plasma polymerization of acetylene and thiopheneonto ... · stress-strain behavior: s-sbr 0 100 200...
TRANSCRIPT
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M. Tiwari, R. N. Datta, A. G. Talma, J. W. M. Noordermeer, W. K. Dierkes
Department of Elastomer Technology and Engineering,
University of Twente, 7500 AE Enschede, The Netherlands
W. J. van Ooij
Department of Chemical and Materials Engineering,
University of Cincinnati, Cincinnati, OH 45221-0012, USA
Plasma polymerization of Acetylene and Thiophene onto
Silica - an Alternative to Improve Reinforcement of Silica
in S-SBR and EPDM
ETE – VKRT MeetingUniversity of Twente, Enschede
December 12, 2008
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2
Contents
ð Introduction
ð Aim
ð Experimental
ð Results & discussion
ð Summary
ð Acknowledgement
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3
Filler reinforcement
Filler dispersion depends onPolymer:
ð Type
ð Molecular weight
Filler:
ð Particle size distribution
ð Structureð Surface activity
Introduction
è Non-uniform dispersion influences the properties
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4
Plasma Polymerization
Monomer Plasma-Polymer - highly crosslinked- disordered structure- two-dimensional network- thermally, chemically stable- very adherent- bulk properties preserved
Introduction
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5
Plasma reactorIntroduction
- RF (13.56MHz) plasma: very stable and reactive
- Tumbler reactor: 350 g capacity
CarrierGas 1
RF Coils
Flange
Monomer 2Vacuum Pump
Thick Pyrex
MotorVacuumGrease
PressureGauge
RF Source13.56MHz
AC
Probe 1 Probe 3
Plate
Baffles Oil Trap
40cm
20cm
20cm
Throttling Valve
Carrier Gas 2
O-ring
or monomer 1
Probe 2
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6
Aim of the work
_ Comparison of the effect of Plasma-thiophene and –acetylene coated silica in terms of their:
…achieved by surface modification by plasma polymerization process
- compatibility
- wettability
- dispersion
with S-SBR and EPDM
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7
Polymers: - S-SBR (Buna® VSL 5025-0 HM, Lanxess GmbH):
25 wt% styrene, 75 wt% butadiene
- EPDM (Keltan® 4703, DSM Elastomers B.V.):
9 wt% ethylidene norbornene, 48 wt% ethylene, 43 wt% propylene
Fillers: - Precipitated silica (Ultrasil VN3, Degussa GmbH)
Plasma monomer: -High purity acetylene (C2H2, Wright Brothers, Inc.)
-High purity thiophene (C4H5S, Sigma-Aldrich, Inc.)
Silica coupling agent: Bis-(triethoxysilylpropyl) tetrasulphide, TESPT (Si69, Degussa GmbH)
MaterialsExperimental
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8
ExperimentalPlasma polymerization
Monomers: - Acetylene- Thiophene
9053100PA-Silica
9020100PTh-Silica
Time (minutes)
Monomer Pressure
(Pa)
Power(W)
Code
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9
ð Thermo-Gravimetric Analysis
(TGA7, Perkin-Elmer; rate of heating 10°C/min.)
ð Time-of-Flight Secondary Ion Mass Spectrometry (ToF- SIMS)
ExperimentalFiller characterization
ðWater penetration measurements
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10
ExperimentalCompounding
U: Untreated; PA: Plasma acetylene coated; PTh: Plasma thiophene coated; T: Silanised with TESPT
S: S-SBR; E: EPDM
1.51.51.51.5--------ZBEC
0.80.80.80.8--------TMTD
--------1.51.51.51.5DPG
1.51.51.51.51.51.51.51.5CBS
1.041.51.51.51.041.51.51.5Sulfur
4------4------Silane (TESPT)
2.02.02.02.02.52.52.52.5Stearic acid
55552.52.52.52.5ZnO
5050505050505050Silica
100100100100--------EPDM
--------100100100100S-SBR
phrphrphrphrphrphrphrphr
ETEPThEPAEUSTSPThSPASU
SamplesComponents
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11ExperimentalMixing procedure
Load compoundDump
05
Step 2:
Filling of the chamber of the Brabender with gum rubber, lowering of the Plunger.Raising of the plunger and adding ZnO, stearic acid, ½ silica and ½ silane (if the masterbatch preparation was with silane), lowering of the plunger.Raising of the plunger and adding ½ silica and ½silane (if the masterbatch preparation was with silane), lowering of the plunger.SweepDump of the masterbatch
0
1
2
46
ActionTime (mins.)
Step 1:
Curatives: added on a two roll mill
Curing: Wickert laboratory press WLP 1600/5*4/3 at
160°C, 100 bar
Mixing: Brabender 350S
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12
ð Payne effect (RPA 2000, Alpha Technologies)
ð Bound rubber content
ð Cure characteristics (RPA 2000, Alpha Technologies)
ð Reinforcement parameter (αF)
ð Tensile properties (Zwick Z020)
ð Relative ranking of cross-link density (1/Q)
ExperimentalCompounds testing
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13
Plasma polymerization of acetylene and
thiophene onto silica fillers
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14Results & discussion
0 2 4 6 8 10 12 14 160,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
1,8
2,0
0 2 4 6 8 10 12 14 160,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
1,8
2,0W
eigh
t of w
ater
pen
etra
tion
(g)
Time (mins.)
Untreated silica PA-silica PTh-silica
Hydrophobicity: penetration
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15Results & discussion
100 200 300 400 500 60088
90
92
94
96
98
100
100 200 300 400 500 60088
90
92
94
96
98
100
100 200 300 400 500 60088
90
92
94
96
98
100W
eigh
t (%
)
Temperature oC
Untreated silica
PTh-silica PA-silica
Weight loss (TGA)
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16
Untreated
Results & discussionChemical composition of the surface: ToF-SIMS
PA-treatedC2H3
PA-clusters
C10H10
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17
Untreated
Results & discussionChemical composition of surface: ToF-SIMS
C10H10
C2H3NaH
PTh-treated
PTh-clusters
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18
Plasma-acetylene and -thiophene silica
reinforced S-SBR and EPDM
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19Results & discussionPayne effect (Filler-filler interactions)
SU SPA SPTh ST EU EPA EPTh ET0.0
0.4
0.8
1.2
1.6G
'(0.5
6%) -
G'(1
00.0
4%) [
MP
a]
Sample code
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20Results & discussionBound rubber content
SU SPA SPTh ST EU EPA EPTh ET0
10
20
30
40
50
60
70
Bou
nd ru
bber
con
tent
(%)
Sample code
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21Results & discussionReinforcement parameter
SU SPA SPTh ST EU EPA EPTh ET0
2
4
6
8
10R
einf
orce
men
t par
amet
er (α
F)
Sample
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22Results & discussionStress-strain behavior: S-SBR
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
Strain (%)
Stre
ss (M
Pa)
SU
ST
SPA SPTh
SU
SPAST
SPTh
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23Results & discussionStress-strain behavior: EPDM
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
0 100 200 300 400 500 600 700 8000
5
10
15
20
25
Strain (%)
Stre
ss (M
Pa)
EU
ET
EPA EPTH
EU
EPAET
EPTh
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24Results & discussionRelative ranking of cross-link density
SU SPA SPTh ST EU EPA EPTh ET0.0
0.1
0.2
0.3
0.4
0.5
0.6R
elat
ive
rank
ing
of c
ross
link
dens
ity (1
/Q)
Sample code
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25
Summary
Acetylene and thiophene plasma coating:_ Silica is coated successfully by plasma acetylene- and thiophene-treatment
_ Reduced polarity of the silica due to plasma coating
Comparison of acetylene and thiophene plasma treatment in S-SBR:
_ Higher reduction in filler-filler interaction (Payne effect) due to PA-silica
_ PTh-silica shows highest bound rubber content
_ Dispersion is improved in the case of PA-silica
_ Compared to PA-silica, PTh-silica shows the best tensile properties whichcorrelates with the relative ranking of cross-link density
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26
Summary
Comparison of acetylene and thiophene plasma treatment in EPDM:
_ PTh-silica shows higher reduction in filler-filler interaction (Payne effect)
_ Bound rubber content is highest in PA-silica
_ PTh-silica shows the best dispersion
_ PA- and PTh-silica shows improved tensile properties but PA-silica shows
higher moduli at 100% and 300%
_ Tensile properties are in correlation with the relative ranking of cross-link
density
_ PA-silica shows improved compatibility and interaction of fillers with
EPDM
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27
Acknowledgements