light-induced gold iridescence (sunburn) of epdm weatherseals
DESCRIPTION
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals. by Bob Ohm* & Dan Patton Lion Copolymer, LLC Compounding and Development Center 5955 Scenic Highway, Baton Rouge, LA 70805. * Speaker. Outline. Introduction Bloom vs. Iridescence - PowerPoint PPT PresentationTRANSCRIPT
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
by Bob Ohm* & Dan PattonLion Copolymer, LLC
Compounding and Development Center5955 Scenic Highway, Baton Rouge, LA 70805
* Speaker
Outline
IntroductionBloom vs. Iridescence23 Designed Experiment: Filler, Oil & CurativeEffect of Cure Temperature & EPDM PolymerSurface AnalysisAntioxidant ComparisonFinal ExperimentsSummary
IntroductionWhy weatherseals are based on EPDM
Excellent WeatherabilityImpervious to OzoneHighly Resistant to Heat and OxidationHighly Extendable
Discoloration in LightInitial colors blue / red / greenChange to bronze / gold
Prior Work
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
•Best viewed at shallow angle•A long-standing issue•Various “solutions” proposed:
–Cure system–Filler–Polymer–Additives
•Root cause & permanent fix elusive
The Iridescent Color depends on the angle of view
Bloom and BleedSurface Discoloration due to powdery solid (bloom) or liquid film (bleed)
The remedy is straightforward:1. Remove the material at the surface2. Determine the composition of the material removed.3. Lower the dose or eliminate the use of the material identified.
Gold IridescenceSurface Discoloration due to
The discoloration can not be readily removed. Methylene chloride removes - but only temporarily!
???
Thermal Desorption ResultsEric Jourdain, Paper #42, 149th ACS Rubber Division meeting (May 1996)
Non-exposed Side
0
500,000
1,000,000
1,500,000
2,000,000
2,500,000
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Time
Ab
un
dan
ce
O
S C N
C
O
OH
O
NH
NH
N
S
HO
Thermal Desorption ResultsEric Jourdain, Paper #42, 149th ACS Rubber Division meeting (May 1996)
Sun Exposed Side
0
500,000
1,000,000
1,500,000
2,000,000
2,500,000
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Time
Ab
un
dan
ce
NH
Light-Induced Gold Iridescence (Sunburn) of EPDM WeathersealsFive Studies:
1. 23 design for: A/ filler (furnace vs. thermal) B/ plasticizer (par oil vs. poly alpha-olefin), C/ cure system (sulfur vs. peroxide) and D/ cure time at 182°C (1.5 vs. 10 minutes)2. effect of: A/ diene content (4 vs. 8%), B/ ethylene content (60 vs. 70%) and C/ cure temperature (230 vs. 340°C)3. surface analysis4. antioxidant comparison5. polymer, filler & other variations
23 Designed Experiment
Filler / carbon black
Oil / plasticizer
Cure System (Sulfur vs. Peroxide)
Additive Package (the 3 Amigos)
Filler Comparison
A. Furnace black:– made from crude oil– made in air– contains aromatic structures (staining)– contains sulfur, nitrogen
B. Thermal black*:– made from natural gas– anaerobic manufacture (no oxygen)– minimum extractables (aromatics)– little/no sulfur, nitrogen
* plus precipitated silica to equalize hardness
Plasticizer Comparison
A. Parafinnic oil:– made from crude oil– contains aromatic structures– contains sulfur, nitrogen
B. Poly -olefin:– made from decene– no residual unsaturation
(removed by hydrogenation)– no sulfur, nitrogen
Cure System ComparisonA. Sulfur cure:
– contains sulfur, nitrogen– little/no oxygen– accelerator fragments found on
surface
B. Peroxide cure:– no sulfur, nitrogen– contains oxygen
Gold Ratings: 1 = best, 5 = worst6 days exposure per SAE J1960 (exterior)
3, 2 5, 4
5, 4 3, 2 (PO)
-2
-1
0
1
2
-2 -1 0 1 2
Filler (-1 = thermal black*, +1 = furnace black)
Cu
re S
yste
m,
(-1
= p
erox
ide,
+1
= s
ulf
ur)
SulfurCure
PeroxideCure
ThermalBlack*
FurnaceBlack
3 Am.= 5
3 Am. = 1
* = mat surface develops during light exposure
Gold Ratings: 1 = best, 5 = worst6 days exposure per SAE J1885 (interior)
2, 3 5, 5
3.5, 3.5 1, 2.5 (PO)
-2
-1
0
1
2
-2 -1 0 1 2
Filler (-1 = thermal black*, +1 = furnace black)
Cu
re S
yste
m,
(-1
= p
erox
ide,
+1
= s
ulf
ur)
SulfurCure
PeroxideCure
ThermalBlack*
FurnaceBlack
3 Am.= 0.5
3 Am. = 1.5
* = mat surface develops during light exposure
Summary of 23 Experiment
A. The filler system is most important for gold iridescence. A thermal black/ppt. silica blend develops a low-gloss (mat) surface during light exposure, minimizing the gold iridescence.
B. The 3 Amigos are effective, esp./SAE J1885.
C. A peroxide cure is poorer than the sulfur cure per SAE J1885 (no effect per SAE J1960).
D. The PAO is better than paraffinic oil per J1960 (no effect or slightly poorer by J1885).
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
Five Studies:1. 23 design for: A/ filler (furnace vs. thermal) B/ plasticizer (par oil vs. poly alpha-olefin), C/ cure system (sulfur vs. peroxide) and D/ cure time at 182°C (1.5 vs. 10 minutes)2. effect of diene content (4 vs. 8%), ethylene content (60 vs. 70%) and cure temperature (230 vs. 340°C)3. surface analysis4. antioxidant comparison5. polymer, filler & other variations
Polymers Evaluated
EPDM563/501
EPDM556
EPDM509
EPDM505
3
5
7
9
50 55 60 65 70 75 80
Ethylene Content, %
Die
ne
Co
nte
nt,
%
Previous workers= best
Previous workers= worst
(Cure Temperature = 230 or 340 °C)Light Exposure = 6 days SAE J1885
Gold Ratings: 1 = best, 5 = worst
4 3
2 2
3
5
7
9
50 55 60 65 70 75 80
Ethylene Content, %
Die
ne
Co
nte
nt,
%
UV* = 1 3 Am.= 1
UV* = 3 3 Am. = 2
Cure Temp. 10’/230, 2’/340 °C = NO EFFECT
However, 10’at 340°C = IMMEDIATE GOLD
* = heavy white bloom on molded samples
Summary of Second Study
A. The gold color can be developed by oxidation without light exposure. (However, this method leads to sample embrittlement.)
B. High diene polymers give lower gold ratings.
C. Gold ratings can be further lowered by addition of the “Three Amigos”.
D. Ethylene level and cure temperature have little effect on gold in our laboratory work.
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
Five Studies:1. 23 design for: A/ filler (furnace vs. thermal) B/ plasticizer (par oil vs. poly alpha-olefin), C/ cure system (sulfur vs. peroxide) and D/ cure time at 182°C (1.5 vs. 10 minutes)2. effect of diene content (4 vs. 8%), ethylene content (60 vs. 70%) and cure temperature (230 vs. 340°C)3. surface analysis4. antioxidant comparison5. polymer, filler & other variations
Surface Analysis Methods
SEM
TOF-SIMS
XPS
AFM
Scanning Electron Microscopy
Time of Flight - Secondary Ion Mass Spectroscopy
X-Ray Photoelectron Spectroscopy
Atomic Force Microscopy
Surface Analysis of Molded Test Pads Scanning Electron Micrograph (SEM)
10 m10 m
Surface Analysis Techniques
TOF-SIMS Time of Flight
Secondary Ion Mass Spectroscopy
* or ESCA, electron scattering for chemical analysis
XPS X-Ray
Photoelectron
Spectroscopy*
Found onlysiloxane
(mold release).
012771130.spe: control sample A Evans East01 Dec 17 Al mono 350.0 W 0.0 50.0° 187.85 eV 2.0460e+005 max 4.50 minSur1/Full/1
200400600800100012000
0.5
1
1.5
2
2.5x 10
5 012771130.spe
Binding Energy (eV)
c/s
-C
KL
L
-Z
n2
p1
-Z
n2
p3
-O
KL
L -
O K
LL
-Z
n L
MM
-O
1s
-Z
n L
MM
-Z
n L
MM
-C
1s
-S
i2s
-S
i2p
-F
1s
-N
1s
-Z
n3
p3
-Z
n3
s
XPS - Black Area
Oxygen
Carbon
012771120.spe: "gold" sample A Evans East01 Dec 17 Al mono 350.0 W 0.0 50.0° 187.85 eV1.8553e+005 max 4.50 minSur1/Full/1
200400600800100012000
0.5
1
1.5
2
2.5x 10
5 012771120.spe
Binding Energy (eV)
c/s
-C
KL
L
-Z
n2
p1
-Z
n2
p3
-O
KL
L -
O K
LL
-O
1s
-Z
n L
MM
-Z
n L
MM
-N
1s
-C
1s
-S
2s
-S
2p
-S
i2s
-S
i2p
-Z
n3
p3
-Z
n3
s
XPS - Gold Area
Carbon
Oxygen
XPS Oxygen Results - 2nd Study
0
5
10
15
20
25
Royalene505
(GR=2)
Royalene556
(GR=3)
Royalene563/501(GR=4)
R-505 +UV Stab.(GR=1)
R-505 + 3AmigosGR=1)
10 min @650F
(GR=10)
Oxy
gen
Co
nce
ntr
atio
n,
% black surfacegold surface
XPS Nitrogen Results - 2nd Study
0.0
0.5
1.0
1.5
2.0
2.5
EPDM505
(GR=2)
EPDM556
(GR=3)
EPDM563/501(GR=4)
505 + UVStab.
(GR=1)
505 + 3AmigosGR=1)
10 min at340ºC
(GR=10)
Nit
rog
en C
on
cen
trat
ion
, %
black surface
gold surface
contains MSDPA amine antioxidant
XPS Zinc Results - 2nd Study
0.0
0.5
1.0
1.5
2.0
2.5
EPDM505
(GR=2)
EPDM556
(GR=3)
EPDM563/501(GR=4)
505 +Ciba
(GR=1)
505 + 3AmigosGR=1)
10 min @650F
(GR=10)
Zin
c C
on
cen
trat
ion
, % black surface
gold surface
Gold Matt Gold Shiny
High Resolution AFM Surfaces
Black
Surface Analysis SummaryA. Molded samples under SEM appear to
develop raised nodules.
B. TOF-SIMS was not successful in identifying the composition of the nodules.
C. XPS finds the gold surface is enriched in oxygen and, to a lesser extent, nitrogen and zinc.
D. AFM finds black regions are smooth; light-exposed gold regions, especially low-gloss, are rough – nano structure.
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
Five Studies:1. 23 design for: A/ filler (furnace vs. thermal) B/ plasticizer (par oil vs. poly alpha-olefin), C/ cure system (sulfur vs. peroxide) and D/ cure time at 182°C (1.5 vs. 10 minutes)2. effect of diene content (4 vs. 8%), ethylene content (60 vs. 70%) and cure temperature (230 vs. 340°C)3. surface analysis4. antioxidant comparison5. polymer, filler & other variations
Comparison of Antioxidantsin the Three Amigos
Blank Bisphenolic ODPA TMQNo AO (liquid)
OH
CH3
CH2H19C9
OH
C9H19
CH3
NH
C8H17
C8H17
N
CH3
CH3
CH3
H n
Light Exposure = 6 days SAE J1885
Comparison of Antioxidantsin the Three Amigos (continued)
MSDPA Sulfonated Bisphenol NBC Diphenyl- Phosphite amine Blend
NH
CCH3
H3C
CH3C
CH3
SO2
H3C
NH
NHNi
S
S
C
S
N (C4H9)2
C N (C4H9)2
S
Light-Induced Gold Iridescence (Sunburn) of EPDM Weatherseals
Five Studies:1. 23 design for: A/ filler (furnace vs. thermal) B/ plasticizer (par oil vs. poly alpha-olefin), C/ cure system (sulfur vs. peroxide) and D/ cure time at 182°C (1.5 vs. 10 minutes)2. effect of diene content (4 vs. 8%), ethylene content (60 vs. 70%) and cure temperature (230 vs. 340°C)3. surface analysis4. antioxidant comparison5. polymer, filler & other variations
Polymer, filler & other variationsGold Ratings = cured / uncured
Peroxide Cures of:N762 black N990 black &
KE clay
EPDM 4345 (DCPD) 5/5 1/1
EPM 404 Copolymer 5/4 2/2
EPDM 509 (ENB) 4*/5 1/1
EPDM 509 / sulfur cure 5*/4 rainbow/ws
The filler system of N990 & KE clay give a dull surfaceAfter SAE J1885 exposure, similar to N990 & ppt. silica.
* Rating improves where Mylar film adhered.
Final ExperimentPhoto of Test Pad with Gold Iridescence Middle portion clamped 1 week at RT removes gold.
10 mm
However:gold returns on oven aging or more light exposure.
Optical Properties of Nano ParticlesChad A. Mirkin, George C. Schatz, et. al., Science, 294, pages 1901-1903 (2001),
as taken from Chemical & Engineering News, page 10 (Dec. 2, 2001)
Silver nanoprisimsscatter red light.
Gold nanorodsscatter orange light.
Gold nanospheresscatter green light.
SummaryA. Compression of the surface can
remove the gold iridescence.
B. However, this is not a practical solution because the gold is redeveloped during brief oven aging or additional light exposure.
C. For future work, a permanent solution may require both chemical and physical (structure) control.
Thanks for your attention
Any Questions?
In the scales of the greenportion of the papillo’s wings,each concavity reflects bright yellow while the outer edges
reflect bright blue…
The papillo butterfly’s wingsare covered with small textured
scales (above right)… Tinyconcavities within these scales(below left) create color through
constructive interference…
The Three AmigosOH
CH3
CH2H19C9
OH
C9H19
CH3
Naugawhite
R
OH
CH2
OH
R
HO
OH
R
CH2 OH
n
Schenctady SP-1066 Phenolic Resin
HO O OHn
Carbowax 3350Polyethyleneglycol
Gold RegionGold Region
250 500 1000 1500
Particle Size, nm
Particle Size of Additives
HardClay
SoftClay
ZincOxide
Precipitated Silica
Whiting
N990N774Carbon
Black
High Resolution XPSMain Peak = C-(C1H)
control sample A-O-C=O
gold sample AC-O
C=O C-N
AFM Surface AnalysisBlack Surface Shiny Sample Black Surface of Matt Sample
Gold Shiny Surface Gold Matt Surface30 m
Gold Matt Gold Shiny
High ResolutionAFM Surfaces
0 2 4 6
350
nm 0
-3500 2 4 6 m
350
nm 0
-350
Black
475 nm665 nm 130 – 250 nm