, 584-590
Dumb-bell shaped clay with latex on the clay
surface
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Electrospinning of Nanofiber

• Incorporation of Nanoparticles into
  Electrospinning solution to create Nanofibers
  with various properties
• (A) Encapsulation of iron oxide Nanoparticles
  into Nanofibers conductive
• (B) Deposition of silver Nanoparticles on the
  NanoFiber surface antimicrobial
• (C) Nanofibers with porous structure scattering
• (D) Uniaxilly aligned Nanotubes scatter or
  perhaps controlled released?

A
C
B
D. Li, Y. Xia, Advanced Materials 2004, 16, No.
14, 1151
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Application of Nanotechnology in Other Areas

• Special Effect Pigments used in printing,
  packaging and specialty coating i.e. Pearl
  Lustre Pigments
• Textile industry Cousin to paper industry (both
  based on cellulose products)
• Water repellant Nanowhiskers and Nanosphere
  (Nanotex and Schoeller)
• UV protection fabric sol gel method to treat
  the cotton fabric or nanorods
• Antibacterial fabric impregnated fabric with
  Nanosilver
• Wrinkle resistant incorporation of Nanosilica
  with maleic anhydride to improve crosslinking to
  create wrinkle resistance in silk
• Catalyst paper - for Photocatalytic degradation
  using TiO2 Nanoparticles
• http//scholar.ilib.cn/A-zgzz200412015.html
• Optically transparent products for
  electronics/displays/packaging
• http//adsabs.harvard.edu/abs/2005ApPhA..81.1109I

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Current Challenges
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Barriers Nano-fractionalization and
nano-catalysis for separations Non covalent
disassembly/re-assembly Entropic effects in the
assembly and disassembly of nanomaterials in
forest materials
Challenge 1 Forest Nanomaterials Goal
Liberation and use of nanocellulose building
blocks
Current solutions Nanofiltration and
low-pressure reverse osmosis membranes http//ww
w.aseanbiotechnology.info/Abstract/21018571.pdf ht
tp//www.ingentaconnect.com/content/els/00151882/1
997/00000034/00000003/art84794 http//cat.inist.fr
/?aModeleafficheNcpsidt16113640 Nanofilters
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Nanocellulose Fiber Nanofilters


http//www.zamslube.com/images/sem_filter.jpg
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http//www.forestprod.org/woodfiber05sain2.pdf
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http//www.forestprod.org/woodfiber05sain2.pdf
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http//www.forestprod.org/woodfiber05sain2.pdf
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http//www.forestprod.org/woodfiber05sain2.pdf
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Challenge 2 Improve strength weight
performance Target 40 fewer materials for
same performance 60 performance with 45 CWF
Mechanical (bonding ) and optical Performances

Barriers Control of Nanostructural
and interface properties Selection of designer
shapes and multiple material compatibility
Control of hierarchical structures Measurement
of nano-scale strain , shear and bulk moduli
Adhesion and bonding at Nano-scale
Current Solutions 1) Plant microfiber bundles
with a nanometer unit web-like network http//cat.
inist.fr/?aModeleafficheNcpsidt15573377 Bending
strength 310 MPa. 2) Soaking cellulose in nylon
6-6 for reinforcement JP 2003128791
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(No Transcript)
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http//www.forestprod.org/woodfiber05sain2.pdf
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http//www.forestprod.org/woodfiber05sain2.pdf
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Double tensile strength of paper with 10 nm LbL
coating

• Zheng, McDonald, Khillan, Su, Shutava, Grodzits,
  and Lvov

J. Nansci. Nanotechnol. 6, 624-632, 2006
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Viscose and Rayon containing Nanoparticles

• Viscose fiber CN 2005-10104905
• Dry breaking strength 2.10 CN/dtex,
• Wet breaking strength 1.20 CN/dtex
• Dry breaking elongation 16
• By adding 2-12 nanoscale carbon colloid with
  particle size 20-40 nm
• Rayon antibacterial CN 2005-10104907
• Nanoscale silver antibacterial agent with
  particle size 50-65 nm

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Challange 3 Water-lignocellulose interaction
Target Understand water forest
materials interactions Control effects of
water on wood and paper properties Shed water
more efficiently
Barriers Interfacial properties at
nanoscale Production of hydrophilic/hydrophobic
switchable surfaces Biological activity control
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News, 45 g/m²
Moisturized sheet
Dry sheet
ESEM - Environmental Scanning Electron Microscope
G. A. Baum 2003
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Barrier Understand control surface
chemical reactivity Characterization of
structures at nanoscale Measurement of
physical properties at nanoscale Multiple
material compatibility Directed self assembly
of nano-components
Challenge 4 Inorganic-organic nanocomposites
nanoscale surface modification Target Produce
nano-composite materials from forest materials
Multiple current applications
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Cellulose Nanocomposites

• Cellulose with Nanoclay
• Flame retardant WO 2007022552
• Composite CN 2005-10033705
• Cellulose with carbon Nanotubes
• For electro active paper http//spiedl.aip.org/ge
  tabs/servlet/GetabsServlet?prognormalidPSISDG00
  6168000001616823000001idtypecvipsgifsyes
• Composite nonwoven fabric for Medical
  applications
• WO 2006060398
• US 2005142973
• US 2003-483839P
• Cellulose Nanocrystals
• http//www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd
  RetrievedbPubMedlist_uids15762677doptAbstrac
  t

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Challenge 5 - Photonics and Electronic/Piezo
properties Target Produce Optically efficient
structures Control electronic properties of
forest materials
Barriers Selection of controlled size and
shape building blocks Characterization of
physical structure, interfaces, material
intermixing and defects Self assembly of
building blocks into controlled structures
Liquid crystal structures of building blocks
(forest based and mineral) Contact effects at
nanoscale Effect of dopants Hybrid
organic/bio/inorganic devices
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Whats a Photonic Crystal

• A material containing two discrete components
  having different indexes of refraction arranged
  in a particular periodic fashion
• 1D is ¼ wavelength dielectric mirror
• 3D is similar scale holes arranged in a
  crystal-like configuration in a dielectric medium

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Steven Johnson, MIT
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What Type of Mirror?

• Standard Aluminum Mirror only lt 90 efficient
• Front-Surface Silver 95, but tarnishes !
• Conventional Broadband Dielectric Mirror can
  exceed 98 but is 200/sq.inch and is not
  flexible (sputtered coatings)
• 3M ESR Polymeric Film is gt 98 over the entire
  visible spectrum and incident angles and costs
  15/sq.ft. and is very flexible.
• 3D Photonic Crystal Slabs gt 99 over the entire
  visible spectrum and incident angles.

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What is possible?

• Nano-optics control of opacity
• Nanoparticle Arrays on Surfaces for Electronic,
  Optical, and Sensor Applications
• Self assembly

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What is possible?

• Electronic devices
• Nanoelectromechanical memory
• Gate dielectrics
• Nanopillars for zero-field microwave generation
• Cellulose as a nanotemplate
• http//pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/20
  04/5/i03/abs/bm034532u.html