Di l t i Di h A C t t dDielectric Discharge: A Concatenated Approach to Fiber ModificationApproach to Fiber Modification

I i f P S i d T h lInstitute of Paper Science and Technology

Lorraine C. Vander WielenDr. Arthur J. Ragauskas

Dielectric Discharge: A gConcatenated Approach to Fiber

M difi tiModification• Connection between• Connection between

dielectric discharge treatment and fibertreatment and fiber surface acid topochemistrytopochemistry.

Hypothesis

DBD i iti t d ti b d t

• DBD-initiated reactions can be used to promote carboxylic acid groups on the surface of pulp fibers, thereby modifying fiber surface topochemistry.y g p y

FiberAcid Groups

Objective

• Use surface analysis techniques to characterize the impact of DBD upon carboxylic acid group topochemistry on the surface of pulp fibers.

Outline

• Background• ExperimentalExperimental

Approach R l• Results

• Conclusions• Acknowledgments

Dielectric Breakdown Discharge –Dielectric Breakdown Discharge Principles

Plasma-air gas-O phase reaction

mechanism involves h d d f

+++++

-----

O3

HO.Increasede-e-

hundreds of reactions and numerous species

++++++

----

e-

hvVoltagee-

e-e- numerous species

which can interact with substrate

+-1O2

Surface oxidation/grafting of polymeric films, biofibers.

Dielectric Breakdown Discharge –Dielectric Breakdown Discharge –Principles

• Compatibilityp y– Surface chemistry

65º 30º

P l t

H2O

Polyester Polyester

DBD Treatment/Modification ofDBD Treatment/Modification of Cellulosics - Past and Present

• Goring & others 1967 • Sakata and GoringGoring & others, 1967• Brown & Swanson (1971)

at IPC

• Sakata and Goring• Sapieha, Bataille and others• Recent Resurgence:at IPC

• Back & Danielsson (1987/1988) at STFI

Recent Resurgence:• SCA Patents, 1998+• Eastman Kodak( )

• Sapieha with Bataille, Belgacem & others at

− 1970’s− 1998 - 2002

Ecole Polytechnic (1990s)• Kempii (1990s)

Fiber Charge

• Acid Groups– Fiber/Process 4

5

km)

Chemical Interactions– Fiber Swelling

1

2

3 BLANK

BULK

SURFACE

ng L

engt

h (k

– Bonding 0170 220 270 320 370

Light Scattering Coefficient (cm2/ g)Bre

akin

Light Scattering(cm2/g)

• Scallan, Grignon, Lindström, Wågberg, Ampulski, Engstrand et al Barzyk et al Sjöström Zhang et alEngstrand et al, Barzyk et al, Sjöström, Zhang et al, Ragauskas et al etc.

Sample Preparation

• Softwood BKP– Long Fiber

FractionsFractions• Softwood Unbleached

TMP– Long FiberLong Fiber

Fractions

Sample Preparation

E t ti• Extraction– 24 Hours

Sample Preparation

F Sh t• Form Sheets• Condition Sheets

Sample Preparation: Dielectric p pBreakdown Discharge Treatment

ElectrodesElectrodes

Fiber Surface Analysis forFiber Surface Analysis for Carboxylic Acid Groupsy p

• Electron Spectroscopy for Chemical Electron Spectroscopy for Chemical Analysis (ESCA)Ti f Fli ht S d I M• Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS)

• Standard Titration MethodsPolyelectrolyte Titration– Polyelectrolyte Titration

– Conductometric Titration

Fib S f A l i ESCAFiber Surface Analysis - ESCA

• Quantitative - Carbon Functional Groups• Qualitative - Species Present• Physical Electronics 5802 Multitechniquey q− Al-K X-ray Source− 1 5 X 0 6 mm Samples1.5 X 0.6 mm Samples− Maximum Depth 5.0 nm

T i li t− Triplicate

Fib S f A l i ESCAFiber Surface Analysis - ESCA

sity

l Int

ens

Sign

a

Binding Energy (eV)

TMP Fiber Surface ChemistryTMP Fiber Surface Chemistry -ESCA

60.070.080.0

e

20 030.040.050.0

Cha

nge C-O

O-C-O/C=OAcidC C C H

-10.00.0

10.020.0

130 160 280 560

% C-C, C-H

-20.0

Dosage (W)

BKP Fiber Surface ChemistryBKP Fiber Surface Chemistry -ESCA

30

40

50

ge C-O

0

10

20

% C

hang C-O

O-C-O/C=OAcidC-C, C-H

-30

-20

-10 1 2 3%

C C, C H

Dosage (W)

BKP Fib S f Ch i t ESCABKP Fiber Surface Chemistry - ESCA

3 4C)

2 83

3.23.4

Tota

l C

Dielectric

2.42.62.8

ds (%

DielectricDielectric-Ext

22.2

0 40 200 560

Aci

d

Dosage (W)

BKP Fib S f Ch i t ESCABKP Fiber Surface Chemistry - ESCA

OH OH OHOO

HOOH

OO

HOOH

OH

O

HOOH

OO

HOOH

O-

OH

O

O OHOH

O OHOH

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O-

OH

OH

O

OHO

HOOH

HOO

HOOH

OH

OH

OH

HOOH

HOO

HOOH

O-

OH

OH

O

OH

O

OH

O

OH

OO

HOOH

OO

HOOH

OH

O

HO OHO

OHO-

OH

OO

OHO

OHO

O

HOOH

OH

O

HOOH

OO

HO OHO-

OH

OOH

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HO OHO-

OH

OH

O

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O-

OH

OH

O

OH

OO

HOOH

OO

HOOH

OH

O

HOOH

OO

HOOH

O-

OH

O

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HO OHO-

OH

OH

O

OH OOH

HOOH

OO

OH

OO

HOOH

OO

HOOH

OH

O

HOOH

OO

HO OHO-

OH

O

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O-

OH

OH

O

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HO OHO-

OH

OH

O

OH OOH OH O

OH

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HO OHO-

OH

OH

O

OHOH O

OH

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HO OHO-

OH

OH

O

OH OH

Paper Oxidized Paper Surface Oxidized materialOxidized material washes out

TMP Fib S f Ch i t ESCATMP Fiber Surface Chemistry - ESCA

6C)

4

5

Tota

l C

1

2

3

ds (%

T

0

1

0 W 280 W 280 W - Extract

Aci

d

Dosage (W)

Fib S f Ch i t T F SiFiber Surface Chemistry - ToF-Sims

• Quantitative (Mass Spectral Data)Q li i (I i )• Qualitative (Imaging)

• Physical Electronics TRIFT III− 69Ga− 400 μm X 400 µm400 μm X 400 µm− Prior Applications:

Kulick and Brinen (1996); Deslandes Pleizier PoireKulick and Brinen (1996); Deslandes, Pleizier, Poire, Sepieha, Wertheimer, Sacher (1998); Kleen (2000) Kleen, Räsänen, Ohra-aho, Laine (2001)

BKP S f Ch i t T F SiBKP Surface Chemistry - ToF-Sims

CHO2 C3H3O2

CNOCNO

O2 C2H3O2

BKP Surface Chemistry - ToF-SIMS

CNO CN C2H3O2 CHO2 OCNO CN C2H3O2 CHO2 O

Control 0.37% 1.8% 2.8% 4.0% 42.1%

DBD 0.47% 1.9% 3.8% 8.0% 44.0%

BKP ToF-SIMS ImagesBKP ToF SIMS Images - Total Ion Spectra

T l I S DBD T d T l I STotal Ion Spectra DBD Treated Total Ion Spectra(Bar = 100 μm)

BKP ToF-SIMS ImagesBKP ToF SIMS Images - C2H3O2 Spectra

Control C2H3O2 Spectra (2.8 %) DBD Treated C2H3O2 (3.8 %)Spectra (Bar = 100 μm)

Standard Titration Methods

• ConductometricConductometric Titration

• Polyelectrolyte• Polyelectrolyte Titration

TMP Fiber ChemistryTMP Fiber Chemistry –Conductometric Titrations

100

80

100

ueq/

g)

40

60

Gro

ups

(u

0

20

Aci

d G

00 50 100 150 200 250 300

Dosage (W)

BKP Fiber ChemistryBKP Fiber Chemistry –Conductometric Titrations

40

50

eq/g

)

20

30

40

Gro

ups

(ue

0

10

0 500 1000 1500 2000

Aci

d G

Dosage (W)

TMP Fiber Surface Chemistry y- Polyelectrolyte Titration

6.5

7.0

ueq/

g)

6.0

Gro

ups

(u

20%

5.0

5.5

Aci

d G

0 100 200 300 400 500 600

Dosage (W)

BKP Fiber Surface Chemistry –yPolyelectrolyte Titration

2.3

2.4

eq/g

)

2.1

2.2

roup

s (u

e

20%

1 8

1.9

2

Aci

d G

r

1.80 500 1000 1500 2000

Dosage (W)g ( )

Conclusions

• Acid groups at the fiber surface are enhanced via DBDAcid groups at the fiber surface are enhanced via DBD treatment

• Surface acids are increased up to 65%W hi l f d idi d– Washing removes newly formed oxidized functionalities for a net increase of approximately 20%

– No detectable increase in bulk acids• DBD operating conditions impact surface modification

Conclusions

• Potential Applicationspp– Composite Structures

• Polymers plastics other materialsPolymers, plastics, other materials– Retention

• Additives• Additives• Fillers

– Create Materials with Novel Properties– Additives/Fines Retention