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Transición vítrea
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Diapositiva 2
melt
undercooled liquid
glass
crystal
Tg Tm
temperature
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Diapositiva 3
veq(T0)
v(Tb,0)
La transición vítrea es
una consecuencia de la
veq(Tb)
existencia del proceso de
relajación estructural.
veq(T0)
v(Tc,0)
veq(Tc)
t0 t time
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Diapositiva 4
φ
χ ( T , t ) − χ eq ( T )
1 φ =
χ ( T , 0 ) − χ eq ( T )
χ puede ser volumen, entalpía etc.
0
time
Distribución de tiempos de
relajación
Modelo de un
Discreta
único tiempo de
relajación ⎛ t ⎞
dφ φ φ (t ) = ∑ g (τ i ) exp ⎜⎜ − ⎟⎟
= − ⎝ τi ⎠
dt t
Continua
⎛ t ⎞
φ ( t ) = exp ⎜ − ⎟ ⎛ t ⎞
τ ⎠
⎝ φ (t ) = ∫ g (τ ) exp ⎜⎝ − τ ⎟dτ
⎠
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Diapositiva 5
veq(T+∆T) veq(T1)
1
1
veq(T) veq(T)
2 2
veq(T-∆T)
log (time) log (time)
volume
volume
1 1
2 2
T-∆T T T+∆T T2 T T1
temperature temperature
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Diapositiva 6
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Diapositiva 7
⎛ B ⎞ D
τ = A' exp⎜⎜ ⎟⎟ τ eq
= A exp
⎝ TS c ⎠ T − T2
1/T2
∆ µ s c* Ecuación de Vogel
log τeq
B =
k
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Diapositiva 8
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Diapositiva 9
8.- Ejemplos
Plastificación
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Diapositiva 10
8.- Ejemplos
R’
COOR’’
CH3
COOCH3
H
COOCH3
CH3
Polimetacrilato de hidroxietilo PHEMA ( CH2 C )n
COOCH2CH2 OH
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Diapositiva 11
8.- Ejemplos
0,100
1,E+09
ε"
0,010
Ensayos DMA
E''
1,E+08
0,001
0 50 100 150 200
Temperature(ºC)
1,E+07
25 75 125 175 ε’’
tem peratura (ºC) 6
4
log(f)
2
Entrecruzada con 0.1%EGDMA E’’
0
10% EGDMA
-2
2.2 2.4 2.6 2.8
1000/T
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Diapositiva 12
8.- Ejemplos
CH3
(CH3 )3 Si O Si O-Si(CH3 )3
n CH3
C 2 H5
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Diapositiva 13
2.4
2
Tg enthalpic Tg midpoint 1J/gK
1.8
1.6
Tg onset
1.4
-10 0 10 20 30 40
Temperature (ºC)
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Diapositiva 14
1.9
temperature
.
log τ ≈2
Q/mT
log τ
. 1.7
1/Tg
1.5
1.3
1/T
Termogramas DSC medidos en una muestra de
1.1
PS después de enfriar desde equilibrio a
345 350 355 360 365 370 diferentes velocidades 0.5ºC/min (
), 2ºC/min (♦),
T (K) 3 (∆), 5 (x), 10ºC/min (*), 20ºC/min (•), 40ºC/min (+)
C.T. Moynihan, A.J. Easteal, M.A. DeBolt and J Tucker, J. Amer. Ceram. Soc. 59 (1976) 12.
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Diapositiva 15
4
PS600000
3
PS200000
2 PS50000
ln(q / K/min )
-1
PS20000
1
-1
-2
150
-3
2.65 2.7 2.75140
-1
1000/T f (K )
h*/R
130
120
110
10000 100000 1000000
Pm PS
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Diapositiva 16
cp - cp ref
cp
enthalpy
Ta
cp - cp ref
cp
enthalpy
Ta
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Diapositiva 17
2 (J/gK) a) 2 (J/gK) b)
6 6
Q/mT
3 3
. 75ºC, 1440min . 60ºC, 180min
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Diapositiva 18
2.2 1.2
2
1J/gK
1
1.8
30ºC
1.6
0.8 20ºC
1.4
Cp-Cpref J/gK
-10 0 10 20 30 40 17ºC
Temperature (ºC) 0.6
13ºC
3 1
10ºC
0.4
0.8 0ºC
(C p -C p r ef) m ax (J/g K)
2 -10ºC
0.2
∆ h a (J/g)
0.6
-20ºC
0.4
1 0 -30ºC
-40ºC
0.2
-0.2
0 0
-50 0 50 100
-50 0 50
Temperatura (ºC)
Ta (ºC)
Entalpía perdida
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Diapositiva 19
IPNs secuenciales
First network
Swollen network
Miscible IPN
Phase separated IPN
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Diapositiva 20
2 (J/gK) 2 (J/gK)
29 24
28 23.5
IPNs PMA-i-PS
27 PMA01 23
ipn01
26
22.5 0.1% EGDMA
25 PS01
. 22
Q/mT
24
.
21.5
23
ipn10 21
22
10% EGDMA
21 20.5
PMA10
PS10
20 20 Termogramas de calentamiento
DSC en muestras no envejecidas
19 19.5 de PMA-i-PS IPNs
-50 0 50 100 150
Temperature(ºC)
J.M. Meseguer, J.L. Gomez Ribelles, J. Therm. Anal. Cal. 72 (2003) 695
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Diapositiva 21
0.85
20ºC 1.3
0.75 10 95ºC
0.2J/gK
1.2
0.2J/gK
0.65 5 85
1.1 80
0.55
Cp-Cpref (J/gK)
Cp-Cpref (J/gK)
1 70
0.45 0
65
0.9 60
0.35 -5
55
0.8 50
0.25 -10 45
-15
0.15 0.7 40
-20
-25
0.05 0.6 30
-30
-35
-0.05 0.5
-25 0 25 50 75 100 125 -25 0 25 50 75 100 125
Temperature (ºC) Temperature (ºC)
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Diapositiva 22
Temperatura de envejecimiento
90ºC
0.8 80
70
0.2J/gK 60
55
PMA-i-PS entrecruzado 0.6 50
45
Cp-Cpref (J/gK)
con 10% EGDMA 40
35
0.4 30
25
20
15ºC
0.2 10
5
0
0 -5
-10
-15
-20
-0.2
-25 0 25 50 75 100 125
Temperature (ºC)
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Diapositiva 23
1.5
∆ henv (J/g)
h env(J/g)
1
1
0.5
0.5
0 0
-50 0 50 100 150 -50 0 50 100 150
T a(ºC) Ta(ºC)
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Diapositiva 24
0,5 0,12
0,45
Cop30%EA net-P(EA-co-HEMA)
PEA 0,1
0,4
0,35
(cp-cpref )max (J/gK)
0,25 0,06
Cp-Cpref (J/gK)
0 0
50ºC
-50 -30 -10 10 30 50 70 90 110 40ºC
temperature/ ºC 0,3
30ºC
20ºC
0,2
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Diapositiva 25
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