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

Nano-Enhanced Paper: CoatingsC S diCurrent Studies

n n

NH3+ Cl- N

+Cl-

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

Nano-Filler PropertiesNano Filler Properties

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: Surface Fibrilation

SEM of FiberFibrilation

SEM of Fiber

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

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2

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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