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Nanotechnologies PotentialNanotechnologies PotentialNanotechnologies Potential Nanotechnologies Potential in in Forest and Paper IndustryForest and Paper Industry
Nano Hemicelluloses ForNano-Hemicelluloses For Barrier/Strength Improvementsg p
Improvements in Tensile Index with 4% Applied Glucuroxylan
40
50
60
e In
dex
20
30
40
Tens
ile
SW ECFP l
BulkE i h
SurfaceE i h dPulp Enrich
XylanEnriched
Xylan
Very recent developments in nano-lignin suggest new barrier opportunities
Nanosized TiO2 materials enhance titania’s i ti b i i l funique properties by giving large surface areas
Hollow ballHollow ball Hollow ballHollow ball TubeTube
BeltBelt FilmFilm
Super hydrophobic Barrier CoatingSuper-hydrophobic Barrier Coating
M th d f h i h d hibi it L i fMethod of enhancing hydrophibicity: Lowering surfaceenergy by coating of hydrophobic material.However the material with the lowest surfaceHowever, the material with the lowest surfaceenergy (6.7 mJ/m2 for a surface with regularlyaligned closest-hexagonal-packed –CF3 groups)
i t t t l f l d 120ogives a water contact angle of only around 120o.
Super-hydrophobic surface: Both receding andSuper hydrophobic surface: Both receding andadvanced water contact angles above 150o.
W t i d bi t i t ill t bWater, ice, grease, and bio contaminants will not beable to deposit on super-hydrophobic surfaces
Lotus Effect
(c)(b)(a)
Figure 1. (a) SEM images of the lotus leaf surface. Schematic representation of the self-cleaning mechanism: moving of water droplet along contaminated smooth (b) and rough (c) surfaces.
http://www.biologie.uni-hamburg.de
Coatings with hydrophobic silica (colloidal silica + FAS-17)
Figure 4. SEM images of films on glass and the shapes of water droplets on the films. (a) glass + heptadecafluorodecyltrimethoxysilan (FAS-17) coating; (b) film from methanol based colloidal silica and (c) film from methyl ethyl ketone (MEK) based silica.
T. Watanabe, et al, “Processing of roughened silica film by coagulated colloidal silica for super-dydrophobic coatng” J Materials Sci Lett 2001, 20, 1975.
Barrier Coating with NanomaterialsBarrier Coating with NanomaterialsBarrier Coating with NanomaterialsBarrier Coating with Nanomaterials
P lP l l h b id i i ll h b id i i l•• PolymerPolymer--clay nanohybrids are important new materialsclay nanohybrids are important new materials–– Improve modules, scratch properties, strength, stiffness, Improve modules, scratch properties, strength, stiffness,
heat resistance and preservation etcheat resistance and preservation etcheat resistance and preservation, etc.heat resistance and preservation, etc.–– Increase barrier properties for gas, water and grease Increase barrier properties for gas, water and grease
C b d f t til i ti ti d thC b d f t til i ti ti d th–– Can be used for textile, painting, coating, and many othersCan be used for textile, painting, coating, and many others•• Barrier properties are very important for some paper products, Barrier properties are very important for some paper products,
such as containers for milk juice ice cream meet fish fruitsuch as containers for milk juice ice cream meet fish fruitsuch as containers for milk, juice, ice cream, meet, fish, fruit, such as containers for milk, juice, ice cream, meet, fish, fruit, microwave fast food, food plates and boxes, drink cups, photo microwave fast food, food plates and boxes, drink cups, photo papers, etcpapers, etcp p ,p p ,
•• Problems of waxed food containers: unProblems of waxed food containers: un--recyclable, cannot be recyclable, cannot be used as containers for milk, juice, ice cream, fast food, food used as containers for milk, juice, ice cream, fast food, food platesplates
Nano-Optical EffectspNew Value Added Features: Opticals
Objective: Develop new fiber-based products that take advantage of the special optical and photonic properties of nanomaterials and that enable manufacturers to:
o Increase opacity and light barrier properties of paper and paperboard o Utilize new methods for holographic imagery and graphics on paper o Utilize new methods for holographic imagery and graphics on paper
surfaces o Employ novel optical effects on paper surfaces and in paper webs
Target market opportunities:
o Lightweight printing papers with high opacity
Abalone Shell o Lightweight printing papers with high opacity
o Paperboard with high light barrier for packaging light-sensitive contents without use of metal foil
o Papers and folding cartons with new security and anti-counterfeiting features
o White-surfaced paper and paperboard with high content of recycled and/or o White surfaced paper and paperboard with high content of recycled and/or unbleached fiber
Enabling technologies – pre-competitive research:
o Photonic effects of nanomaterials for light scattering, light absorption, light transmission wavelength shifting etc
Source: Belcher et al 1999
transmission, wavelength shifting, etc. o Imaging and holography with nanoparticles o Nanomaterials that react to ambient stimuli optically, electronically, or
mechanically Processes for preparing commercial quantities of photonic nanomaterials and for applying ultra-thin coatings onto paper surfacesapplying ultra-thin coatings onto paper surfaces
Nanostructured Filler Engineering: Mg(OH)2Nanobelts synthesized by Y. Deng
Low cost Low cost Low density (2.4)Low density (2.4)High brightness High brightness No retention aid is needed (good formation) No retention aid is needed (good formation) L i t t thL i t t thLess impact on paper strengths Less impact on paper strengths
Nanostructured Filler EngineeringNanostructured Filler EngineeringNanosilicate Fibril Fillers
Vijay Mathur, 2004 TAPPI Paper Summit, May 3-5, 2004, Atlanta, GA, USA
Nanostructured Filler EngineeringNanostructured Filler Engineering
Clay
Charge Charge Charge
Polymer Polymer Polymer
34
36
Control Coated clay
30
32
34
ile In
dex
- Layer-by-layer coating on clay fillers- Tailor fill surface properties- Enhances tensile and other physical
properties
26
28
Tens
i properties-
5% 10% 15% 20% 9 layer
Percentage clay
Nano-Enhanced Paper:p
ZDT Strength Improvement
90
100
60
70
80
90
SI)
30
40
50
ZDT
(PS
0
10
20
Control Nano fibrilControl Nano fibril
33% increase in ZDT
Nano-Enhanced Paper:
Folding Strength Improvement
p
Folding Strength Improvement4
3
3.5
4
*cm2 /g
)
1 5
2
2.5
ndex
(tim
es*
0.5
1
1.5
Fold
ing
In
0Control Nano fibril
3.5 time increases in the folding strength
PolymerPolymer--Nanoclay CompositesNanoclay Compositesyy y py p
Th thi k fTh thi k fThe thickness of The thickness of nanoclay in the nanoclay in the composite is aboutcomposite is aboutcomposite is about composite is about 1nm.1nm.
B i ti fB i ti fBarrier coating for Barrier coating for food containers and food containers and paper packages paper packages
Water and vapor Water and vapor resistance, fatty and resistance, fatty and oil resistance, board oil resistance, board ,,strengthstrength
Key Issues Using Polymer-Nanoclay for Barrier Coating
•• Water BasedWater Based–– Emulsion/miniemulsion polymerizationEmulsion/miniemulsion polymerization H2OH2OEmulsion/miniemulsion polymerizationEmulsion/miniemulsion polymerization
•• Uniformed Distribution (no aggregates in the Uniformed Distribution (no aggregates in the polymer matrix)polymer matrix)polymer matrix)polymer matrix)–– Correctly using surfactant Correctly using surfactant
•• Strong affinity between polymer and nanoclayStrong affinity between polymer and nanoclay–– Seeding and modification technologySeeding and modification technology
H2OH2O
Functional PaperFunctional Paper PackagingPackagingFunctional PaperFunctional Paper--PackagingPackaging
NN i l b dd d i ll l ii l b dd d i ll l iNN i l b dd d i ll l ii l b dd d i ll l i•• NanoNano particles embedded in cellulosic particles embedded in cellulosic fibers can provide:fibers can provide:
•• NanoNano particles embedded in cellulosic particles embedded in cellulosic fibers can provide:fibers can provide:pp–– Unique antiUnique anti--bacterial fungal propertiesbacterial fungal properties
Ti d lTi d l
pp–– Unique antiUnique anti--bacterial fungal propertiesbacterial fungal properties
Ti d lTi d l–– Timed releaseTimed release–– Environmentally responsive signalsEnvironmentally responsive signals–– Timed releaseTimed release–– Environmentally responsive signalsEnvironmentally responsive signalsy p gy p gy p gy p g
Advanced Bio-Based Materials
1 μm100 μmmm Research Opportunities
110 μm
μ
10 nm nm Nanocellulose
H+/Enzyme/M h i l
1 cm
OHO
OAcO
AcOOH
O-XylanO
MechanicalAFM of Cellulose
NanowiskersBirefringence of
Cellulose Nanowiskers
TEM of Cellulose Nanowiskers1AFM of Cellulose
NanowiskersBirefringence of
Cellulose Nanowiskers
TEM of Cellulose Nanowiskers1
OO HO
OHO
O
W t V T i i /h
Xylan FilmsCrosslinked
200
300
400Water Vapour Transmission/h
0
100
0% 5 10
% Sulfonated WhiskersO2 &strengthGreen Package
•• NanoNano in Pulp and Paper in Pulp and Paper –– NanofillerNanofiller EngineeringEngineering–– SuperhydrophobicSuperhydrophobic –– SuperhydrophilicSuperhydrophilic FibersFibers–– Barrier Barrier coatings and Filmscoatings and Films–– NanostructuredNanostructured Papermaking AdditivesPapermaking Additives–– NanostructuredNanostructured Papermaking AdditivesPapermaking Additives–– Optical Optical PropertiesProperties–– Improved PrintingImproved Printing–– Higher BulkHigher Bulk–– Porous StructuresPorous Structures–– FoamsFoamsFoamsFoams–– CompositesComposites
llilli–– Intelligent PaperIntelligent Paper