25-3 Coughlin Nanotechnology and Cellulose Rev 2 (No LAgrmt by Desgn)

8/11/2019 25-3 Coughlin Nanotechnology and Cellulose Rev 2 (No LAgrmt by Desgn)

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Nanotechnology andthe paper/forest product

industry

Dan Coughlin

Paul GilbertSteven MasiaTety Roper


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Growing Trend in Nanotechnology

Number of Publications in Nanotechnology Area

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NumberofPublishedJournals

Growing Trend in

Nanotechnology


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Nanotechnology Based on the Application inVarious Market Segment

Nanotechnology Application

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Coated

pap

er

Auto

motive

Food

Archite

ctural

Cosm

etic

Packagin

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nducto

r

Pharmac

eutic

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Plastic

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NumberofPublishedJournals

Nanotechnology Sector


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Mechanical Tailoringand control

(Lightweight paperwith high strength=

Aerogel)

LignocelluloseControl and

conformationtailoring

( Improvedconstruction

materials)

Thermal Propertiesand functionality( Controlled heatconductivity and

capacity)

Nano scalePolysaccharide

Processing( New

biopolymersEthanol

biorefinery)

Surface Functionalityand Tailoring( Hydrophobic/Hydrophilic

Biosensors)

Electronic Functionalityand Sensing

(Printed electronicsdisplays, solar cells,

fuel cells, medicalsensors)

Optical properties(Specialized optics

by photonicnanostructure)

Modeling Smart

Cellulose structures(Piezoelectric-

Electro-rheostatic andMagneto-rheostatic )

Polymer Interactionand control of water

interaction(Improve dimensional

stability)

Particle interactionand Grafting

(Self assembly andreinforcement for

tensile strength, andelasticity)

Nanoscalecomposites

(Formation ofnanofibers for

compositeprocessing)

Porosity andControl

( Improvedfiltration andmembranes

Improved

printability)

Application Areas

Nano-lignocellulosics
http://www.emlab.ubc.ca/imagesElaine/motheye_mp_thmb.gif


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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 Electron ic/Piezo propert ies 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 calciumcarbonate nanoparticles.

US patent: 20050247421

Retention systems: http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=52660

1

http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526602

http://www.papermaking-chemistry.com/spring05.htm
http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526601http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526601http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526602http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526602http://www.papermaking-chemistry.com/spring05.htmhttp://www.papermaking-chemistry.com/spring05.htmhttp://www.papermaking-chemistry.com/spring05.htmhttp://www.papermaking-chemistry.com/spring05.htmhttp://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526602http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526602http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526601http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=5071&DID=526601


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Cellulose nanofiber bundles

6 Assembly

proteins

(rosette)

which

produces

cellulose

nanofibers

Candace Haigler and Larry Blanton, Cellulose: You'resurrounded by it, but did you know it was there?

jupiter.phys.ttu.edu/corner/1999/dec99.pdfwww.ita.doc.gov/td/forestprod/

Cellulose Synthesis and Material Production:Nature Working Across a Length Scale >1010!

~28nm

Source: Jeffer Catchmark Penn State Universit


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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

NanofiberKeyUtilized key learning in other areas. For example: nanotechnologybased on sol-gel reaction has been known in semiconductor for a longtimere-inventing this (architectural coating, abrasive resistant topcoat inautomotive)


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Controlled Modification of Clay platelets

Physical Approachdriven by electrostatic interactions

between oppositely charged species that generates astable end product

Chemical Approachfunctionalization of clay surfaceusing covalent bonded molecules allowing the tuning ofhydrophobicity and functionality

Dumb-bell shaped clay withlatex on the clay surface

D.J. Voorn, W. Ming, A.M. van Herk,Macromolecular Symposia 2006, 245-246, 584-

590


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Electrospinning of Nanofiber

Incorporation of Nanoparticles intoElectrospinning solution to create

Nanofibers with various properties (A) Encapsulation of iron oxide

Nanoparticles into Nanofibersconductive

(B) Deposition of silver Nanoparticles on

the NanoFiber surfaceantimicrobial (C) Nanofibers with porous structure

scattering

(D) Uniaxilly aligned Nanotubesscatteror perhaps controlled released?

A

B C

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 coatingi.e. Pearl Lustre Pigments Textile industryCousin to paper industry (both

based on cellulose products) Water repel lantNanowhiskers and Nanosphere (Nanotex and Schoeller)

UV protect ion fabr icsol gel method to treat the cotton fabric or nanorods

An tibacterial fabricimpregnated fabric with Nanosilver

Wrinkle resistantincorporation of Nanosilica with maleic anhydride toimprove crosslinking to create wrinkle resistance in silk

Catalys t paper- for Photocatalytic degradation using TiO2Nanoparticles

http://scholar.ilib.cn/A-zgzz200412015.html

Optical ly transparent produ ctsfor electronics/displays/packaging

http://adsabs.harvard.edu/abs/2005ApPhA..81.1109I
http://scholar.ilib.cn/A-zgzz200412015.htmlhttp://adsabs.harvard.edu/abs/2005ApPhA..81.1109Ihttp://adsabs.harvard.edu/abs/2005ApPhA..81.1109Ihttp://scholar.ilib.cn/A-zgzz200412015.htmlhttp://scholar.ilib.cn/A-zgzz200412015.htmlhttp://scholar.ilib.cn/A-zgzz200412015.html


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Current Challenges


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Barriers

Nano-fractionalization and nano-

catalysis forseparations;

Non covalent disassembly/re-assembly

Entropic effects in the assembly anddisassembly of nanomaterials inforestmaterials

Challenge 1: Forest Nanomaterials

Goal:

Liberation and use of nanocellulose

building blocks

Current solutions:

Nanofiltration and low-pressure reverse osmosis membranes:

http://www.aseanbiotechnology.info/Abstract/21018571.pdfhttp://www.ingentaconnect.com/content/els/00151882/1997/00000034/00000003/art84794http://cat.inist.fr/?aModele=afficheN&cpsidt=16113640

Nanofilters
http://www.aseanbiotechnology.info/Abstract/21018571.pdfhttp://www.ingentaconnect.com/content/els/00151882/1997/00000034/00000003/art84794http://www.ingentaconnect.com/content/els/00151882/1997/00000034/00000003/art84794http://cat.inist.fr/?aModele=afficheN&cpsidt=16113640http://cat.inist.fr/?aModele=afficheN&cpsidt=16113640http://www.ingentaconnect.com/content/els/00151882/1997/00000034/00000003/art84794http://www.ingentaconnect.com/content/els/00151882/1997/00000034/00000003/art84794http://www.aseanbiotechnology.info/Abstract/21018571.pdf


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Nanocellulose Fiber: Nanofilters

http://www.zamslube.com/images/sem_filter.jpg
http://www.zamslube.com/images/sem_filter.jpghttp://www.zamslube.com/images/sem_filter.jpg


17/36http://www.forestprod.org/woodfiber05sain2.pdf


18/36http://www.forestprod.org/woodfiber05sain2.pdf


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B i


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Chal lenge 2: Improv e strength

weight per formance

Target:

40% fewer materials for sameperformance

60# performance with 45# CWFMechanical (bonding ) and optical

Performances

Barriers

Control of Nanostructural andinterface properties

Selection of designer shapes andmultiple material compatibility

Control of hierarchical structures

Measurement of nano-scale strain ,

shear and bulk moduli

Adhesion and bonding at Nano-scale

Current Solutions1) Plant microfiber bundles with a nanometer unit web-like network

http://cat.inist.fr/?aModele=afficheN&cpsidt=15573377Bending strength 310 MPa.

2) Soaking cellulose in nylon 6-6 for reinforcement

JP 2003128791
http://cat.inist.fr/?aModele=afficheN&cpsidt=15573377http://cat.inist.fr/?aModele=afficheN&cpsidt=15573377


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Double tensile strength of paper with 10 nm LbL coating

Zheng,McDonald,Khillan, Su,Shutava,Grodzits, andLvov

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 size20-40 nm

Rayonantibacterial: CN 2005-10104907 Nanoscale silver antibacterial agent with particle size 50-65 nm


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Challange 3 : Water-lignocelluloseinteraction

Target

Understand water forest materialsinteractions

Control effects of water on wood andpaper properties

Shed water more efficiently

Barriers

Interfacial properties at nanoscale

Production of hydrophilic/hydrophobicswitchable surfaces

Biological activity control


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ESEM - Environmental Scanning Electron Microscope

Dry sheetMoisturized sheet

News, 45 g/m

G. A. Baum 2003

BarrierChallenge #4: Ino rganic -org anic


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Barrier

Understand & control surface chemicalreactivity

Characterization of structures atnanoscale

Measurement of physical properties atnanoscale

Multiple material compatibility

Directed self assembly of nano-

components

Challenge #4: Ino rganic -org anic

nanocomposi tes nanoscale sur face

modi f icat ion

Target:

Produce nano-compositematerials 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/getabs/servlet/GetabsServlet?prog=normal

&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yes

Composite nonwoven fabric for Medicalapplications WO 2006060398

US 2005142973 US 2003-483839P

Cellulose Nanocrystals http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=

PubMed&list_uids=15762677&dopt=Abstract

Chal lenge 5 Photo nics and Barriers
http://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yeshttp://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yeshttp://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yeshttp://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=15762677&dopt=Abstracthttp://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=15762677&dopt=Abstracthttp://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=15762677&dopt=Abstracthttp://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=15762677&dopt=Abstracthttp://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yeshttp://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yeshttp://spiedl.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PSISDG006168000001616823000001&idtype=cvips&gifs=yes


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Chal lenge 5 - Photo nics and

Electro nic /Piezo p ropert ies

TargetProduce Optically efficient structures

Control electronic properties of forestmaterials

Barriers

Selection of controlled size and shapebuilding blocks

Characterization of physical structure,interfaces, material intermixing anddefects

Self assembly of building blocks intocontrolled structures

Liquid crystal structures of buildingblocks (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 discretecomponents having different indexes ofrefraction arranged in a particular

periodic fashion

1D is wavelength dielectric mirror

3D is similar scale holes arranged in

a crystal-like configuration in adielectric medium


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Steven Johnson, MIT


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What Type of Mirror?

Standard Aluminum Mirror only < 90%efficient

Front-Surface Silver = 95%, but tarnishes ! Conventional Broadband Dielectric Mirror

can exceed 98% but is $200/sq.inch and isnot flexible (sputtered coatings)

3M ESR Polymeric Film is > 98% over theentire visible spectrum and incident angles

and costs $15/sq.ft. and is very flexible. 3D Photonic Crystal Slabs > 99% over the

entire visible spectrum and incident angles.


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What is possible?

Nano-opticscontrol 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/bomaf6/2004/5/i03/abs/bm034532u.html
http://pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/2004/5/i03/abs/bm034532u.htmlhttp://pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/2004/5/i03/abs/bm034532u.htmlhttp://pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/2004/5/i03/abs/bm034532u.htmlhttp://pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/2004/5/i03/abs/bm034532u.htmlhttp://pubs.acs.org/cgi-bin/abstract.cgi/bomaf6/2004/5/i03/abs/bm034532u.html

Documents

25-3 Coughlin Nanotechnology and Cellulose Rev 2 (No LAgrmt by Desgn)