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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