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  • Improved Pulp PropertiesImproved Pulp Properties thru Fiber Modificationthru Fiber Modification

    Art J. Ragauskas School Chemistry & BiochemistrySchool Chemistry & Biochemistry

    Institute of Paper Science & Technology Georgia Institute of TechnologyGeorgia Institute of Technology

    Atlanta, GA

  • Fiber Modification: Addressing the Challenge

  • Fiber Modification: The World is not Flat

    What is Needed to Make Stable Complex Curved Paper Structures B Fib Fib B di• Better Fiber-Fiber Bonding

    • Moisture insensitivity • Nano coatings

    C li ki• Crosslinking • Grafting • Resins • LbL• LbL

    • Better Stress Transfer • Engineered fiber surfaces • Fibers reinforced with bio-composites• Fibers reinforced with bio-composites

    • Thermo/chemical responsive green composites/resins

  • Fiber Modification: Southern SW Fiber vs Northern

    SW/Tropic HW for Tissue/TowelSW/Tropic HW for Tissue/Towel Southern Fiber Suffers from fiber coarseness

    Ti d i d i b l f lTissue and tissue products requires a balance of several competing effects including tensile strength, absorbency and softness. Of these three parameters, the strength of the sheet and its corresponding softness often exhibit a

    ftn es

    s

    sheet and its corresponding softness often exhibit a dependency on each other. For example, mechanical treatments that enhance softness also decrease tensile strength which for many applications is not a preferred

    So f strength, which for many applications is not a preferred

    outcome.

    Strength Fiber Notching of SW Fibers

    - Yields a ‘softer feel fiber’ - Fibers with reduced dry zero-span

    tensile have improved hand feel

  • Fiber Modification: Southern SW Fiber vs Northern

    SW/Tropic HW for Tissue/TowelSW/Tropic HW for Tissue/Towel Fiber Notching of SW Fibers

    ZÜxtàxÜ Y|uxÜ YÄxåtu|Ä|àç

    Chemical/Physical Approachesy pp - Chemical etching - Hot blow kraft cooks - Chemical/physical treatments

  • Fiber Modification: Green Paper & Packaging

    Need to Develop Enhanced Moisture/O2/BacterialNeed to Develop Enhanced Moisture/O2/Bacterial Barrier Properties

    • Consumer driven to be green • Replace plastic/metal barriersp p • Replace petroleum based papermaking additives with biobased materials

    Development Opportunities: H i ll l b i f i t d O2• Hemicellulose barriers for moisture and O2

    • Functional fibers for antibacterial • Nano-particles

    Grafted/LbL/antibacterial agents• Grafted/LbL/antibacterial agents • Nanocellulose/starch/lignin strength/crosslinking

    • Coatings/films • Wet end applications

    200

    300

    400 Water Vapour Transmission/h

    • Wet-end applications • Fire resistant fibers

    • Green home insulation market & structural market 0

    100

    0% 5 10

    % Sulfonated Whiskers

  • Fiber Modification: Green Paper & Packaging

    Need to Develop Enhanced Moisture/O2/BacterialNeed to Develop Enhanced Moisture/O2/Bacterial Barrier Properties

    • Consumer driven to be green • Replace plastic/metal barriersp p • Replace petroleum based papermaking additives with biobased materials

    35.0

    15.0

    20.0

    25.0

    30.0

    Te ns

    ile In

    de x

    Hot Pressing With Resins 0.0 5.0

    10.0

    Control 2% PVA 5% PVA 20% PVA

    Control and PVA TMP Sheets Hot Pressed

    • Hydrophobic Bonding • Dry Formingy g • Air-laid Papermaking

  • Fiber Modification: Enhanced Water Absorption

    Water Absorption of SW Kraft Fibers/Fluff

    Cross-linked Fibers

    Water RetainedWater Absorbed

    120

    140

    te ria

    l

    Milled Pine Water Retained

    Pine Water Retained 150

    175

    200

    ia l

    Milled Pine Thermal

    Pine Pulp Thermal

    40

    60

    80

    100

    w at

    er / g

    d ry

    m at

    75

    100

    125

    150

    w at

    er / g

    d ry

    m at

    er i Pine Pulp Thermal

    0

    20

    40

    0 10 20 30 40 50 60 70

    % PMVEMA

    g w

    0

    25

    50

    0 10 20 30 40 50 60 70

    g w

    % PMVEMA% PMVEMA

  • Fiber Modification: Enhanced Water Absorption

    Water Absorption of SW Kraft Fibers/Fluff

    189.2 180

    210

    240

    Uncrosslinked

    Crosslinked

    Cross-linked Fibers

    Functionalized Fluff • Develop new crosslinking agents • New oxidation protocols

    137.9

    86.5

    60

    90

    120

    150

    W A

    A R

    V (g

    /g )

    p • Greater Water Absorbency • Reduced Bonding

    4.97 4.72 3.82 0

    30

    2.41 0.97 0.50 Fiber length (mm)

    Functionalized Fibers

  • Fiber Modification: Fiber – Fiber Bonding

    Benefits of Fiber Charge/Hemicellulose Retention/GenerationBenefits of Fiber Charge/Hemicellulose Retention/Generation • Enhanced Strength

    • Tensile/Burst/(STFI) • Refinability Peroxidey • Fold • Recyclability

    12 Tensile stiffness Ultrasonic in Plane specific stiffness:longitudial

    5.0

    60

    70

    80

    ol /g

    ,H ol

    oP ul

    p

    21.42

    21

    22

    9

    10

    11

    Ultrasonic in Plane specific stiffness:longitudial Ultrasonic in Plane specific stiffness:shear

    or k

    m 2 /s

    ec 2 4.5

    se c2

    30

    40

    50

    C ar

    bo xy

    lic a

    ci d,

     m

    o

    18.35

    16

    17

    18

    19

    20 Tensile index

    (N.m/g)

    44.82 61.79 Carboxylic acid, mol/g Holopulp

    7

    8

    9

    S tif

    fn es

    s, kN

    /m m

    2 o 3.5

    4.0

    Sh ea

    r,k m

    2 /s

    0.0 0.1 0.2 0.3 0.4 0.5 20

    Catalyst, % 44.8 67.02 80.04

    6

    Carboxylic acid, mol/g HoloPulp

    3.0

  • Fiber Modification: Fiber – Fiber Bonding

    55

    60

    50

    55

    60

    ex

    40

    45

    50

    Te ns

    ile In

    de x

    35

    40

    45

    50

    Te ns

    ile In

    de

    Control Birch Oat Hulls

    30

    35

    100% SW 1% Birch 2% Birch 4% Birch 8% Birch 2% Oats 5% Oats 8% Oats

    30

    35

    8.0% 8.5% 9.0% 9.5% 10.0% 10.5%

    Xylan %

    Oat Hulls

    5.9

    6

    Burst Index

    5 6

    5.7

    5.8

    5.9

    5 3

    5.4

    5.5

    5.6

    5.2

    5.3

    Control 2% Ag 5% Ag 8% Ag

  • Fiber Modification: Fiber – Fiber Bonding

    46 150 3.4

    Birch Xylan on Eucalyptus BKP - Virgin

    44

    45 Tensile index TEA Strain

    m /g

    )

    141

    144

    147

    3.2

    4.3

    4.4

    4.5

    Tear index Retention of tear index 54

    55

    56

    R

    42

    43

    en si

    le in

    de x

    (N m

    135

    138

    141 TEA (J/m 2)

    3.0

    S train(%

    )

    3 9

    4.0

    4.1

    4.2

    nd ex

    ( m

    N .m

    2 /g )

    50

    51

    52

    53

    R etention of tear in

    -1 0 1 2 3 4 5 6 7 8 9 10 11 40

    41

    Te

    126

    129

    132

    2.6

    2.8

    3.6

    3.7

    3.8

    3.9

    Te ar

    i

    46

    47

    48

    49

    dex (% )

    -1 0 1 2 3 4 5 6 7 8 9 10 11 Xylan dosage(%) -1 0 1 2 3 4 5 6 7 8 9 10 11

    Xylan dosage(%)

    Birch Xylan on E l t BKP O D i dEucalyptus BKP – Once DriedResearch Opportunities

    • Oxidative treatments of linerboard – bleach grades • Profiling hemicellulose retention during kraft pulping • Co-pulping with Ag resources • Recovery of hemicelluloses from black liquor

  • Fiber Modification: Fiber – Fiber Bonding

    90

    Starch Grafting on Bleached SWKP

    60

    70

    80

    N m

    /g

    30

    40

    50

    le in

    de x,

    10

    20

    30

    Te ns

    il

    0 0 1 3 5 10

    Starch content, %

  • Hornification Can be MinimizedHornification Can be Minimized 190 Dried in H-form

    Fiber Charge

    160 170 180 190 Dried in H-form

    Dried in ionized form Never dried

    120 130 140 150

    W R

    V , %

    80 90

    100 110

    0 5 10 15 20 25 30 35 40 Carboxyl Group Content, meq/100 g

    • Bleached sulfate pulp that was enriched in acid groups • The H-form has fully protonated acid groups • The ionized forms are negative with accompanying

    metal

  • Dry Kraft Pulping at Ambient Pressure for Cost Effective Energy Saving and PollutionCost Effective Energy Saving and Pollution

    Deduction Funded by DOE Grand Challenge Program PI: Yulin Deng, Co-PI: Art Ragauskas

    Goals: Develop a novel pulping technology that can replace the current Kraft

    l i t h i b t ith i ifi t l ti (>30%)p