This paper describes objective technical results and analysis.

Any subjective views or opinions that might be expressed

in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Polymer Network Formation in Epoxy/Acrylate SAND2020-2596C

Dual-Cure Thermoset Resins for Direct Ink Write

Additive Manufacturing
0.20 iwomarawdin--

\go **iir
0.15

0.10

0.05

Temperature Ramp 0.00

e Temperature Ramp - 3

cc 0 -0.05
50 100 150 200 250 300
SW •1000 WO• 70.0••••
Temperature (°C)

PRESENTED BY

Leah Appelhans, Sandia National Laboratories

- .
• ••• ..•••• = -me

,
111/IP
. m

Adam Cook, Jessica Kopatz, Jackie Unangst, Derek Reinholtz •••-••41•

_
- --.•
•'' ... • •,

APS March Meeting, Denver 2020

1.111Miffr
Sandia Nationat Laboratories is a multirnission Laboratory
managed and operated by NationaL Technology Et Engineering
Solutions of Sandia, LLC, a whotty owned subsidiary of HoneyweLL
internationat inc., for the U.S. Departrnent of Energys National
Nuclear Security Administration under contract DE-NA0003525.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned
subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
 21 Interpenetrating Polymer Networks (IPNs)
How do different resin components change IPN formation, printability, mechanical
properties, and cure kinetics?

Phase separation and domain sizes depend on:

AG mix = AH mix - TASmix

109 0.20
cure order

109
cure kinetics

0.3 109
IPN

0.5
1
0
(Pa)

- 0.15

( )uet (etiap)uei
- 0.2

Storage modulus ::::

0-
Storage modulus

108 0.10
108 108 -

0.2
a)
- 0.1
0.05 0
co 01

■
107 0.00 10 7 0.0 10 7 00
0 50 100 150 200 250 300 0 50 100 150 200 250 300 0 50 100 150 200 250 300

Temperature (°C) Temperature (°C) Temperature (°C)

Phase-separated systems exhibit Tg broadness correlates to distribution

Homogeneous* IPNs exhibit single Tg
multiple Tgs of compositions in interphases
 31 UV-Thermal Dual Cure Resin Formulation
UV-thermal Epoxy/acrylate Formulation <
fumed silica
0 ° (rheology modifier)
01
dimethacrylate radical photoinitiator
(2,2-dimethoxy-1,2-diphenylethanone)
c) <
o
l o

triepoxy \,
,N

NC—N—CN
oV

epoxy latent cure initiator

diepoxy 1-ethyl-3-methylimidazolium dicyanamide

Sequential IPN's

UV cure thermal cure

4%Aft,1
),% ePoIcY hv A

ivy acrylate

uncured resin mixture acrylate network forms epoxy network forms

 4 UV-Thermal Dual Cure: Acrylate Network Formation
Characterizing UV-cure kinetics by UV-Differential Scanning Calorimetry (UV-DSC): Different wt% diacrylate
Pulsed UV-DSC: 2.4s pulses followed by 5 min. equilibration Continuous UV-DSC: 10 min UV exposure followed by 5 min.
109mW/cm2(10% UV-DSC intensity) equilibration and 10 min background
170
Enthalpy with varying NM% Dimethacrylate 160 -
150 -
140 -
130 -
720-

-8-50 wt% 110 -

E 101)-
90 7
acquisition
3
-8-30 wt% 80 7
70 7
4-•
MI 60 7
-8-15 wt% -
0 50 7
40 7

-8-10 wt% 30 7
20 7
background
10 7
5 wt% 0 —
-10
2 3 4 5 6 7 8 9 10 11 12 14 15 17 18 19 21 22 24 25 26 28
time (min)
10
Pulsed Continuous
wt% dimethacrylat z kJ/mol kJ/mol
methacr late FG methacr late FG
0 2 4 6 8
Pulse # 50 36 53(4)
6

4
2.05rnin
Background is taken when peak integrations are 30 47 45(3)
constantfor successive pulses. 15 50 44(1)
2

7.08rnin 12.13min 17 17min

22.22rren
10 49 54(1)
2.0Orriin 7.04min 12.09min 17.13min 22 17min
50.50J/g 7.069J/g 3.007J/g 1 995J/g 825J/g

Exo UP
10 15
Time(min)
20 25 3
Unh
AEI poly (methacryiate)= -56 kJ/mol
 5 I Dual-cure Components: Acrylate Network
Storage modulus Cure Only (Print Only
measurements by
torsional DMA at 30°C Acrylate network
Resin Formulation Storage Modulus(MPa)
controls the green
Longitudinal Transverse Print Direction L T
strength
15 wt% dimethacrylate 4(1) 9(1) 1
30 wt% dimethacrylate 30(1) 24(7) No consistent L vs T
differences in modulus
50 wt% dimethacrylate 184(25) 199(6)

Modulus increases after I

UV Cure Only (Print + UV Flood
oscillates flood cure.
Resin Formulation Storage Modulus(MPa)
UV-cure profile
In situ UV during printing Print Direction L T Dimethacrylate
(varying exposure time
15 wt% dimethacrylate 6(1) 9(4) conversion incomplete
6.9 mW/cm2) after UV cure.
30 wt% dimethacrylate 41(5) 31(6)
30-minute flood cure
50 wt% dimethacrylate 240(12) 281(20)
(5.7 mW/cm2)
6 I Acrylate Network and UV Power Determine Printability

15 wt% dimethacrylate at 5% UVP

(7 W/cm2)

15 wt% dimethacrylate at 25% UVP 10 wt% dimethacrylate at 85% UVP

(35 W/cm2) (115 W/cm2)
 10' _ 0.2C
.
:.. .. ......
!MID!::::
- 0.17

7 Thermal Cure and IPN Formation varying wt% - 0.14

Temperature Ramp - 2
acrylate resin e Temperature Ramp - 3
- 0.11
Resin composition and cure profile determine post-thermal cure 1 108

properties. 5 wt% £ - 0.0£

- 0.0.£

0.02
In 50wt% acrylate systems there is distinct phase separation.
10 0.0C
25.0 62.5 100.0 137.5 175.0 212.5 250.0

108 Te erature °C 0.20

UV cure
wt% Tg ramp Tg ramp 0.15

in situ cure Temperature Ramp Up

dimethacrylate up (°C) down (°C) 30 wt% E'Temperature Ramp Down

0-
CD

30 min flood 0.10

5 213 197 Thermal Cure

0.05

100°C/4hrs 107 0.00

30 195 183 150°C/2hrs 25.0 62.5 100.0 137.5

Temperature
175.0

(°C)
212.5 250.0

109 0.20

94 115 0.15

50
190 183 0.10

50 wt% 10

Temperature Ramp 0.05

Temperature Ramp - 3
_...aguaB440-2 -
0.00

Resin composition: varying diacrylate, remainder 1:1 diepoxy:triepoxy

107 , 0.05
25.0 62.5 100.0 137.5 175.0 212.5 250.0
Temperature (°C)
 8 Dual-cure Components: Varying wt% Acrylate Resins
1 09 0 20
Phase separation depends on thermodynamic miscibility
and cure kinetics. 0 15
50wt% acry.
50wt% acrylate: Epoxy gelation is slow due to inhibition 0.10
74 UV cure
108 -
by the acrylate network. Allows time for phase separation. 100°C/4hrs
Temperature Ramp - 0 05
e Temperature Ramp - 3 150°C/2hrs I
0 00

10 7 0.05
25.0 62.5 100.0 137.5 175.0 212.5 250.0

Lower wt% acrylate: Epoxy gelation is faster and phase Temperature (°C)

separation is reduced. 109 0.20

SA:44:4441.1:2'.44: `
`44,42:244.4.44."4444

- 0.15 30wt% acry.

— Temperature Ramp Up §I UV cure
a
Temperature Ramp Down
- 0.10 E 100°C/4hrs
5 150°C/2hrs
Weight %Itartomer
- 0.05
Onset Time of
821 910 2106
Gelation (s)
107 0 00
25.0 62.5 100.0 137.5 175.0 212.5 250.0
Temperature (°C)
 9 Dual-cure Components: 50wt% Acrylate Resin
109 0.20

Phase separation and stability depends on

thermodynamic miscibility and cure kinetics. - 0.15

Storage modulus t (Pa)

e- Time - 1
Temperature Ramp - 2 I UV cure
Minix = Al-Imix — TASmix 108 - e Temperature Ramp - 3 - 0.10
100°C/4hrs
200°C/2hrs
At low curing temperatures (TASmix)smaller than 0.05

unfavorable AH mix
107 0.00
At higher cure temperature (-TASmix)contribution 25.0 62.5 100.0 137.5 175.0 212.5 250.0

overcomes unfavorable ¿Hmix Temperature (°C)

109 0.25

0.20
Kinetics at higher curing temperature are faster, trap
system before phase separation. e Time - 1

Storage modulus 1-.

- 0.15
Temperature Ramp - 2
108 - e Temperature Ramp - 3 UV cure
200°C/2hrs
Additional cure increases acrylate network Tg and phase
separation cannot be detected by Tg.
107 0.00
25.0 62.5 100.0 137.5 175.0 212.5 250.0
Temperature (°C)
10 Post-cure: additional network conversion
DSC shows significant additional cure after 150°C cure, no additional cure after 200°C cure or post-cure.
0.0 0.6
AMT 1-41 1_UV+150C_RT300: AMT 1-38-1 200 2hr post cure.001
AMT 1 38 1_UV+150C_RT300, AMT 1-35-1 200 2hr post cure.001
AMT 1 35 1_UV+150C_RT300,
AMT 1 37 1_UV+150C_RT300,
DSC AMT 1-45-1 15 wt% Sarto
AMT 1-44-1 1 Owt%S 150C Cun 0.4 -
-0.2

0.2 -

Heat Flow (W/g)

-a -0.4

0.0 -
E
-0.6

-0.2 -

-0.8
-0.4-

-0.6
-1.0
0 50 100 150 200 250 300
0 dO lOo ido 200 250 300
Exo Up Temperature(°C) Universal V4.5A TA in;
Exo Up Temperature (°C)

5Owt% acrylate:

FTIR-ATR also shows an cure Tmax (C C)/(C 0)

increase in % acrylate reacted 150°C 0.85*
after thermal post-cures. 200°C 0.95*
250°C 0.98*
 11 IPN Network Formation: 50wt% Acrylate Formulations
109 0 300

Post-cure can result in a single Tg but post-cure

temperature must significantly exceed Tg. - 0 225

Temperature Ramp Up 100°C/4hrs

= Temperature Ramp Down
108 -
. ......;;!'
0.150
150°C/2hrs
200°C/2hrs
200°C/2hr post-cure - 0 075

Two Tgs 10 7 , . 0.000

i .
25.0 62.5 100.0 137.5 175.0 212.5 250.0

1
Temperature (°C)

109 0.3

250°C/2hr post-cure - 0.2

-6- Temperature Ramp - 2
e Temperature Ramp - 3
100°C/4hrs
108
TSingle broad Tg 150°C/2hrs
_01 250°C/2hrs

10 0.0
25.0 62.5 100.0 137.5 175.0 212.5 250.0
Temperature (°C)
 12 IPN Network Formation: 50wt% Acrylate Formulations 109 0.25

hermal Post 100C 4h 100C 4h

+150C 6h + 200C 2h + 250C 2h 200C 2h - 0.20
rofi 150C 2h 200C 2
94 119 127 Time - 1
Tg Transition (°C) 180 196 192 - 0.15
190 183 182 7v Temperature Ramp - 2
108 - Temperature Ramp - 3
Storage Mod
802 767 777 777 712 859 - 0.10
(MPa)

- 0.05

109 0.20 I..

" '
.!4
' 1 .8 .... .::0;r°111'.
.1.tt:IttattitA
107 0.00
25.0 62.5 100.0 137.5 175.0 212.5 250.0
- 0.15
Temperature (°C)

- 0.10

108 - 109 0.3

109 0.300
Temperature Ramp - 2 - 0.05
9 Temperature Ramp - 3
........................

0.00 - 0.225

-& Temperature Ramp - Temperature Ramp - 2

e Temperature Ramp - 3 e Temperature Ramp - 3
107 0.05 108 -
•
108 - - 0.150
25.0 62.5 100.0 137.5 175.0 212.5 250.0

Temperature (°C)

- 0.075
n
,17reitr..
107 0.0
107 • 0.000 25.0 62.5 100.0 137.5 175.0 212.5 250.0
25.0 62.5 100.0 137.5 175.0 212.5 250.0
Temperature (°C)
Tctrtnnetrmti inn fors\
13 Summary

For diepoxy/triepoxy/dimethacrylate dual-cure resins developed for DIW thermoset printing:

For UV cure of the acrylate component the UV exposure profile has a significant impact on
conversion.
Acrylate network formation kinetics and green strength are key to printability.
In tricomponent diepoxy/triepoxy/dimethacrylate resin systems there is complex IPN phase
behavior dependent on both thermodynamic miscibility and cure kinetics.

Understanding resin structure-function relationships and reaction and cure kinetics is

required to tune final properties and printability.
In-depth knowledge of UV cure kinetics is necessary to enable print-process scale-up and
successful translation to more complex geometries.
The effects of thermal cure and subsequent thermal exposures on microstructure formation
and evolution are key to understanding environmental performance limits, property
stability, and aging.
14 Acknowledgements

Jess Kopatz, PhD candidate (Penn State) Jackie Unangst, post doc

Also thanks to:

Adam Cook, Derek Reinholtz

Kylie Manning (now at Dow), Mat Celina

Brad Jones, Erica Redline, Nick Wyatt

Lindsey Hughes, Patti Sawyer, Mark Stavig

$$$ NNSA NA-115 Additive Manufacturing Development Program

15

Questions?
16 Supplementary Slides
17 Approaches to DIW Printing of Thermoset Resins

1) In situ cure — full or partial cure during printing

Single mechanism cure (e.g. UV curable)

Dual-cure (UV/thermal, UV/UV,
thermal/thermal)
Printed shape maintained by 'green strength' of
partially cured resin

100000

10000
2) Increase zero-shear viscosity

Viscosity (Pa*s)
1000
Moderate-to-high filler loadings
B-staging 100

• Shear thinning 10
—N—Unfunctionalized Si02
—N—Hexyltdmethoxysilylated Si02

O High zero-shear viscosity maintains printed —N—Epoxy Silylated Si02

shape 0.01 0.1 1 10 100

Shear rate (1/s)
18 Why AM Printing of Thermosets?

May offer specific AM advantages relative to thermoplastics

lnterlayer adhesion/homogeneity
Key for mechanical and dielectric properties

Pm EHT = 10.00 kV WD = 24.5 mm Signal A = SE2 Width = 4.764 mm

1'4"ni EHT = 10.00 kV WD = 10.2 mm Signal A = SE2 Width = 2.761 mm

SEM of cross section of DIW printed thermoset resin SEM of cross section of FFF printed Nylon
19 Sandia's Approach
Development of thermoset resins for DIW

Develop dual-cure systems to target specific materials

requirements.
Epoxy/acrylate (UV/thermal)
Other dual-cure mechanisms and polymer systems

Characterize resin component contribution to physical

properties and cure kinetics to enable design of tunable resin
systems. -
-40
Characterize DIW-uniquefactors that impact network
formation, extent of cure, and final properties.

Characterize thermoset stability and aging characteristics.

>10:1 w:h

Develop printability metrics and optimize print techniques for

thermoset systems.
20 Sandia's UV-assisted Direct-Ink Write Capability

Adam Cook/Derek Reinholtz

• LED spot-curing system, 365 nm, max

power 40 W/cm2

• Controllable UV intensity (0-100%)

• Print nozzle diameter from 0.15-1.55 mm

• Table speed 0.01 mm/s to —60mm/s

• Print volume 300x300x200 mm

 21 Dual-cure Components: 50wt% Acrylate Resin
Resin composition: 50wt% diacrylate, 23wt% diepoxy, 19wt% triepoxy
100/150 °C
UV-cured only samples cycled to 250°C show only one Tg on ramp down. thermal-cure profile

100/150°C UV+thermal cured samples have two Tgs, which evolve but do 100 °C for 4 hours
not coalesce with short duration temperature cycle. 150 °C for 2 hours

109
UV-cured only sample 0.3 109
UV 100/150°C cured sam•le 0.20
IA
'-
::::: :
111111411.-
Ternperature RamP U
Temperature Ramp Down 0.15

)uel (ellep)uei
(_ )uel (euep)uei
108 - 0.2
0.10
Storage modulus

108

(
0.05
10 7 - 0.1

*
AI
Temperature Ramp Up 0.00
::::::::::::::::: A:;';
-EF Temperature Ramp Down
[112 !!!!!!!!! !!! !

106 0.0 107 0.05

0 50 100 150 200 250 300 0 50 100 150 200 250 300
Temperature (°C) Temperature (°C)
 22 Dual-cure Components: 50wt% Acrylate Resin
Thermal-cure profile
For cycling to 250°C for short dwell times no further evolution of Tg is
100 °C for 4 hours
observed.
150 °C for 2 hours
Resin composition: 50wt% diacrylate, 23wt% diepoxy, 19wt% triepoxy

UV-cured only sample: UV+100/150°C thermal cure sample:

VT to 250 °C cycles 2 and 3 VT to 250 °C cycles 2 and 3
109 10° 109 10°

co
o_

(,_, )uel (eliep)uei

( )1-lel (ellep)uei
10-1

-4:
Storage modulus

Storage modulus
108 - 108 -

10-2

107
107 I I I 10-3
0 50 100 150 200 250
0 50 100 150 200 250 300
Temperature (°C)
Temperature (°C)
 23 Dual-cure Components: 50wt% Acrylate Resin
The dynamic evolution of the epoxy/acrylate interpenetrating polymer
network is observed during thermal cure.

Longer post-cure does lead to Tg/microstructure evolution, depending on Tmax of post-cure.

Microphase-separated 100/150°C system Microphase-separated 100/150°C sample

stable with 200°C/2hr post cure homogenizes with 250°C/2hr post cure
109 0.20 109 0.3

173°C
180°C

cTs
o_
- 0.15 cTs
o_

1
L )uel (euep)uei
Temperature Ramp Up

Storage modulus
Storage modulus

0 Temperature Ramp Down

108 - - 0.10 108

- 0.05
Temperature Ramp Up
1111:4118,7-
Temperature Ramp Down
//420010.2:AWAI:No
107 0.00 107 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300

Temperature (°C) Temperature (°C)

 109 0.14

- 0.1

24 Dual-cure Components: Acrylate Resin varying wt%

0.1
acrylate resin'
- 0.08
-g

(_ )uel (eIla
Storage modulus measured at RT before thermal cycling on 5 wt% 0.06

samples printed in a transverse geometry. g,

0.04
(7,
0.02

Tg measured by VT DMA to 250°C. 108 0.00

25.0 62.5 100.0 137.5 175.0 212.5 250.0
No significant differences between transverse and longitudinal Tg. 109 0.2

0.1

)uel (ellap)uei
Temperature Ramp Up

30 wt% -1Er Temperature Ramp Down 0.1

T
wt% Storage Tg up Tg down
dimethacrylate Modulus (MPa) (°C) (°C) 0.0

10' 0.0
25.0 62.5 100.0 137.5 175.0 212.5 250.0
5 wt% 870 (40) 213 197
0.20

co - 0.15
30 wt% 779 (173) 195 183
- 0.10

50 wt%
oscillates 94 115 - 0.05
50 wt% 700 (20)
190 183
- 0.00

Resin composition: varying diacrylate, remainder 1:1 diepoxy:triepoxy 150 200 250 300
0.05

Temperature (°C)
 25 Dual-cure Components: Triepoxy Resin
varying wt% triepoxy resin
-30wt% acrylate, 63wt% epoxy (di/tri). 109 05 10 10°

0 wt% 20 wt%
The triepoxy component moderately increases - 0.4

(Pa)
the Tg but has no significant effect on the - 10-1
Temperature Ramp-2 - 0.3
storage modulus of the 150°C cured samples.

Storage modulus
108 - e Temperature Ramp --3 108 -

Triepoxy
Tg Up Tg Down Storage Modulus
1 107 -
0
- 0.2

- 0.1

300
0.0 107
0 50
Temperature Ramp
s Temperature Ramp

100 150 200 250 300

1 0-3

(°C) (°C) (MPa) Temperature (°C) Temperature (°C)

0 wt% 159 156 776 (156)

109 0.2C10o 0.20
30 wt% 40 wt%
20 wt% 191 177* 771 (125) - 0.15 - 0.15
F

)uel (ellaP)uei
(Pa)
Temperature Ramp -
Temperature Ramp - 1 s Temperature Ramp
30 wt% 195 184 836 (116) 108 -
s Temperature Ramp - 2
- 0.1C108 - 0.10

Storage modulus
40 wt% 199 192 643 (113) - 0.05 - 0.05

107 0.0C107 0.00

25.0 62.5 100.0 137.5 175.0 212.5 250.0 25.0 62.5 100.0 137.5 175.0 212.5 250.0
Tg measured by torsional VT DMA to 250°C. Temperature (°C) Temperature (°C)
Storage modulus at room temperature.
*additional peaks in loss modulus plot due to sample slipping
20 wt% Tactix comparison of VT 1st cycle from 2 the different batches with UV sample

20 wt% Tactix samples VT

0.25

AMT 1-33-1 VT Ramp Up

AMT 1-33-1 VT Ramp Down - 0.20
AMT 1-39-1 VT Ramp Up
AMT 1-39-1 VT Ramp Down
AMT 1-33-1 UV VT Ramp D

"•••••••0

- 0.05

0.00
25.0 62.5 100.0 137.5 175.0 212.5 250.0

Temperature (°C)
27 Sandia's UV-Thermal Dual Cure: Rheology

— 0% Tadix; 0.6.1
096 Tactix; 2.4:1
Rheology of resins is not 10000 - — 0% Tach: 1:1
..zo- — 5viA% Tack:2.75:1
highly sensitive to k.ft,
0_ — lOvirt% Tadix: 3.3:1
monomer compositions. -,. 1000 7 —30virt% T Kik: 2:1
a EPON 828
8
100
Allows broad variation of _
resin compositions while i
10
maintaining printability. ,
.t-
1
0.001 0.01 01 1 10 100 1000
Shear Rate Ws)
 /EXPORT CONTROLLED INFORMATION

28 Supplementary: UV Exposure and Dose for Different Sources

Measured
Wavelength power % Intensity
Device
& Dose
10 &20
Measured
365nm 1.2 6.9 14.3 29.0 57.3 106.3 intensity
Dual UV source
(mW/cm2)
(printer)
Dose (190s) 228 1,311 2,717 5,510 10,88720,197

365nm 5.7
Post-print UV
cure Dose
10,260
(1800s)
365nm - 45 109 207 327 413
Dose
Photo-DSC 539 1313 2,486 3,918 4,958
(12s)
Dose
- 108 263 497 784 992
(2.4s)
Dosage: Intensity*time of exposure

Dual UV source: continuous coverage for 190s

Post-print UV: continuous coverage for 1800s(30 min)
Photo-DSC: 5 x 2.4s flashes
29 UV-Thermal Dual Cure
Characterizing UV-cure kinetics by UV-DSC
Photo-DSC @365nm 80%
Measured intensity 5 pulses at 10% power
45 109 207 327 413
(mW/cm2) in UV-DSC matches
Dose calculated dose for
539 1313 2,486 3,918 4,958
(5 pulses, 12s)
printing at 5% power
Dose
108 263 497 784 992
(1 pulse, 2.4s)

UV-DSC of 2:1 epoxy:acrylate

formulation at different
irradiation powers
-0-5% POWer

-0-110% Power

-a-2M Power

40% Power

-0-80% POWeir

0 2
30 Baseline problem in continuous exposures with low acrylate %?
Expt ID = AMT1-43-1 50wt% long Mean Expt ID = AMT1-44-1 lOwt% long

170 34-
160 32-
150 30 -
140 28-
130 26 -

heat flow (mW)

120 24-
110 22-

E 100 20 -
90 18-

o 80 16 -
..F 70 14 -
++
to 60 12 -
co
-c 50 10 -
8-
40
6-
30
4-
20
2-
10
0 o
10 r 1 1
2 3 4 5 6 7 8 9 10 11 12 14 15 17 18 19 21 22 24 25 26 28 -4l -2 0l 2 al 6 8 10 12 14 16 18 20 22 24 26 28 30
time (min) time (min)

1 .
.11/1 111
150 - 15 -
140 - 14-
13 -
130 -
12-
120 -
11 -

heat flow (mW)

110 -
10 -
100- 9-
E 90- 8-
80- 7-
0 70 _ 6-
5-
4-

40- 2-
30-
20-
10-
o -1441rtii t i tiiiii t I
10 1 . 1 . 1 1 .
-5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
time (min) time (min)