From Miscibility to Nano or Macroseparation in Thermoset ...20Poster/Maider%… · From Miscibility...
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1 1st NanoSpain Workshop 10-12 March, 2004 From Miscibility to Nano or Macroseparation in Thermoset of Epoxy Resin and PEO-PPO-PEO Block Copolymers M. Larrañaga, N. Gabilondo, E. Serrano, M.D. Martin, G. Kortaberria, I. Mondragon “Materials + Technologies” Group Dpto. Ingeniería Química y Medio Ambiente Universidad País Vasco/Euskal Herriko Unibertsitatea Escuela Universitaria Politécnica Donostia/San Sebastián
Transcript of From Miscibility to Nano or Macroseparation in Thermoset ...20Poster/Maider%… · From Miscibility...
11st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or Macroseparation in Thermoset of Epoxy Resin and PEO-PPO-PEO
Block Copolymers
M. Larrañaga, N. Gabilondo, E. Serrano, M.D. Martin, G. Kortaberria,
I. Mondragon
“Materials + Technologies” GroupDpto. Ingeniería Química y Medio Ambiente
Universidad País Vasco/Euskal Herriko UnibertsitateaEscuela Universitaria Politécnica
Donostia/San Sebastián
21st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
Introduction
• Block copolymers/Thermoset ⇒ Generation of Nano or macrostructures
Blocks of copolymersContent of CopolymerCure Conditions
• Techniques
DSC, Study of Tg-s (initial miscibility)AFM and OM, Morphological Study DMA, Mechanical Dynamic Behaviour
31st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
Experimental
DGEBA Tg= -19 ºC n=0.03
DDM
Tg= -72 ºC Mw=3400 0.33:1 ⇒ EP1PEO-PPO-PEO Tg= -71 ºC Mw=2900 0.8:1 ⇒ EP2
Tg= -70 ºC Mw=13300 3:1 ⇒ EP3
PPO Tg= -73 ºC Mw=2000
PEO Tg= -40/-60 ºC Mw=8000
Cure cicles
DGEBA/DDM/MODIFICADORT= 80 ºC 6 h, T= 190 ºC 2 h T= 140 º C 3 h, T= 190 ºC 2 h
CCH3
CH3
OO CH2 CH
OH
CH2CH2CHCH2 CCH3
CH3
OO CH2 CH CH2
O O
n
CH2NH2 NH2
CH2 CH2 O CH2 CH
CH3
HO O CH2 CH2 O Hn m n
CH2HO CH
CH3
O Hn
CH2HO CH2 O Hn
41st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
Initial Conditions:
Mixtures are initially miscible ⇒ only one Tg , intermediate between both components(DGEBA/DDM/Modifier)
-80 -60 -40 -20 0
Hea
t Flo
w (m
W/g
)
T (ºC)
DGEBA/DDM 0min
DGEBA/DDM/ EP1 20 % 0min
DGEBA/DDM/PPO 20 % 0min
DGEBA
EP1
PPO
EP2
DGEBA/DDM/ EP2 20 % 0min
DGEBA/DDM/ EP3 20 % 0min
EP3
51st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
MorphologiesT= 80 ºC, 190 ºC
DGEBA/DDM/PPO 20 %
PPO Mw= 2000 macroseparated at all contents and curing temperatures ⇒
1127 µm x 1407 µm 287 µm x 230 µm
DGEBA/DDM/PEO 20 %
PEO Mw= 8000 miscible at all contents and curing temperatures
61st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
Mechanical Dynamical Behaviour DGEBA/DDM/PPO DGEBA/DDM/PEO
Tg similar to matrix Tg decrease with PEO content Macroseparated at all PPO contents and temperatures Miscible at all PEO contents and temperatures
50 100 150 200 250106
107
108
109
T (ºC)
E'
Matrix
10 %
20 %
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
50 100 150 200 250106
107
108
109
T (ºC)
E'
Matrix
10 %20 %
30 %
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
50 100 150 200 250106
107
108
109
T (ºC)
E'
20 %
10 %
Matrix
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
50 100 150 200 250106
107
108
109
T(ºC)
E'
30%
20%
10%
Matrix
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
T= 80 ºC, 190 ºC
T= 140 ºC, 190 ºC
Curing Conditions
71st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
MorphologiesDGEBA/DDM/PEO-PPO-PEO 90:10
T= 80 ºC, 190 ºC T= 140 ºC, 190 ºC
Self-assembling at both temperatures ⇒ high level of PEO (block compatible with the crosslinking resin)
Macrostructures at both temperatures ⇒ high level of PPO (block incompatible with the crosslinking resin)
EP3
EP1
81st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of Epoxy Resin and PEO-PPO-PEO Block Copolymers
Mechanical Dynamical BehaviourDGEBA/DDM/PEO-PPO-PEO 90:10
T= 80 ºC, 190 ºC T= 140 ºC, 190 ºC
System modified with EP1 ⇒ high Tg at both temperatures, Macroseparation
System modified with EP3 ⇒ intermediate Tg at both temperature, NanoseparationPhase behaviour mainly controlled by miscible block content more than by molecular weight
50 100 150 200 250106
107
108
109
T (ºC)
E'
PEOEP3
EP1
PPO
Matrix
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
50 100 150 200 250106
107
108
109
T (ºC)
E'
PEOEP3
Matrix
EP1
PPO
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tanδ
91st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
MorphologiesDGEBA/DDM/PEO-PPO-PEO 70:30
T= 80 ºC, 190 ºC T= 140 ºC, 190 ºC
Nanostructures at high EP3 content ⇒ increase micelles content
1127 µm x 1407 µm
Macrostructures at high EP1 content ⇒ co-continuous and inverted structures
EP3
EP1
101st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermost of EpoxyResin and PEO-PPO-PEO Block Copolymers
Mechanical Dynamical BehaviourDGEBA/DDM/PEO-PPO-PEO 70:30
T= 80 ºC, 190 ºC T= 140 ºC, 190 ºC
System modified with EP2 dependent on curing temperature ⇒ T↑ , high Tg , MacroseparationT↓ , intermediate Tg, Nanoseparation
Macroseparation with EP1 and Nanoseparation with EP3 at all curing conditions and for both copolymercontents
50 100 150 200 250106
107
108
109
T (ºC)
E'
PEOEP3
EP2
EP1
Matrix
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
50 100 150 200 250106
107
108
109
T (ºC)
E'
PEO
EP3
EP2
Matrix
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
tan δ
111st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermoset of EpoxyResin and PEO-PPO-PEO Block Copolymers
Conclusions
Nanostructures or Macrostructures are obtained depending on miscible block content.
Molecular weight does not determine final morphologies.
Mixtures are initially miscible. Nanoseparation or Macroseparation take place during reaction.
Different structures, nano or macrostructures, may be obtained depending on the curing temperature.
By increasing the copolymer content the amount of micelles may be increased.
121st NanoSpain Workshop 10-12 March, 2004
From Miscibility to Nano or macroseparartion in Thermost of EpoxyResin and PEO-PPO-PEO Block Copolymers
Referencies:
* M.A. Hillmyer, P.M. Lipic, A. Hajduk, K. Almdal, F.B. Bates, J. Amp. Chem. Soc., 119,2749 (1997).* S. Ritzenthaler, F. Court, E. Girard-Reydet, L. Leibler, J.P. Pascault, Macromolecules, 36, 118 (2003).* S. Ritzenthaler, F. Court, L. David, E. Girard-Reydet, L. Leibler, J.P. Pascault, Macromolecules, 35, 6245 (2002).* Q. Guo, R. Thomann, W. Gronski, T. Thurn-Albrecht, Macromolecules, 35, 3133 (2002).* R.B. Grubbs, J.M. Dean, M.E. Broz, F.B. Bates, Macromolecules,33, 9522 (2000).* J. Mijovic, M. Shen, J.W. Sy, y I. Mondragon, Macromolecules, 33, 5235 (2000).* J.M. Dean, P.M. Lipic, R.B. Grubbs, R.F. Cook, y F.S. Bates, Journal of Polymer Science: Part B: Polymer Physics, 39, 2996 (2001).* S. Zheng, N. Zhang, X. Luo, y D. Ma, Polymer, 36, 3609 (1995) .* Q. Guo, C. Harrats, G. Groeninckx, M.H.J. Koch, Polymer, 42, 4127 (2001).
Acknowledgment:
The authors wish to express their gratitude to the Ministerio de Ciencia y Tecnologia for funding this work (MAT2000-0293 y MAT2001-0714) and also to the Diputación de Gipuzkoafor its financial support.
