AIMCAL Fall Technical Conference

October 19 – 22
North Myrtle Beach, SC

Over-Treatment of PET: Fact or Fiction.

Part I – Corona and Part II
Atmospheric Plasma
A study of the following variables: watt
density, treatment dwell time, film
selection, dyne level and water-soak
bond strength
Presented by:
Jessica Bodine
Technical Sales Representative
Mica Corporation
Typical Properties of PET*
† Tensile Strength = 2,250 kg/cm2
† Yield Strength = 1050 kg/cm2
† Elongation = 110%
† Modulus = 42,200 kg/cm2
† CoF = .40/.36 (Static/Kenetic)
† Density = 1.395 g/cm3
† Haze (48 ga) = 3%
* As provided by Mitsubishi for Hostaphan 2261N
PET and Corona Treatment

-OOC-Ar-COO-CH2 CH2-O- + O3

OOC-Ar-COOH + HOCH 2CH2 O

 Low Molecular Weight Fragments
(LMWF)
† C-OH
† C=O
† COOH
† C-O-C
† Epoxy
† Esters
† hydroperoxide
Analytical Techniques
† X-ray spectroscopy
† Atomic Force Microscopy
† Scanning Force Microscopy
† TOF Simms
† Contact angle measurement
(advancing and receding)
† Standard dyne level testing (dyne
solutions)
† See References 1 – 4 in full published paper
Confirmation of LWMF
† Well known and confirmed that higher
watt density corona treatment
produces more LWMF (References 1-
5)
† Some oxidized species are necessary
for adhesion
† Tipping point: Corona no longer
beneficial – but detrimental to
adhesion = “over-treatment”
Atmospheric Plasma Treatment
(APT)
† Both corona and APT = ionization of
gas at surface of the film
† Corona = high voltage for initiation
† Corona = directional discharge
between 2 electrodes, may cause
micro re-treatment due to tendency
to be attracted to already ionized
point
† (Ref 8)
Advantaged of APT process
† Lower initiation voltage
† Cloud-like discharge, more even
distribution
† In addition to ionization of the air
already present at the film surface,
chemistries can be introduced by
specific selection of gas used
Real World Converting
† Instrumental analysis = $$$
† Is dyne level testing enough?
† What tests can the average
manufacturer run to make
understand the “tipping point”
† What manufacturer controllable
variables contribute the most to “over
treatment”?
Converting
† Printing
† Coating
† Adhesive Lamination
† EXTRUSION LAMINATION
Variables
† Film selection
† Watt density
† How to achieve watt density? With
one electrode or multiple electrodes?
† APT = gas, ratios and flow rate =
100s of combinations, only 1 was
choosen of each and kept constant
Watt Density - Corona
† Watt-Density (WD) =
power/area/time

† Units = W/m2/minute

† Calculation:

(KW setting x 1000)/[Line speed (m/min) x width (m)]

Watt Density – Electrode
Assemblies
† W/m2/minute
† “W” can be supplied by 1 or more assemblies
† “W” is additive
† WD was held constant but was achieved either
by treating with 1 electrode assembly or with 2
in sucession
† For example: films treated to 10 WD
„ 1 electrode assembly set at 10
„ 2 electrode assemblies each set at 5
Watt Density – Atmospheric Plasma
† Same units and calculation
† Controllable variables
„ Power Level (same as corona)
„ Gas chemistries
„ % of gas mix
„ Flow rate
Films and Treatment
† Control Film – 48 g unknown polyester
† Experimental Film Misubishi Hostaphan
2261N (untreated, uncoated, unfilled
PET film)

† Watt Densities chosen for experiment:

„ 5,10,20,30,40,50,60,70,80 and 100
(one electrode)
„ 10,20,40,60,80,100 (two electrodes)
Experimental
† Treatment (Corona) – Compac Universal 2000
manufactured by Enercon, ceramic ground rolls
and ceramic electrodes, gap = 0.13 cm, line
speed = 61 m/min
† Treatment (APT) – 60” Wide Enercon Plasma3
supported by a RF power supply at high
frequency. Gas Mix = 90% argon, 10% oxygen
† “Simulated Extrusion Coating” – prime with
0.03 dry grams/meter2, heat seal to
polyethylene at 163°C for 3 seconds, 6 mm
width, age at least 24 hours
Testing
† Dyne Level was tested using ASTM
method D2578-79
† Dyne Solutions ranging from 28 – 64
were employed
Testing
† Except for the non-treated samples,
all samples (both corona and APT)
were found to have destructive, film
tear (FT), bonding while dry
† Water-soak bond strength was used
to differential samples
† 25mm X 6 mm seal areas were
immersed into 22°C water for one
hour
Bond Strength Unit
† 5 samples of each variable were tested
† The average bond strength and the peak bond
strength were recorded. The average value was
averaged and the peak value was averaged
† Peelable samples failure analysis – primer did not
bond effectively to the PET
† Despite the stringent test, some samples remained
destructive (FT) and the PET tore. The peak value of
these samples is a measure of the strength of the 6
mm wide PET, rather than the bond strength
† Number of FT samples for each variable was recorded
as well.
Dyne Level Results (Control Film)
Plamsa Treatment - Dyne Levels of Control Film 1 and 2 Assemblies

70

60

50

40
Dyne Level

Plasma - Control Film 1 Assembly

Plasma Control film 2 Assembly
30

20

10

0
0 20 40 60 80 100
Watt Density
Dyne Level Results (2261 Film)
Plasma Treatment Dyne Levels 2261 Film 1 and 2 Electrode Assemblies

70

60

50

40
Dyne Level

Plasma Treament - 2261 Film 1 Assembly

Plasma 2261 Film - 2 assembly
30

20

10

0
0 20 40 60 80 100
Watt Density
Maximum Dyne Level
† Maximum dyne level achieve at lower
WD
† Maximum level = 60 (even though
tested for levels as high as 64)
† “Saturation Phenomena” well
documented (ref. 5)
† Do all film with a 60 dyne level
behave the same? BOND TESTING!
 Corona: Control Film - Bond
Strength Data (g/6mm)
Watt # of Avg / avg # of FT Weighted Avg. peak
Density electrodes avg. avg.
0 0 0 0 0
.5 1 179.25 3 254.25 439.5
1 1 221 4 321 398.2
2 1 203.8 1 228.8 379.4
3 1 165 3 240 410.2
4 1 153.8 1 178.8 341.8
5 1 111.2 2 161.2 351.8
6 1 55 55 152.4
8 1 95.5 95.5 185.5
10 1 91.25 91.25 187.5
 Corona: Control Film – Bond
Strength Data (g/6mm)
Watt # of Avg / avg # of Weighted Avg. peak
Density electrodes FT avg. avg.
1 2 225.2 2 275.2 382.6

2 2 343.6 5 468.6 586.2

4 2 67.2 1 92.2 194.4

6 2 131 1 156 263.2

8 2 8.8 8.8 51.2

10 2 69.25 69.25 201.5

 Corona: 2261 Film – Bond Strength
Data (g/6mm)
Watt # of Avg. avg # of FT Weighted Avg peak
Density Electrodes Avg. avg.
0 0
0 0 0
.5 1
206.5 206.5 468
1 1
41.25 41.25 144
2 1 137.2 1 162.2 309.8
6 1
70.8 70.8 136.8
8 1
139.2 139.2 293.4
10 1 192.2 2 242.2 355.4
Corona: 2261 Film – Bond Strength
Data (g/6mm)
Watt # of # of Weighted
Density Electrodes Avg. avg FT Avg. avg. Avg peak
1 2
102.2 3 177.2 422.6
2 2
218 3 293 428.2
4 2
206.2 4 306.2 436.4
6 2
135 135 273.6
8 2
201.6 2 251.6 389.4
10 2
124.8 124.8 281.8
 Corona Treated Films
Watt density vs. weight Avg.
500

450

400

350

300
WD (1) weigthed avg control
g/.5 inch

WD (2) weighted avg control

250
WD (1) weighted avg 2261
WD (2) weighted avg 2261
200

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
WD
 Corona treatment:
Control Film - Watt density vs. weight avg
500

450

400

350

300
g/.5 inch

WD (1) weigthed avg control

250
WD (2) weighted avg control

200

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
WD
 2661 Film - Watt density vs. weight avg

500

450

400

350

300
g/.5 inch

WD (1) weighted avg mit

250
WD (2) weighted avg mit

200

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
WD
Corona Conclusions
† Dyne level testing does not tell the whole
story
† When using a primer, water soak bonds
may help determine over-treatment
† Film selection is biggest variable
† Using multiple electrode assemblies may
produce more consistent results
(confirmation of micro re-treatment
theory?)
APT: Control Film - Bond Strength
Data (g/6mm)
Sample ID Watt # of Avg / avg # of FT Avg. peak
Density electrodes
PA1 0 0 0 0
PB1 5 1 91 274.2
PC1 10 1 181.2 2 403.4
PD1 20 1 7.6 38
PE1 30 1 120.6 1 287
PF1 40 1 36.6 153.8
PG1 50 1 9 48.6
PH1 60 1 21.8 134.6
PI1 70 1 15.2 72
PJ1 80 1 46.6 72.4
PK1 100 1 56.8 155.8
APT: Control Film - Bond Strength
Data (g/6mm)
Sample ID Watt # of Avg / avg # of FT Avg. peak
Density electrodes
PB2 10 2 96.8 1 243.4
PC2 20 2 20.2 93
PD2 40 2 13.4 68
PE2 60 2 27.5 109.5
PF2 80 2 10.4 53
PG2 100 2 10.3 71.6
APT: 2261 Film - Bond Strength
Data (g/6mm)
Sample Watt # of Avg / avg # of FT Avg. peak
ID Density electrodes
PA1 0 0 0 0
PB1 5 1 45.4 171.6
PC1 10 1 23.2 127.4
PD1 20 1 71 285.2
PF1 40 1 4.2 29.4
PH1 60 1 5.5 31.5
PJ1 80 1 4.8 25.4
PK1 100 1 5.6 19.2
APT: 2261 Film - Bond Strength
Data (g/6mm)
Sample ID Watt # of # of
Density electrodes Avg / avg FT Avg. peak
PB2 10 2 110.75 1 356.5
PC2 20 2
61.75 136
PD2 40 2
3.2 12.2
PE2 60 2
5 21.2
PF2 80 2
5.5 18
PG2 100 2
6.6 45.2
 APT - Wt. avg bonds vs. WD

500

450

400

350

300
control 1 assembly
g/inch

control 2 assembly
250
2261 1 assembly
2261 2 assembly
200

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
wd
Comparisons:
† Corona – concluded that 2261 film
and 2 electrode assembly highest
bonds across wides range of watt
density
† APT – much smaller difference
between films and # of assemblies
† APT - control film with 1 assembly
might be slightly better
 Plasms vs. Corona 2261 film

500

450

400

350

300
bond stregth

250 Corona 2 assembly 2261

Plasma 2 assembly 2261
200

150

100

50

0
0 20 40 60 80 100 120
watt density
 Plasam vs. Corona - Control film

500

450

400

350

300
bond strength

Corona control 1 assembly

250
Plasma control 1 assembly

200

150

100

50

0
0 20 40 60 80 100 120
watt density
 Highest bond Values of Corona vs. APT

500

450

400

350
Bond Strength (g/6mm)

300

Corona 2261 2 assembly

250
plasma control film 1 assembly

200

150

100

50

0
0 20 40 60 80 100 120
Watt Density
Discussion
† Dyne leve testing does not indicate
over-treatment
† Using a primer allows for all
conditions to be destructive for dry
bonds
† Water-soak data may differentiate
over-treatment
Discussion
† Corona treatment + primer =
advantage in water soak bond
strengths as compared to APT under
these specific conditions (90% argon,
10% oxygen)
† APT = little differentiation between
films or # of electrode assemblies
(confirmation of better uniformity?)
† Clear point of over treatment
More work needs to be done…
† Although, water-soak bond data is higher
for corona in these experiments, a process
that is less dependent on film selection and
electrode assemblies may be useful to the
converter
† Can the poor water-soak bond strength be
over-come?
† Are other gas chemistries better at water-
soak tests?
PART III: More APT variable
† Use first two studies to narrow processing
conditions
† Look at other APT variables
„ Gas chemistry
„ Gas ratios
„ Air flw

„ STAY TUNED…Part III – Available in November,

e-mail contact information to author!
Acknowledgement
† Thank you

„ Rory Wolf and Dave Mandel, Enercon

Industries

„ Jeff Toke, Mitsubishi Films

 Thank You
PRESENTED BY

Jessica Bodine
Mica Corporation
9 Mountain View Drive
Shelton, CT 06484
(203) 922-8888
Jbodine@mica-corp.com