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.