Diapositiva 1

Viscoelasticidad lineal

Contenido

• Tensor de tensiones
• Ensayo de fluencia. Componentes de la respuesta del material.
Procesos de relajación. Componente viscosa, flujo irreversible.
• Comportamiento lineal. Principio de superposición.
• Ensayo de relajación de tensiones
• Modelos mecánicos: Kelvin-Voigt , Maxwell, Zener.
• Tiempos de relajación
• Distribución de tiempos de relajación.
• Efecto de la temperatura. Principio de superposición tiempo-
temperatura.
• Espectroscopía dinámico-mecánica
Bibliografía

A. Horta. Macromoléculas. UNED. Capítulos 33 y 34

J.M.G. Cowie. Polymers: Chemistry & Physics of Modern Materials. Blackie Academic &
Professional. 1991

R.J. Crawford, Plastics Engineering, 3rd ed Butterworths 1998

N.G. McCrum, C.P. Buckley, C.B. Bucknall, Principles of Polymer Engineering, Oxford Sci.
Pub, 1988

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Diapositiva 2

Proceso de compresión de un conjunto de cadenas de polímero

Respuesta
elástica, sin
rotaciones en los
enlaces
Movimientos locales de
las cadenas laterales o
incluso de pequeñas
partes de la cadena
principal. Procesos de
relajación secundaria

Movimientos conformacionales.
Relajación principal o relajación α

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Diapositiva 3

Tensión y deformación en un sólido elástico

⎛ σ xx σ xy σ xz ⎞
Tensor de tensiones ⎜ ⎟
σ ij = ⎜ σ xy σ yy σ yz ⎟
⎜σ σ yz σ zz ⎟⎠
⎝ xz

Tensor de deformación
⎛ ∂u ∂u ∂v ∂u ∂w ⎞
⎜ + + ⎟
⎛ γ xx γ xy γ xz ⎞ ⎜ ∂ x ∂y ∂x ∂z ∂x ⎟
⎜ ⎟ ⎜ ∂u ∂v ∂v ∂v ∂w ⎟
γ ij = ⎜ γ xy γ yy γ yz ⎟ = ⎜ + +
⎜γ ⎟ ∂y ∂x ∂y ∂z ∂y ⎟
⎝ xz γ yz γ zz ⎠ ⎜ ∂ u ∂ w ∂v ∂w ∂w ⎟
⎟
⎜
⎜ ∂z + ∂x +
∂z ∂y ∂z ⎟
⎝ ⎠

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Diapositiva 4

Viscoelasticidad lineal

σ xx
Ley de Hooke generalizada γ xx =
E
Tension σxx ν
γ yy = − σ xx
E
ν
γ zz = − σ xx
ν: Coeficiente de Poisson E
E: Módulo de Young
σxx

σ xz
γ xz =
G
y
σ xy
σxy Cizalla pura γ xy =
G
σ yz
γ yz =
G
x
E
z Módulo de cizalla G=
2(1 +ν )

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Diapositiva 5

Viscoelasticidad lineal

Comportamiento puramente
(σ )
xy E = Gγ xy
elástico. Ley de Hooke

dγ xy
Comportamiento puramente viscoso
Ley de Newton (σ )
xy V =η
dt
σxy

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Diapositiva 6

Viscoelasticidad lineal

σ Fluencia

σ0

time
γ (t ) = J (t )σ 0
γ

γ2
γ1 γ3 Log J(t)

time Relajación principal

goma Flujo
irreversible

vidrio

10-9 Pa-1

log t

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Diapositiva 7

Viscoelasticidad lineal

Influencia de la temperatura

T0 > T1 > T2 > T3 > T4

Log J(t)

10-9 Pa-1

log t

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Diapositiva 8

Viscoelasticidad lineal

γ Relajación de Tensiones

γ0

time
σ (t ) = G(t )γ 0
σ

log G(t)

time 109 Pa
Flujo
goma Irreversible

vidrio
Relajación
principal

log t

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Diapositiva 9

Viscoelasticidad lineal
σ
El modelo de Maxwell γ1 =
Em
∂γ ∂γ 1 ∂γ 2 1 ∂σ σ
σ γ = γ1 +γ 2 = + = +
∂γ ∂t ∂t ∂t Em ∂t η m
σ = ηm 2
Em γ1 ∂t

η m ∂σ ∂γ
ηm γ2 σ+ = ηm
Em ∂t ∂t
σ
γ = γ 0
Ensayo de relajación de tensiones ∂γ
= 0
∂t
Tiempo de relajación
∂σ E ∂σ dt σ t
=− mσ =− ln =− ηm
∂t ηm σ τ σ0 τ τ=
Em

⎛ t⎞ t→ 0 σ =σ0
σ = σ 0 exp⎜ − ⎟
⎝ τ⎠ t→ ∞ σ =0 ???

Ensayo de fluencia σ =σ0 ∂γ puramente viscoso

σ = ηm
∂σ ∂t
=0
∂t

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Diapositiva 10

Viscoelasticidad lineal

El modelo de Zener
σ = σ1 + σ 2 = Eaγ + σ 2

∂σ ∂γ ∂σ 2
σ = Ea +
∂t ∂t ∂t
σ1 σ2
Em γ1 σ2 ∂γ 2 σ 2
Ea γ1 = =
Em ∂t η m
ηm γ2
∂γ ∂γ 1 ∂γ 2 1 ∂σ 2 σ 2
= + = +
∂t ∂t ∂t E m ∂t η m
σ
∂σ ∂γ ∂γ Em
= Ea + Em − (σ − Eaγ )
∂t ∂t ∂t η m

∂σ ∂γ E E
= (E a + E m ) − m a γ
Em
σ+
ηm ∂t ∂t ηm

σ+
η m ∂σ
= ηm
( E a + E m ) ∂γ + E aγ
E m ∂t Em ∂t

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Diapositiva 11

Viscoelasticidad lineal
γ = γ
Ensayo de relajación de tensiones
σ+
ηm ∂σ
= ηm
(Ea + Em ) ∂γ + E aγ
0

∂γ
Em ∂t Em ∂t = 0
∂t
η m ∂σ
σ+ = E aγ 0 Tiempo de relajación
E m ∂t
ηm GUγ0
∂σ τ= σ
σ +τ = E aγ 0 Em
∂t
⎛ t⎞
σ = Eaγ 0 − (Eaγ 0 − σ 0 ) exp⎜ − ⎟ GRγ0
⎝ τ⎠
t→ 0 σ = σ 0 = GU γ 0
t→ ∞ σ = E aγ 0 = G Rγ 0

log t

⎡ ⎛ t ⎞⎤ ⎡ ⎛ ⎛ t ⎞ ⎞⎤
σ = γ 0 ⎢ G R − (G R − GU ) exp ⎜ − ⎟ ⎥ = γ 0 ⎢ GU − (GU − G R )⎜ 1 − exp ⎜ − ⎟ ⎟ ⎥
⎣ ⎝ τ ⎠⎦ ⎣ ⎝ ⎝ τ ⎠ ⎠⎦

⎛ ⎛ t ⎞⎞
⎛ t⎞
G (t ) = G R + (GU − G R ) exp ⎜ − ⎟ G(t ) = GU − (GU − GR )⎜1 − exp⎜ − ⎟ ⎟
⎝ τ⎠ ⎝ ⎝ τ ⎠⎠

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Diapositiva 12

Viscoelasticidad lineal

Fluencia
σ =σ0
σ+
ηm ∂σ
= ηm
(Ea + Em ) ∂γ + E aγ ∂σ
Em ∂t Em ∂t =0
∂t

σ 0 = ηm
( E a + E m ) ∂γ + E aγ
Em ∂t
Tiempo de retardo
σ0 ∂γ
=τ' +γ
Ea ∂t (E a + E m ) = η ⎛ 1 1 ⎞
dγ dt τ ' = ηm m
⎜⎜ + ⎟⎟
= Ea Em ⎝ a
E E m ⎠
σ0
−γ τ'
Ea t → 0 γ = γ 0 = JUσ 0
σ0⎛σ ⎞ σ0
⎛ −t ⎞ t → ∞ γ = = J Rσ 0
γ = − ⎜ 0 − γ 0 ⎟⎟ exp⎜ ⎟
Ea ⎜⎝ Ea
Ea
⎠ ⎝ τ' ⎠
⎛ −t ⎞ γ
γ = J Rσ 0 − (J R − J U )σ 0 exp⎜ ⎟ JRσ0
⎝ τ' ⎠
⎛ −t ⎞
J (t ) = J R − (J R − J U ) exp⎜ ⎟ JUσ0
⎝ τ' ⎠
⎡ ⎛ − t ⎞⎤
J (t ) = J U + ( J R − J U )⎢1 − exp⎜ ⎟⎥ log t
⎣ ⎝ τ ' ⎠⎦

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Diapositiva 13

Viscoelasticidad lineal

Relación entre tiempo de relajación y tiempo de retardo

1
Módulo antes de la relajación: GU = = Ea + Em
JU
1
Módulo después de la relajación: G R = = Ea
JR

⎛ 1 1 ⎞ ηm
Tiempo de retardo τ ' = η m ⎜⎜ + ⎟⎟ =
⎝ a
E E m ⎠ J U E a E m

η η
Tiempo de relajación τ = m
= m
E m J R EaE m

τ J
= R
τ ' J U

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Diapositiva 14

Viscoelasticidad lineal
J (t ) − J U ⎡ ⎛ t ⎞⎤
Modelo de un único tiempo de relajación ψ (t ) = = 1 − exp ⎢− ⎜ ⎟⎥
Un tiempo de relajación J R − JU ⎣ ⎝ τ ' ⎠⎦
1.2 0.4
1.2
0.35
1 1
relaxation function

0.3

relaxation function
0.8
0.8 0.25

d (t) / dlogt
0.6 0.2
0.6
0.4 0.15

0.2 0.4 0.1

0 0.05
0.2
0 100 200 300 400 500 600 700 800 900 100 0
0
0 -0.05
t (s)
-4 -2 0 2 4
log(t / s)

1.2

Single relaxation time

1 model

∞ ⎛ t⎞
KWW b=0,2

Distribución de G (t ) = GR + ∫ H (τ ) exp⎜ − ⎟d ln τ

Relaxation function
0.8

⎝ τ⎠
KWW b=0,4
−∞
tiempos de 0.6
KWW b=0,6

relajación y de KWW b=0,8

∞ ⎡ ⎛ − t ⎞⎤ 0.4
retardo J (t ) = J U + ∫ L (τ ) ⎢1 − exp⎜ ⎟⎥ d ln τ
−∞
⎣ ⎝ τ ' ⎠⎦ 0.2

0
-4 -2 0 2 4 6
log (t / s)

⎧⎪ ⎛ t ⎞ β ⎫⎪
Ecuación de Kohlrausch-Williams-Watts ψ (t ) = 1 − exp ⎨− ⎜ ⎟ ⎬
⎪⎩ ⎝ τ ⎠ ⎪⎭

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Diapositiva 15

Viscoelasticidad lineal
El principio de superposición de Boltzmann

Stress
Respuesta a un programa de
multiples escalones de carga
∆σ3
∆σ2
γ (t ) = ∆σ 1 J (t − t1 ) + ∆σ 2 J (t − t2 ) + ∆σ 3 J (t − t3 ) + ... ∆σ1
Strain
t
γ (t ) = ∫−∞
J (t − t ' ) d σ (t ' )

Respuesta a dos escalones de carga t1 t2 t3

σ(t) σ(t)

∆σ2
∆σ1 ∆σ1 ∆σ2= - ∆σ1

γ(t) γ(t)

t1 t2 t1 t2

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Diapositiva 16

Viscoelasticidad lineal

Una fibra larga se carga con una masa de 0.1 kg unida a su extermo inferior. El alargamiento (%)
se mide en varios instantes de tiempo después de la aplicación de la carga

Alargamiento (%) t(min)

0.3 0
0.328 10
0.350 20
0.390 40
0.428 60
0.462 80
0.490 100
0.514 120
0.535 140
0.555 160
0.572 180
0.585 200
0.593 220
0.6 240

La lectura en t=0 da la respuesta elástica.

Suponiendo que el comporamitnto del material es viscoelástico lineal, calcular el alargamiento
bajo las siguientes condiciones:
Se carga el hilo con 0.1kg en t=0, se quita la carga en t=40min, se vuelve a cargar a t=80min, se
quita la carga en t=120min. Calcular el alargamiento residual en t=240min.

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Diapositiva 17

Viscoelasticidad lineal
Espectroscopía dinámico-mecánica
Muestra sometida a una deformación sinusoidal γ (t ) = γ 0 cos ω t

Medida de la respuesta en tensión σ (t ) = σ 0 cos(ωt + δ )

σ (t ) = σ 0 cos (ω t ) cos (δ ) − σ 0 sin (ω t )sin (δ ) = E1(t ) + E 2 (t )

σ0
3
σ

E' = cos(δ ) E 1

γ0
2
E 2
γ
σ 1

E ' ' = 0 sin (δ )

γ0 0

E'' -1

tanδ =
E' -2

-3
0 1 2 3 4 5 6
ω t/π

Deformación y tensión alternativas con

ω=1s-1 and δ=0.5 rad
Modulo complejo E*
Deformación ≡ Parte real de γ* = γ0 eiωt

Tensión ≡ Parte real de σ* = E*γ∗

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Diapositiva 18

Compatibilización forzada Viscoelasticidad lineal

Ensayos dinámico-mecánicos

1.00 10 10

0.00
0.80
9 9
IPNs PMA-i-PMMA IPN y
0.60
-2.00
las redes puras de PMA y
log tan

log tan
log E'

log E'
8 8 PMMA entrecruzadas con
0.40
5% de EGDMA
-4.00
7 7
0.20 IPN PMA-i-PMMA 5%EGDMA
PMA 5% EGDMA
PMMA 5% EGDMA

0.00 6 -6.00 6
-50.00 0.00 50.00 100.00 150.00 200.00 -50.00 0.00 50.00 100.00 150.00 200.00

Temperature / ºC Temperature / ºC

0.0
%EGDMA

0.1
0.5

-0.5 1
5

log tanδ
10

-1.0

PMA-i-PMMA con diferente

densidad de entrecruzamiento -1.5

-2.0

-50 0 50 100 150 200

Polymer Communications 42, 10071 (2001) Temperature / ºC

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Diapositiva 19

Viscoelasticidad lineal

PBA
Ensayos dinámico-mecánicos PMMA

tanδ
20/80
0.1

40/60

80/20 60/40
0.01
-100 -50 0 50 100 150 200

Temperature (ºC)

Tangente de pérdidas de copolímeros al azar poly(butyl acrylate – co –

methyl methacrylate) PBA/PMMA

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Diapositiva 20

Viscoelasticidad lineal

Una barra de polímero con una longitud de 60 mm tiene sección

rectangular, con dimensiones 10mm x 4 mm. La barra está sometida a una
fuerza en sentido longitudinal, oscilando sinusoidalmente entre -150 y +150
N a una frecuencia de 50Hz. La componente imaginaria del módulo de
fluencia complejo es D’’ = 3.7 10-9 Pa-1. Calcular la potencia necesaria para
mantener la oscilación.

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Diapositiva 21

Viscoelasticidad lineal
Principio de superposición tiempo-temperatura
Curva de KWW con β=0.6
PMMA entrecruzado con desplazada hacia bajas frecuencias buscando
1% EGDMA la claridad en el diagrama
PM M A EG D M A1% P M M A E G D M A1%

3.2 3.2

3 3
153.6
2.8 153.6 2.8
149.0
2.6 149.0 2.6
144.3
144.3 2.4 139.7

log(Da v)
2.4
log(D )

2.2
139.7 2.2 Curva 135.2
135.2 130.6
2
130.6
2
maestra a 126.3
1.8
1.8 126.3
1.6
144.3ºC 121.8
1.6 121.8 KW W
1.4
1.4
1.2
1.2
-6 -4 -2 0 2 4 6
0 1 2 3 4
lo g (ta T)
lo g (t / s)

Diagrama de Ahrrenius. 6

4
Dependencia con la temperatura 3
log τ

de los tiempos de relajación 2

τ(144.3)=4s
0

-1

-2
2.3 2.35 2.4 2.45 2.5 2.55
1000/T

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Diapositiva 22

Viscoelasticidad lineal
Principio de superposición tiempo-temperatura

Tanδ de una red de poliestireno entrecruzada con un 0.1% en peso de

EGDMA.

Ensayos dinámico-mecánicos en tensión.

114.759
3 113.341 3

111.646
109.849
2.5 2.5
108.16
106.408 111.646

2 104.666 109.849
2
108.16
102.879
106.408
tan( δ )

100.939
104.666
1.5 99.1933 1.5
102.879
99.4766 100.939

97.1199 99.1933
1 1 97.1199
95.6455
95.6455
93.9324
0.5 92.2005 0.5
90.439
88.5715
0 86.7315
0
0.01 0.1 1 10 100 0.01 0.1 1 10 100 1000
85.0308
F(Hz) 83.2035
81 4147

Curva maestra superpuesta sobre la

isoterma de 108ºC.

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Diapositiva 23

Viscoelasticidad lineal

El módulo elástico de un polímero amorfo, cuya temperatura de transición vítrea es 70ºC,

medido en un ensayo de relajación de tensiones en el rango lineal a la temperatura de
90ºC viene dado por la siguiente ecuación:

⎛ ⎛ t ⎞ 0 .5 ⎞
E (t ) = 2 + 1200 exp⎜ − ⎜ ⎟ MPa
⎜ ⎝ 5000 ⎟⎠ ⎟
⎝ ⎠

con t en minutos. El factor de deslizamiento que permitiría construir una curva maestra
para E(t) puede calcularse de acuerdo con la ecuación de Williams-Landel y Ferry.

17.4(T − Tg )
log aT =
51.6 + (T − T g )

(a) Calcula la deformación, un mes después de la aplicación de la carga, de una barra de

ese polímero con sección transversal de 3 x 5 mm y longitud inicial 100mm de la que se
cuelga un peso de 200g a la temperatura de 90ºC. (b) Repite el cálculo si la carga se
aplica a 70ºC. (c) Repite el cálculo si la carga se aplica 130ºC. (d) Explica los resultados
ayudándote de un diagrama esquemático que represente E(t) a las tres temperaturas
utilizando las escalas adecuadas.

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