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Estudio Morfológico de Polímeros por medio de Luz Sincrotrón
Instituto de Estructura de la Materia,CSIC
Serrano 119, Madrid 28006,
Spain
T. A. Ezquerra
Escuela en Ciencia e Ingeniería de Materiales ( 27 de junio al 1 de julio, 2005) , México D.C.
3.Dispersión de Rayos X con luz sincrotrón en materiales poliméricos (dos horas)
a. Conceptos generales de física de polímeros: estructura y dinámica
b. Cristalización en polímeros
c. Caracterización de la estructura en polímeros mediante dispersión de rayos X a ángulos altos y bajos con resolución temporal.
d. Cristalización de polímeros en medios confinados: mezclas poliméricas
e. Transformaciones de fase en cristales líquidos poliméricos.
f. Estructura en materiales compuestos poliméricos basados en nanotubos de carbono.
Estudio de morfología de polímeros por medio de sincrotón de rayos X y métodos combinados con él
Brevísima Bibliografía
1. B. Chu, B.S. Hsiao, Chem. Rev. 2001, 101, 1727-17612. A. Nogales, I. Sics, T. A. Ezquerra, Z. Denchev, F. J. Balta Calleja,B. S. Hsiao,
Macromolecules 2003, 36, 4827-48323. I. Sics, A. Nogales, T. A. Ezquerra, Z. Denchev, and F. J. Balta –Calleja, Review
of Scientific Instruments, 71,4, 20004. A. Nogales, T. A. Ezquerra, Z. Denchev, I. Sics, F. J. Balta-Calleja, J. of Chemical
Physics,115, 8, 20015. C. Alvarez, I. Sics, A. Nogales, Z. Denchev, S.S. Funari, T.A. Ezquerra, Polymer
45 (2004) 3953–3959.
Resultados obtenidos por:
Aurora NogalesMari Cruz GarcíaAlejandro Sanz
Cristiana AlvarezIgors Sics
Daniel RuedaTiberio Ezquerra
Cristalización de Polímeros: Jerarquía Estructural
10–1 m
10-5 m
10-8 m
5x10-10 m
Tg <T < Tm
X-ray DiffractionNeutron Diffraction
SAXS
SANS
AFM
Light ScatteringOptical MicroscopyAFM
Eyes
PHB-AFM
M.J. Capitán, D.R. Rueda IEM-CSIC
-
Técnicas Experimentales
( b )
s ( A-1
)
0 .1 8 0 .2 4 0 .3 0 0 .3 6
WAXS( a )
s ( A - 1 )
0 .0 0 0 .0 1 0 .0 2
I(a .
u.)
SAXS
q =2π/Lmax
Estructura
Fase cristalinaFase amorfa
L
t t t1 2 3
110
111
200
Tc=433KWAXS SAXS
¿Porqué luz Sincrotrón? Procesos Dinámicos
tiempo
SAXS interfaceWAXS interface
Esquema del sistema experimental
Ley de Bragg d = λ/(2 sin θ)
WAXS
SAXS
Muestras Poliméricas
C
OO
C CH2O ( )2
O( )n
PET
CO H2C C 2CH
O
O
O m
PEN
C
O
OO
m
PEEK
Tg ( C)
75
117
145
o
T 433K
I(u.a
.)
q(Å-1)
1.0 1.2 1.4 1.6 1.8 2.0
tc(min)
0
3
10
25
110111
200
T 433KT 433K
I(u.a
.)I(u
.a.)
q(Å-1)
1.0 1.2 1.4 1.6 1.8 2.0
q(Å-1)
1.0 1.2 1.4 1.6 1.8 2.0
tc(min)
0
3
10
25
110111
200
Rayos-X : PEEK
WAXS 110
111
200
Tc = 160 Co
Fracción de cristalesFracción totalCristalinidad =
SAXS
γr
( ) ( )1 ˆ ˆ iqr
V
r I q Ie dqγ − −⎡ ⎤= ℑ =⎣ ⎦ ∫
Rayos-X PEEKTc = 160 Co
WAXS 110
111
200
a a rV
daγ ρ ρ ρ ρ += ∗ = ∫
Ángulos pequeños en polímeros: función de correlación
0
( ) cos( )corrr I qr dqγ∞
= ∫
1 2 Mc
Bx xL
⋅ =
1 2 1x x+ =
1 1M
cl x L= ⋅
1 2Mcl l L+ =
r(nm)x10
0 50 100 150 200 250 300
γ(r)
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
B LcM
Modified self-correlation triangle
lc la LcMlc la LcM
Xc, Q
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Log10[tc/min]0 1 2
XL
0.1
0.2
0.3
0.4
0.5
(a)
(b)
Log10[tc/min]0 1 2
Å
20
30
40
70
80
90
100
Å
70
80
90
100
110
120
130
140(a)
(b)
LcM
Lcm
1
2
Rayos-X PEEK
cLLsc XXXX ⋅⋅=
Cristalización Primaria
Cristalización Secundaria
Fig. 2
Xc,
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Log10[tc/min]0.5
(a)
Cristalización Secundaria
Cristalización Primaria
-
Técnicas Experimentales
( b )
s ( A-1
)
0 .1 8 0 .2 4 0 .3 0 0 .3 6
WAXS( a )
s ( A - 1 )
0 .0 0 0 .0 1 0 .0 2
I(a .
u.)
SAXS
q =2π/Lmax
-1 0 1 2 3 4 5 60.0
0.2
0.4
0.6 T = 90 o C
Log 10 [F/Hz]
ε ''
α
Dinámica
DS
Estructura
Crystalline PhaseAmorphous Phase
L
Espectroscopía DielectricaI
V=VoeiωVoltage
generatort
Current Analyzer
d
Electrode
Sample
Voltage Analyzer
A
Ic = i ω Co ε’ V Ir = ω Co ε’’ V
Co = eo A/d
0.0
0.2
0.4
0.6
-150-100
-500
50100
150200
-1.00.0
1.02.0
3.04.0
ε ''
T(o C)
Log (F/ Hz)
0.0
0.2
0.4
0.6
-150-100
-500
50100
150200
-1.00.0
1.02.0
3.04.0
ε ''
T(o C)
Log (F/ Hz)
0.0
0.2
0.4
0.6
-150-100
-500
50100
150200
-1.00.0
1.02.0
3.04.0
ε ''
T(o C)
Log (F/ Hz)
C
OO
C CH2O ( )2
O( )n
α
β
DS- medida
PET
β
α
C
OO
C CH2O ( )2
O( )n
αβ
DS- medidas
ε''
0.0
0.2
0.4
0.6
Log10 [F/Hz]-1 0 1 2 3 4 5 6 7 8 9
ε'
3
4
5
6
7
7580
85 9095 100 105
β
β
α
α
PET
αβ
( )x
x,x
(ε ε )oε* (ε ) cb1 iωτ
x
xβ
α β=
− ∞= +∞⎡ ⎤+⎢ ⎥⎣ ⎦
∑
SAXS interfaceWAXS interface
Esquema del sistema experimental SWD
DS interface
WAXS
SAXS
1
X-Raybeam
2
7
8
3
4
6 6
32
45 5
1.Sample2.Aluminum foils3.Electrodes4.Heating blocks5.Insulating film6.Heating elements7. Cooling pipes8.Thermometer
SWD-cell
I Sics et al, Rev. Sci. Instrum. 71,1733 (2000).
A2 @ HASYLAB, Hamburg, Germany
PET @ 96 Co
s (nm-1)1.5 2.0 2.5 3.0 3.5
tc = 0 min
tc = 180 min
tc = 360 min
s (nm -1)0.05 0.10 0.15 0.20 0.25
tc = 0 min
tc = 180 min
tc = 360 min
WAXS SAXS
( ) ( ) ( )α
'α*
'dc
n0
β( ε )
1
σε εε ω
( ε ) '
1 ωτ' ω
( )
1 ω τ
ε
τcb
HN
c
Hb
HNb
N iiii∞
⎡ ⎤⎢ ⎥⎣ ⎦
⎡ ⎤⎢ ⎥
⎡ ⎤⎢ ⎥⎣⎣
+
⎦ ⎦
= + ++
−∆
+
∆ ∆
+
C. Alvarez et al, Polymer 45 (2004) 3953
0.0
0.2
0.4
ε''
0.0
0.2
0.4
log 10(F/ Hz)0 1 2 3 4 5
0.0
0.2
0.4
tc = 0 min
tc = 180 min
tc = 360 min
DS
PET @ 96 Co
log 10
τ
-5
-4
-3
-2
b
0.0
0.2
0.4
0.6
0.8
1.0
c
0.2
0.4
0.6
0.8
1.0
∆ε
0
1
2
t (min.)0 60 120 180 240 300 360
Xc
0.0
0.1
0.2
0.3
0.0
0.2
0.4
0.6
0.8
1.0
1.2
dXc dt
αα'
α+α'
α
α'
α
α
α'
(a)
(b)
(c)
(d)
(e)
(a) Estado amorfo
(b) cristalización primaria
(c) cristalización secundaria
Modelo
•Lin J., Shenogin S., Nazarenko S. Polymer 2002; 43:4733•Ivanov D.A., Pop T., Yoon D.Y., Jonas A.M. Macromolecules 2002; 35: 9813
C
O
C O CH2 CH2 O
O
n
Poly(ethylene-2,6-naphthalene dicarboxylate)PEN
Poly(ethylene terephthalate)PET
C C O CH2 CH2 O
O O
n
* Handbook of thermoplastic polyesters,S. Fakirov Ed. ,vol.2, cap. 19, Wiley-VCH, Germany, 2002
Properties* PET PEN
O2 Permeability at 20 ºC( cm3 mm m-2 d-1 bar-1 )
CO2 Permeability at 20 ºC( cm3 mm m-2 d-1 bar-1 )
1.16-1.55
5.81-9.86
0.31
2.40
Melting Temperature (ºC) 255
Glass Transition (ºC) 75 117
265
Tensile Modulus (Kg/mm2)
Tensile Strength (kg/mm2)
1700
50
2000
83
Transesterificación de mezclas poliméricas
PET/PEN son inmiscibles
Transesterificación
T > Tm ( 300 ºC)
t: 1 – 35 min.
Molido de la granza a temperatura de N2 lìquidoTemperature
transreacciones iniciales se minimizan
C C O CH2 CH2 O
O O
C C
O O
C C O CH2 CH2 O
O OC
O
C
O
C
O
C O CH2 CH2 O
O
C
O
C
O
T-E-T
T-E-N
N-E-N
Molido Criogénico
50 100 150 200
T (oC)
250 300
ENDOTHERM
t p= 3 min.
0/100
50/50
100/0
Propiedades térmicas
Tg(ºC)
0 5 10 15 20 25 30 35 40
80
100
120
TgPET-co-PEN
TgPEN
TgPET
tp (min.)
PET/PEN 50/50 wt. %
PET/PEN wt. %
DS-medidas
0.0
0.1
0.2
0.3
0.4
0.5
01
23
45
67
050
100150
Log[F/
Hz]
T( ºC)
ε’’
α -PENα -PET
PET/PEN 50/50 wt. %
0.00.10.20.30.40.5
01
23
45
67
050
100150
Log [
F/Hz]
T (ºC)
ε’’
3 min. @ 300 C ,f =11 %TENo
15 min. @ 300 C ,f =20 %TENo
( ) ( ) ( )α
'α*
'dc
n0
β( ε )
1
σε εε ω
( ε ) '
1 ωτ' ω
( )
1 ω τ
ε
τcb
HN
c
Hb
HNb
N iiii∞
⎡ ⎤⎢ ⎥⎣ ⎦
⎡ ⎤⎢ ⎥
⎡ ⎤⎢ ⎥⎣⎣
+
⎦ ⎦
= + ++
−∆
+
∆ ∆
+
tc = 360 min
DS WAXS SAXS
tc = 0 min
tc = 360 min
S(nm-1)1.5 2.0 2.5 3.0 3.5
tc = 600 min
0.05 0.10 0.15 0.20
tc = 600 min
tc = 0 min
tc = 360 min
Is2
S(nm-1)
0.0
0.1
0.2tc = 0 min
0.0
0.1
0.2tc = 360 min
1 2 3 4 50.0
0.1
0.2tc = 600 min
log 10(F/ Hz)
ε''
PET/PEN 50/50 @ 96 C , f = 11 %TEN
o
PET/PEN mezclas ligeramente transesterificadas
PET/PEN 50:50, f =11 %TEN
0 100 200 300 400 500 600
Xc
0.0
0.1
t (min.)
∆ε
0.5
0.6
0.7
0.8
Log
F max
1
2
3
4
PEN
PEN-b-PET
PET
PEN-b-PET
PEN
Tc
tc
PEN
PEN-b-PET
PET
PEN-b-PET
PEN
PEN
PEN-b-PET
PET
PEN-b-PET
PEN
Tc
tc
Tc
tc
0 500 nm
annealing at 120ºC, 14 hours
AFM-phase
Ordenamiento en Cristales líquidos Poliméricos*
0.67
0.33
C
O
O CH2 CH2 CH2 O CH2
O
CO
CH3
CHCH2
C
O
O CH2 CH2 CH2 O CH CH2 O C
O
CH2
CH3
C31DTB
n
0.67
0.33
C
O
O CH2 CH2 CH2 O CH2
O
CO
CH3
CHCH2
C
O
O CH2 CH2 CH2 O CH CH2 O C
O
CH2
CH3
C31DTB
n
0.67
0.33
C
O
O CH2 CH2 CH2 O CH2
O
CO
CH3
CHCH2
C
O
O CH2 CH2 CH2 O CH CH2 O C
O
CH2
CH3
C31DTB
n
0.67
0.33
C
O
O CH2 CH2 CH2 O CH2
O
CO
CH3
CHCH2
C
O
O CH2 CH2 CH2 O CH CH2 O C
O
CH2
CH3
C31DTB
n
*A. Martínez-Campo, A. Bello, E. Pérez-Tabernero. ICTP-CSIC
DSC
0 20 40 60 80 100
endo
T (ºC)
quenched
S-CT=40 Co
0 min
40 min10 min
nα
Esméctico-C
t = 0
ε''(t
)/ ε''
(0)
0.0
0.5
1.0
1.5
t = 6
0.0
0.5
1.0
1.5
t = 12
0.0
0.5
1.0
1.5
t = 48
-1 0 1 2 3 40.0
0.5
1.0
1.5
Log10[F/Hz]
max
T=35 Co
0.2
0.4
0.6
0.8
1.0
1.2
0 1 2 3 4 50
1224
3648
ε''(t )
/ ε''
(0 )
Log10[F/Hz]
t(min.
)
max
DS
0.50 0.55 0.60 0.65 0.700
1224
3648
I (a.
u.)
s(nm-1)
t(min)
MAXS
1.5 2.0 2.5 3.00
1224
3648
I (a.
u.)
s(nm-1)
t(min)
WAXS
T=35 Co
b
0.0
0.2
0.4
0.6
0.8
1.0
c=0.9 0.1+--+c=0.3 0.1
t (min)
∆ε(
t )/∆ε(0)
0.00.20.40.60.81.01.2
Log
10[ τ
/s]
-5
-4
-3
-2
-1
0
(a)
(b)
(c)
s max
(nm
-1)
0.5460.5480.5500.5520.5540.5560.558
Am
ax(a
.u.)
0.00.10.20.30.40.50.60.70.8
t (min)0 10 20 30 40 50 60
I max
(a.u
.)
0
10
20
30
40
50
b
0.0
0.2
0.4
0.6
0.8
1.0
c=0.9 0.1+--+c=0.3 0.1
t (min)
∆ε(
t )/∆ε(0)
0.00.20.40.60.81.01.2
Log
10[ τ
/s]
-5
-4
-3
-2
-1
0
smax
Amax
I max
, A
max
(arb
. uni
ts)
t (min)0 10 20 30 40 50 60
Imax
0
5
10
15
s max
(nm
-1)
(a)
(b)
(c)
(d)
Esfuerzo-Deformación (Stress-Strain)
strain(%)0 20 40 60 80 100 120 140
Stre
ss (a
.u.)
0
5
10
15
20
25
30
35I II III
1
2
3 45 6 7
strain(%)0 20 40 60 80 100 120 140
Stre
ss (a
.u.)
0
5
10
15
20
25
30
35I II III
1
2
3 45 6 7
Stress-Strain : Arnitel (PBT-PO4))1
8
Cristalización anisotrópica enpoly(butylene terephthalate) (PBT) inducida por
nanotubos de carbono
Mauricio Terrones, Annu. Rev. Mater.Res. 2003. 33:419–501Advanced Materials Department, San Luis Potosí, SLP, México
Nanocomposite samples
1. Oxidized single wall carbon nanotubes (SWCNT) (CNI Technology Co)Thickness:0.7-1.2 nm, length: several µm
2. PBT , poly(butylene terephthalate)
Method ( Roslaniec Z., Broza G., Schulte K., Composite Interface 2003, 10, 95.) :
1.Mixture with the monomer and subsequent polycondensation
2.Pelletized and injection molded into rectangular ( 2mm thick)
3.Compression molded @ 240oC,2 min. and subsequently quenching.
Structure: X-ray scattering
WAXS
SAXS
•X3A2 beamline @ National Synchrotron Source (NSLS) (USA).λ=0.154 nm. Fuji HR-VTM image plates
•ID13 ESRF, Grenoble (France) (Microfocus)
PBT
PBT 0.2 % SWCNT
Structure: X-ray scattering
SWCNT
PBT
PBT 0.2 % SWCNT
WAXSSAXS
Structure: X-ray scattering
1,5 2,0 2,5 3,0 3,5
I(a.u
.)
PBT
0.2
s(nm -1)
0,05 0,10 0,15 0,20 0,25
Ixq2
0.2
PBT
WAXS
SAXS 1.5 2.0 2.5 3.0 3.5
I(a.u.)
PBT-F
0.2-IM
s(nm -1)
0.05 0.10 0.15 0.20 0.25
I xq
0.0
0.1
0.2
0.3
0.4
0.5
0.2-IM
PBT-E
PBT-IM
0.2-F
PBT-E
0.2-E
PBT-IM
0.2-E
PBT-F
0.2-F
(a)
(b)
100 200 300 400 500
SWCNT
d /nm
ν/cm-1
2.4 2 1.6 1.2 0.8
Raman Spectroscopy
Renishaw Raman Microscope System RM2000 @ 785 nm
PBT pure
Beam path
Scan direction
Beam path
Scandirection
Flow
dire
cctio
n
equator
WAXS
SAXS
Microfocus: 5 µm
Beam path
Scan direction
Flow
dire
cctio
n
equator
50 µm
PBT+0.2% SWCNTMicrofocus: 5 µm
Microfocus: 5 µm
Beam path
Scan direction
q (nm-1)
2 4 6 8 10 12 14 16 18 20 22
Inte
nsity
(a.u
.)
0
200
400
600
800
1000
1.1
mm
1 m
m
0010-11 010 100 1-11
WAXS
Flow
dire
cctio
n
Beam path
Scan direction
q (nm-1)
2 4 6 8 10 12 14 16 18 20 22
Inte
nsity
(a.u
.)
0
100
200
300
400
500
600
700
Microfocus: 5 µm
WAXS
SWCNT aggregates SWCNT
Flow direcction
Brevísima Bibliografía
1. B. Chu, B.S. Hsiao, Chem. Rev. 2001, 101, 1727-17612. A. Nogales, I. Sics, T. A. Ezquerra, Z. Denchev, F. J. Balta Calleja,B. S. Hsiao,
Macromolecules 2003, 36, 4827-48323. I. Sics, A. Nogales, T. A. Ezquerra, Z. Denchev, and F. J. Balta –Calleja, Review
of Scientific Instruments, 71,4, 20004. A. Nogales, T. A. Ezquerra, Z. Denchev, I. Sics, F. J. Balta-Calleja, J. of Chemical
Physics,115, 8, 20015. C. Alvarez, I. Sics, A. Nogales, Z. Denchev, S.S. Funari, T.A. Ezquerra, Polymer
45 (2004) 3953–3959.