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Page 1: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Kraft and Mechanical Pulps

Page 2: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Importance of carboxyl (acid) groups on pulps.• Main group responsible for surface and bulk charge of kraft

fibers.

• Important for pulp swelling.

• Increase pulp fiber softness and collapsibility.

• Improve pulp strength properties.

• Improve beatability.

• Capable of ion-exchange reactions.

Page 3: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Two methods developed for measurement of surface and bulk acid groups:

1. UV/VIS measurement of iodide counterion released from electroneutralization reaction – attempting to make it an automated measurement

2. On-line HSGC measurement of carbon dioxide released from acid/base reaction of HCl and carboxylates

Page 4: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

It has been found that O and EOP increase overall acid levels, but D sequences tend to decrease it

00 .010 .020 .030 .040 .050 .060 .070 .08

BS O

D(EOP )ODE

D (EOP )DE

D (EOP)DED

[CO

OH

], m

mol

/g p

ulp

0102030405060708090100

TAPPI B

rightness

[C O O H]B rig h tn ess

BS Kappa =26

Page 5: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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OD(EOP)D Mill Tensile Strength and Bulk/Surface Acid Groups.

50

55

60

65

70

75

80

85

90

95

100

Refere

nce C

ookBro

wn StockO2 F

eedO2 W

asher M

atD0 M

at(E

OP) Mat

D1 Mat

(R1-3

)*

D1 Transfe

r (R1-3)

*D1 M

at (R

4)*

D1 Transfe

r (R4)*

Stage

Tens

ile In

dex

0

20

40

60

80

100

120

Aci

d C

onte

nt, µ

eq/g

Tensile IndexBulk AcidSurface Acidx10

Fiber Engineering

Page 6: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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OD(EOP)D Mill Loss in Fiber Strength

130

135

140

145

150

155

160

165

170

Referen

ce C

ookBro

wn StockO2 F

eed

O2 Was

her M

atD0 M

at(E

OP) Mat

D1 Mat

(R1-3

)*

D1 Tran

sfer (

R1-3)*

D1 Mat

(R4)*

D1 Tran

sfer (

R4)*

Stage

Zero

Spa

n Te

nsile

Inde

x

Fiber Engineering

Page 7: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

• Primary losses in OD(EOP)D Mill fiber strength from digester, and O2 stages, and to a lesser extent, across the (EOP) stage.

0%Lab reference cook

-15.6%Bleached Hi-D pump (R4)-18.6%D1 washer mat (R4)-16.8%Bleached Hi-D pump (R1-3)-15.6%D1 washer mat (R1-3)-14.4%(EOP) washer mat-10.2%D0 washer mat-13.2%O2 washer mat

-8.4%O2 Feed-6.6%Brown stock washer mat

% Loss in ZST

Composite Samples

Page 8: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Fiber Length and Curl from OD(EOP)D Mill Pulps

00.020.040.060.08

0.10.120.140.160.18

0.2

Lab R

efere

nce C

ookBro

wn StockO2 F

eed

O2 was

her mat

D0 was

her mat

(EOP) w

asher

mat

D1 was

her mat

(R1-3

)*

Bleach

ed H

i-D pum

p (R1-3

)*

D1 was

her mat

(R4)*

D1 Hi-D

pump (R4)*

LW C

url I

ndex

22.12.22.32.42.52.62.72.82.93

LW F

iber

Len

gth,

mm

Curl Index Curl Index, PFI refined LW Fiber Length LW Fiber Length, PFI refined

Page 9: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Fiber Length and Curl from Mill D(EOP)D Pulps

0.040.060.08

0.10.120.140.160.18

0.2

Lab R

efere

nce c

ook

Knotte

r Fee

d

BS Was

her L

ine 2 M

at

Pre-was

her Fe

ed

Pre-was

her Disc

harge

D0 was

her fee

d

D0 was

her disc

harge

(EOP) s

tage f

eed

(EOP) w

ash fe

ed

(EOP) w

ash disc

harge

D1 fee

d before

ClO2

D1 fee

d after

ClO

2

D1 was

h feed

D1 was

h discharg

e*

Bleach

ed pulp to

Hi-D

LW C

url I

ndex

2

2.2

2.4

2.6

2.8

3

3.2

LW L

engt

h, m

m

Curl Index Curl Index, PFI refined Fiber Length Fiber Length, PFI refined

Page 10: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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• Across the whole bleach plant, there is a loss in bulk acid group content and a potential decrease in bonding capability. Combined with fiber strength loss, this leads to an overall lossin tensile strength.

• Largest single stage loss in bulk acid groups are in chlorine dioxide stages (D0 and D1) due in part to HexA loss. Need to examine further the effect of D stage conditions on acid groups.

• The capability to add or retain acid groups in the bleach plant would provide a means to better tailor fiber properties.

Fiber Engineering

Page 11: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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• Loss in fiber strength (zero span) across bleach plant with greatest loss in O2 stage and smaller loss in (EOP) stage. Previous work indicated that O2 stage loss is more of a function of mechanical treatment than chemical conditions. (Allison, et al. 1998) This needs to be investigated further.

• Significant curl imparted to Mill C pulps in oxygen stage with little additional increase in other stages.

• Only small effect on curl in Mill D bleach plant despite MC processing. (Potentially equipment related)

Fiber Engineering

Page 12: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber EngineeringResearch Objectives for Subtask III

1.Understand the mechanism of bond strength in TMP sheets by clarifying the morphological factors which hinder strong bond formation.

2.Understand the bond enhancement mechanism of reinforcement fibers.

Page 13: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

632.842.20.3829.61092592

303.126.00.2623.03951762

86.212.40.2217.0679883

TEA Index(mJ/g)

TensileIndex(Nm/g)

SheetDensity(g/cm3)

FinesContent

(%)CSF (ml)

SpecificEnergy

Consumption(kWh/t)

Page 14: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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883 kWh/t

Fiber Engineering

Page 15: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Description of Previous Slide

Specific energy consumption: 883 kWh/t

• Majority of the long fibers keep S1 layer

• S1 layer keeps the cross section squared

• The pulp has abundant shives

Fiber Engineering

Page 16: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

1762 kWh/t

Specific energy consumption: 1762 kWh/tMore fibers lose the S1 layerSquared fibers (cross section) are still notable

Page 17: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

2592 kWh/t

Specific energy consumption: 2592 kWh/t

Majority of long fibers lost the S1 layer

Fibers appear more collapsible

Page 18: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Modification/Fiber-Fiber BondingResults from Enhancement of Fiber-Fiber Bonding

883 kWh/t 2592 kWh/t

Fines Morphology

Fines consist of peeled S1 layer, cut fibers, ray cells, fibrils, pit borders, etc

Fines of peeled S1 layer are fibrillated and flattened with intensive refining

Fines appear more conformable

Page 19: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Effect of refining energy input on handsheet (60 g/m2) structure

• Thick-walled fibers are resistant to collapse regardless of refining energy

• Thin-walled fibers tend to collapse more with increased refining

• Reduction of caliper appears be largely dependent on the flattening of thin-walled fibers

Fiber Engineering

Page 20: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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883 kWh/t

thin-walled fibers

thick-walled fibers

Page 21: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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1762 kWh/t

Page 22: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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2592 kWh/t

Page 23: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Two newsprints, made of black spruce and southern pine TMPs, were compared to understand how pulp morphology affects the structure of commercial products

Structure of newsprints made ofblack spruce and southern pine TMPs

Page 24: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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1.6840.03429.7Black Spruce Newsprint

1.5780.04431.1Southern

Pine Newsprint

Fiber Length (mm)Curl IndexFine Content

(%)

Fiber Engineering

Page 25: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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375.419.5445.963.348.2Black

Spruce Newsprint

393.317.1343.050.549.2Southern

Pine Newsprint

TEA Index,

CD, mJ/g

Tensile Index,

CD, Nm/g

TEA Index,

MD, mJ/g

Tensile Index,

MD, Nm/g

Basis Weight g/m2

Fiber Engineering

Page 26: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Cross Sections of Newsprints (high density area)

Southern Pine Black Spruce

Fiber Engineering

Page 27: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Description of Previous Slide

• Both thin-walled and thick-walled fibers are notably deformed and collapsed by calendering in dense areas

• Black spruce has more fibers in cross section than southern pine*

*compared at the same basis weight

Fiber Modification/Fiber-Fiber BondingResults from Enhancement of Fiber-Fiber Bonding

Page 28: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Cross Sections of Newsprints (low density area)

Southern Pine Black Spruce

Fiber Engineering

Page 29: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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fines

Southern Pine Newsprint

Thin-walled fibers are less collapsed in the low density areaThick-walled fibers are uncollapsed

There is noticeable difference in location of fines between southern pine and black spruce newsprintsSouthern pine newsprint: fines are filtered at the pocket of coarse fiber network at low density area fewer fines are located in high density areasBlack spruce: fines are more or less uniformly distributed

Page 30: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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• Bonded areas in southern pine and black spruce newsprints, as visualized by vapor phase osmium coating, are notable as the dark areas (areas of bond breakage)

• Southern pine newsprints seem to have fewer bonded areas than black spruce

Fiber Engineering

Page 31: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Fiber Engineering

Page 32: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Bonded area in black spruce newsprint

Fiber Engineering

Page 33: Kraft and Mechanical Pulpsbiorefinery.utk.edu/technical_reviews/Fiber Engineering.pdf · Lab reference cook 0% Bleached Hi-D pump (R4) -15.6% D1 washer mat (R4) -18.6% Bleached Hi-D

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Research Team

Chuck CourcheneHiroki NankoArt Ragauskas

Fiber Engineering